Laminate

Abstract

To provide a laminate that has excellent processability and anti-blocking properties, and prevents generation of crack or peeling even after heat-drying.SOLUTION: A laminate comprises a decorative layer and a clear layer, where the decorative layer is formed of an active energy ray-curable ink composition containing a coloring agent, the clear layer is formed of an active energy ray-curable ink composition which does not contain a coloring agent, a ratio of polyfunctional polymerizable monomer in the ink composition is less than 50 mass%, the pencil hardness of the decorative layer is hardness B or less, the pencil hardness of the clear layer is hardness H or more, and the clear layer is scattered on the decorative layer, and coats the ratio of 60 area% or more and 90 area% or less of the decorative layer surface.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate including a decorative layer and a clear layer formed from an active energy ray-curable ink composition, and in particular to a laminate that has excellent processability and blocking resistance and is prevented from cracking or peeling even after thermal drying. [Background technology]

[0002] Conventionally, when printing on a steel plate, the use of multiple layers formed from ink compositions has been considered for the purpose of imparting various properties such as adhesion and high hardness to the layers formed.

[0003] In JP 2020-90682 A (Patent Document 1), for an inkjet printed steel plate having a plating layer, a primer layer, a color coating layer, a pretreatment layer, an inkjet color printing layer, and, if necessary, a transparent coating layer or a transparent film layer, in that order on a metal substrate, it is proposed to use an ink composition for inkjet printed steel plates, which has excellent ink jetting properties and printing workability, high hardness and adhesion to metal materials, and can provide printability without using a solvent, for the inkjet color printing layer. Patent Document 1 describes that using a specific linear acrylate oligomer in the ink composition for inkjet printed steel plates is advantageous in improving the coating adhesion and hardness with the steel plate.

[0004] JP 2017-164942 A (Patent Document 2) describes a method for manufacturing decorative panels in which a primer layer, a base coat layer, a picture layer, a matte printed layer that forms irregularities on the picture layer, and a clear coat layer that fills in the irregularities in the matte printed layer are formed in that order on a metal plate, with the aim of providing a printed decorative panel with improved design, and describes a method for adjusting the height of the convex parts of the matte printed layer and the thickness of the clear coat layer.

[0005] On the other hand, printed steel sheets are often subjected to processing such as bending and deformation after printing (also called post-processing), and simply imparting high hardness to the printed layer increases the possibility of defects such as cracks in the printed layer during post-processing. For this reason, a soft printed layer is required for printing on a substrate that will be post-processed, but a soft printed layer poses an issue of reduced blocking resistance, such as a blocking phenomenon occurring during winding, etc. Patent Documents 1 and 2 do not consider a printed layer that has processability and blocking resistance that can withstand post-processing.

[0006] JP 2014-240153 A (Patent Document 3) describes an image forming method including, in this order, an image layer forming step of discharging at least one colorant-containing actinic radiation curable inkjet ink composition onto a recording medium to form an image layer, and a clear layer forming step of discharging an actinic radiation curable inkjet clear ink composition onto the image layer to form a clear layer, the colorant-containing actinic radiation curable inkjet ink composition contains 50% by mass or more of a monofunctional polymerizable compound in the polymerizable compound, the actinic radiation curable inkjet clear ink composition contains 50% by mass or more of a multifunctional polymerizable compound in the polymerizable compound, and in the clear layer forming step, the actinic radiation curable inkjet clear ink composition is scattered on the image layer to form a discontinuous clear layer. Patent Document 3 describes that this image forming method can provide an image forming method capable of forming an image having excellent stretchability and suppressed sticking to a mold.

[0007] The image formed by the image forming method described in Patent Document 3 is described as having excellent stretchability and being suppressed from sticking to a mold, and therefore seems to be applicable to printing on steel plates. However, the inventors' investigations revealed that the clear layer on the image layer formed by the image forming method described in Patent Document 3 cracks and peels off after thermal drying. Printed steel plates are often top-coated and thermally dried for finishing. For this reason, the image forming method described in Patent Document 3 has a problem with respect to thermal drying for finishing. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2020-90682 A [Patent Document 2] JP 2017-164942 A [Patent Document 3] JP 2014-240153 A Summary of the Invention [Problem to be solved by the invention]

[0009] SUMMARY OF THE PRESENT EMBODIMENT An object of the present invention is to provide a laminate which is excellent in processability and blocking resistance and which is prevented from cracking or peeling even after thermal drying. [Means for solving the problem]

[0010] As a result of intensive research into achieving the above-mentioned object, the present inventors have found that in a laminate comprising a decorative layer formed from an active energy ray-curable ink composition containing a colorant, and a clear layer formed from an active energy ray-curable ink composition not containing a colorant, the pencil hardness of the decorative layer and the clear layer are set to a hardness of B or less and a hardness of H or more, respectively, the clear layer is scattered on the decorative layer so as to cover 60% or more by area and 90% or less by area of ​​the surface of the decorative layer, and the proportion of polyfunctional polymerizable monomer in the active energy ray-curable ink composition used to form the clear layer is less than 50% by mass, thereby providing a laminate which is excellent in processability and blocking resistance and which is prevented from cracking or peeling even after thermal drying, and have thus completed the present invention.

[0011] Therefore, the laminate of the present invention is a laminate including a decorative layer and a clear layer, the decorative layer is formed from an active energy ray-curable ink composition containing a colorant, and the clear layer is formed from an active energy ray-curable ink composition that does not contain a colorant, and a ratio of a polyfunctional polymerizable monomer in the ink composition is less than 50 mass%, The pencil hardness of the decorative layer is B or less, and the pencil hardness of the clear layer is H or more; The laminate is characterized in that the clear layer is scattered on the decorative layer and covers 60% to 90% by area of ​​the surface of the decorative layer.

[0012] In a preferred embodiment of the laminate of the present invention, the active energy ray curable ink composition constituting the decorative layer contains a monofunctional polymerizable monomer in a proportion of 70% by mass or more in the ink composition.

[0013] In another preferable embodiment of the laminate of the present invention, the active energy ray curable ink composition constituting the clear layer contains urethane acrylate in a ratio of 3% by mass or more and 8% by mass or less in the ink composition.

[0014] In another preferable embodiment of the laminate of the present invention, the laminate further comprises an undercoat layer, and the decorative layer is located on the undercoat layer.

[0015] In another preferable embodiment of the laminate of the present invention, the laminate further comprises a topcoat layer, the topcoat layer being located on the clear layer and on the decorative layer where the clear layer is not present. Effect of the Invention

[0016] According to the laminate of the present invention, it is possible to provide a laminate which is excellent in processability and blocking resistance, and which is prevented from cracking or peeling even after thermal drying. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention relates to a laminate including a decorative layer and a clear layer formed from an active energy ray-curable ink composition.

[0018] The laminate is a laminate of a plurality of layers, and the laminate of the present invention includes at least a decorative layer and a clear layer, and may include additional layers such as an undercoat layer and a topcoat layer as necessary. The laminate of the present invention is formed on at least a part of the surface of an object to be decorated, and can provide decoration to the object. Decoration means providing a design. The design is a shape, a pattern, a color, or a combination of these.

[0019] In the present invention, the decorative layer is a layer intended to provide a design to an object to which the laminate of the present invention is applied. The object to which the laminate of the present invention is applied is also called a substrate.

[0020] In the present invention, the clear layer means a layer having a visible light transmittance of 60% or more.

[0021] The visible light transmittance means the total light transmittance in the visible region (360 nm to 750 nm), and can be measured in accordance with JIS K 7375:2008.

[0022] In the laminate of the present invention, the decorative layer is formed from an active energy ray-curable ink composition containing a colorant, and the clear layer is formed from an active energy ray-curable ink composition not containing a colorant. By using the active energy ray-curable ink composition to form the decorative layer and the clear layer, excellent adhesion can be imparted to the decorative layer and the clear layer.

[0023] In the present invention, the actinic radiation-curable ink composition refers to an ink composition that can be cured by irradiation with actinic radiation such as ultraviolet rays, visible light, or electron beams.

[0024] In the laminate of the present invention, the pencil hardness of the decorative layer is a hardness of B or less, and preferably a hardness of 3B to 2B. By making the pencil hardness of the decorative layer B or less, it is possible to prevent cracks from occurring in the decorative layer even when the laminate of the present invention is formed on a substrate and the substrate is subjected to post-processing (such as bending or deformation).

[0025] In the present invention, the pencil hardness is measured according to JIS K 5600-5-4:1999. The pencil hardness increases in the order of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H. Pencils of various hardness are applied to the decorative layer or the clear layer at an angle of 45°, and a scratch test is performed under load. The hardness of the hardest pencil that does not scratch the decorative layer or the clear layer is defined as the pencil hardness of the decorative layer or the clear layer.

[0026] In the laminate of the present invention, the active energy ray curable ink composition constituting the decorative layer preferably contains a monofunctional polymerizable monomer in a proportion of 70% by mass or more in the ink composition. By increasing the proportion of the monofunctional polymerizable monomer in the active energy ray curable ink composition constituting the decorative layer, the decorative layer can be softened. The proportion of the monofunctional polymerizable monomer in the active energy ray curable ink composition constituting the decorative layer is more preferably 80 to 90% by mass. In the present invention, the monofunctional polymerizable monomer refers to a monofunctional polymerizable monomer having one functional group exhibiting radical polymerizability described below.

[0027] Of the monofunctional polymerizable monomers that can be used in the active energy ray-curable ink composition, from the viewpoint of reducing the hardness of the decorative layer, preferred examples include methoxydipropylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate.

[0028] In the laminate of the present invention, the decorative layer has a thickness of, for example, 1 to 30 μm.

[0029] In the laminate of the present invention, the clear layer has a pencil hardness of H or more, is scattered on the decorative layer, and covers 60% to 90% of the surface of the decorative layer. Since the laminate of the present invention has a soft decorative layer, there is a concern that the blocking resistance may decrease, but the blocking resistance is improved by disposing a clear layer having a pencil hardness of H or more on the decorative layer. On the other hand, in order to prevent the clear layer from cracking due to post-processing, the clear layer is scattered on the decorative layer. And, by scattering the clear layer on the decorative layer to the extent that it covers 60% to 90% of the surface of the decorative layer, it is possible to achieve both improvement in blocking resistance and prevention of cracking of the clear layer due to post-processing.

[0030] In the laminate of the present invention, the clear layer has a pencil hardness of H or more, and preferably a hardness of H to 3H.

[0031] In the laminate of the present invention, the active energy ray curable ink composition constituting the clear layer contains a polyfunctional polymerizable monomer in a proportion of less than 50 mass % in the ink composition, as described below, which can prevent cracking or peeling of the clear layer after thermal drying. However, from the viewpoint of maintaining a certain degree of hardness, the proportion of the polyfunctional polymerizable monomer in the active energy ray curable ink composition constituting the clear layer is preferably 25 mass % or more and less than 50 mass %. In the present invention, the polyfunctional polymerizable monomer refers to a polyfunctional polymerizable monomer having two or more functional groups exhibiting radical polymerizability, as described below.

[0032] Of the polyfunctional polymerizable monomers that can be used in the active energy ray-curable ink composition, from the viewpoint of increasing the hardness of the clear layer, preferred examples include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, dicyclopentanyl diacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerin tri(meth)acrylate.

[0033] In the laminate of the present invention, the clear layer covers 60% to 90% of the surface of the decorative layer, and preferably 70% to 80% of the surface of the decorative layer. The decorative layer surface here refers to the surface of the decorative layer on which the clear layer is scattered, excluding the surface of the decorative layer facing the substrate.

[0034] In the laminate of the present invention, the clear layer is preferably made of a plurality of cured inks in the form of dots. For example, an active energy ray curable ink composition is discharged by inkjet printing, scattered on the decorative layer, and the ink is cured while still in the form of dots, thereby forming a clear layer made of a plurality of cured inks in the form of dots. In the laminate of the present invention, the dot-shaped cured inks on the decorative layer are preferably scattered apart from each other, but may be partially overlapped.

[0035] In the present invention, the percentage of the decorative layer surface that is covered by the clear layer can be calculated by dividing the total area of ​​the decorative layer surface that is covered by the dot-shaped clear ink by the total area of ​​the decorative layer surface, and multiplying the resulting value by 100, as shown in the following formula. Coverage area = (Total area of ​​decorative layer surface covered by dot-shaped clear ink / Total area of ​​decorative layer surface) x 100 In the formula, the "covered area" is the percentage of the decorative layer surface covered by the clear layer when the total area of ​​the decorative layer surface on the side where the clear layer is scattered is taken as 100. The covered area can be adjusted by changing the print density (image density) when printing the clear layer. In this case, by using image data that has been image-processed by an error diffusion method or the like for the clear layer, a clear layer with relatively little overlap of dots can be obtained. The "total area of ​​the decorative layer surface covered by dot-shaped clear ink" is calculated by measuring the average dot radius r of 10 dot-shaped clear inks (clear dots) using an optical microscope and calculating πr 2 The area of ​​the decorative layer surface covered by one clear dot is calculated from the above, and this value is multiplied by the total number of dot-shaped clear inks on the decorative layer. It should be noted that, as the coverage area increases, overlapping of clear dots may occur, but as the clear dots for determining the average dot radius, clear dots that do not overlap with other clear dots were selected. The surface of a clear dot that does not overlap with other clear dots that comes into contact with the decorative layer is circular, and the diameter of the circle is called the dot diameter, and the radius of the circle is called the dot radius. The "total area of ​​the decorative layer surface" refers to the area of ​​the entire decorative layer surface on the side where the clear layer is scattered.

[0036] In the laminate of the present invention, the clear layer is formed from an active energy ray curable ink composition that does not contain a colorant, and the ratio of the polyfunctional polymerizable monomer in the ink composition is less than 50% by mass. By suppressing the ratio of the polyfunctional polymerizable monomer in the ink composition that constitutes the clear layer, it is possible to prevent cracking or peeling from occurring in the clear layer after thermal drying. The ratio of the polyfunctional polymerizable monomer in the active energy ray curable ink composition that constitutes the decorative layer is preferably 0 to 15% by mass.

[0037] In the laminate of the present invention, the active energy ray curable ink composition constituting the clear layer preferably contains urethane acrylate in a ratio of 3% by mass or more and 8% by mass or less in the ink composition. From the viewpoint of preventing cracking or peeling of the clear layer after thermal drying and improving the processability of the laminate, it is preferable to use urethane acrylate in the active energy ray curable ink composition constituting the clear layer. On the other hand, if the ratio of urethane acrylate is too high, blocking resistance may decrease, so the ratio of urethane acrylate in the ink composition is preferably 8% by mass or less. It is more preferable that the ratio of urethane acrylate in the active energy ray curable ink composition constituting the clear layer is 5 to 8% by mass.

[0038] In the present invention, the urethane acrylate is a compound having a urethane bond and an acryloyl group or a methacryloyl group, and is preferably a polymerizable oligomer described below.

[0039] In the laminate of the present invention, the thickness of the clear layer is, for example, 8 to 34 μm. When the clear layer is made of a plurality of dot-shaped cured inks, the thickness of the clear layer refers to the height of the cured inks.

[0040] The laminate of the present invention preferably further comprises an undercoat layer in addition to the decorative layer and the clear layer. The undercoat layer is preferably a coating film formed from an acrylic resin paint or a polyester resin paint, and by providing the undercoat layer using such a paint, it is possible to impart adhesion to various substrates (particularly metal substrates). When the laminate of the present invention comprises an undercoat layer, the decorative layer is located on the undercoat layer. In this case, the laminate of the present invention has a laminate structure in which the undercoat layer, the decorative layer, and the clear layer are formed in this order.

[0041] In the laminate of the present invention, the undercoat layer is a layer (coating film) formed from a paint. In the present invention, the paint used to form the undercoat layer is also called an undercoat paint. The thickness of the undercoat layer is, for example, 10 to 25 μm.

[0042] The laminate of the present invention preferably further comprises a topcoat layer in addition to the decorative layer and the clear layer. The topcoat layer is preferably a coating film formed from an acrylic resin paint, a urethane resin paint, or a fluororesin paint, and by providing the topcoat layer using such a paint, it is possible to impart surface performance and weather resistance to the laminate. When the laminate of the present invention comprises a topcoat layer, the topcoat layer is located on the clear layer. In addition, in the laminate of the present invention, since the clear layer is a layer that covers a part of the surface of the decorative layer, it is preferable that the topcoat layer is also located on the decorative layer where the clear layer is not present. When the laminate of the present invention comprises a topcoat layer, the laminate has a laminate structure in which the undercoat layer, the decorative layer, the clear layer, and the topcoat layer are formed in this order.

[0043] In the laminate of the present invention, the topcoat layer is a layer (coating film) formed from a paint. In the present invention, the paint used to form the topcoat layer is also called the topcoat paint. The thickness of the topcoat layer is, for example, 10 to 25 μm.

[0044] Next, the substrate to which the laminate of the present invention is applied will be described.

[0045] The substrate to which the laminate of the present invention is applied is not particularly limited, and examples thereof include metal substrates containing at least a metal or alloy such as steel, galvanized steel (e.g., galvanized iron sheet), tin-plated steel (e.g., tin plate), stainless steel, magnesium alloy, aluminum, aluminum alloy, etc., wood substrates such as wood, inorganic substrates such as gypsum, calcium silicate, glass, ceramic, concrete, cement, mortar, slate, etc., and plastic substrates such as acrylic resin, polyvinyl chloride, polycarbonate, ABS resin, polyethylene terephthalate, polyolefin, etc. In addition, composite substrates such as wood fiber reinforced cement board, fiber reinforced cement board, fiber reinforced cement-calcium silicate board, etc. can also be exemplified. Metal substrates include substrates that have been subjected to various surface treatments, such as oxidation treatment. In addition, plastic substrates whose surfaces are covered with inorganic substances (e.g., plastic substrates covered with glass) are included in inorganic substrates.

[0046] The substrate may have various shapes, for example, a two-dimensional substrate such as a film, sheet, or plate, or a three-dimensional substrate that is a complex three-dimensional object, etc. The surface of the substrate may be smooth or may have irregularities.

[0047] The surface of the substrate may be subjected to pretreatment such as degreasing, chemical conversion treatment, and polishing, or may be coated with a sealer or primer.

[0048] Specific examples of the substrate include steel materials such as bar bars, steel plates, and steel pipes.

[0049] Next, an active energy ray-curable ink composition that can be used to form the decorative layer and the clear layer of the laminate of the present invention will be described.

[0050] The active energy ray-curable ink composition preferably contains a polymerizable compound and a photopolymerization initiator.

[0051] The polymerizable compound is a compound that undergoes a polymerization reaction via a functional group exhibiting radical polymerization (for example, a photopolymerizable unsaturated group such as a carbon-carbon double bond constituting an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group). A carbon-carbon double bond exhibiting radical polymerization is also called an "ethylenically unsaturated double bond." The polymerizable compound may be used alone or in combination of two or more kinds.

[0052] Polymerizable compounds are classified into monofunctional polymerizable compounds or polyfunctional polymerizable compounds. Here, examples of monofunctional polymerizable compounds include monofunctional polymerizable monomers having one functional group exhibiting radical polymerizability (e.g., monofunctional polymerizable monomers having one polymerizable unsaturated group) and monofunctional polymerizable oligomers having one functional group exhibiting radical polymerizability (e.g., monofunctional polymerizable oligomers having one polymerizable unsaturated group). Examples of polyfunctional polymerizable compounds include polyfunctional polymerizable monomers having two or more functional groups exhibiting radical polymerizability (e.g., polyfunctional polymerizable monomers having two or more polymerizable unsaturated groups) and polyfunctional polymerizable oligomers having two or more functional groups exhibiting radical polymerizability (e.g., polyfunctional polymerizable oligomers having two or more polymerizable unsaturated groups). Polymerizable compounds are usually used in combination of two or more kinds.

[0053] In the active energy ray-curable ink composition for the decorative layer, the proportion of the polymerizable compound in the ink composition is preferably 70 to 90 mass %, the proportion of the monofunctional polymerizable compound in the ink composition is preferably 80 to 90 mass %, and the proportion of the polyfunctional polymerizable compound in the ink composition is preferably 0 to 15 mass %.

[0054] With respect to the active energy ray-curable ink composition for the clear layer, the proportion of the polymerizable compound in the ink composition is preferably 85 to 90 mass %, the proportion of the monofunctional polymerizable compound in the ink composition is preferably 30 to 40 mass %, and the proportion of the polyfunctional polymerizable compound in the ink composition is preferably 25 mass % or more and less than 50 mass %.

[0055] Specific examples of monofunctional polymerizable monomers include isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, 2-(2'-vinyloxyethoxy)ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, N-(meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-Dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, γ-butyrolactone (meth)acrylate, N-vinyl caprolactam, N-(meth)acryloyloxyethyl hexahydrophthalimide, N-vinyl-2-pyrrolidone, N-vinylimidazole, dimethylacrylamide, hydroxyethyl (meth)acrylamide, diethylacrylamide, isopropylacrylamide, dimethylaminopropyl (meth)acrylamide, diacetone acrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methyl Examples of the acrylates include roll acrylamide, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, and the like, and those modified with alkylene glycol.

[0056] Among the polyfunctional polymerizable monomers, specific examples of polyfunctional polymerizable monomers (bifunctional polymerizable monomers) having two functional groups exhibiting radical polymerization include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ) acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, PO (propylene oxide) modified neopentyl glycol di(meth)acrylate, cyclohexane dimethanol diacrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and the like.

[0057] Specific examples of polyfunctional polymerizable monomers having three or more functional groups exhibiting radical polymerization (polyfunctional polymerizable monomers having three or more functions) include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, and glycerin tri(meth)acrylate.

[0058] In this specification, the term (meth)acrylate means methacrylate or acrylate. For example, 2-hydroxyethyl (meth)acrylate is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. In addition, when a prefix indicating a plurality is added to (meth)acrylate, such as di(meth)acrylate, tri(meth)acrylate, etc., each (meth)acrylate may be the same or different. In addition, (meth)acrylic acid means acrylic or methacrylic acid, and (meth)acrylamide means acrylamide or methacrylamide.

[0059] The polymerizable oligomer is preferably an acrylic oligomer, which is an oligomer having an acryloyl group or a methacryloyl group as a functional group exhibiting radical polymerizability.

[0060] The polymerizable oligomer is preferably a polyfunctional polymerizable oligomer, more preferably a polyfunctional acrylic oligomer. The number of functional groups of the polymerizable oligomer is preferably 2 to 6, and the molecular weight of the polymerizable oligomer is preferably 800 to 20,000.

[0061] In the present invention, when the polymerizable compound is an oligomer, the molecular weight thereof is a weight average molecular weight calculated in terms of polystyrene measured by gel permeation chromatography.

[0062] Specific examples of acrylic oligomers include polyurethane acrylic oligomers [acrylic oligomers with multiple urethane bonds (-NHCOO-)], polyester acrylic oligomers [acrylic oligomers with multiple ester bonds (-COO-)], and polyamino acrylic oligomers [amino groups (-NH 2 ) acrylic oligomer], polyepoxy acrylic oligomer [acrylic oligomer with multiple epoxy groups], silicone acrylic oligomer [acrylic oligomer with multiple siloxane bonds (-SiO-)], polybutadiene acrylic oligomer [acrylic oligomer with multiple butadiene units], etc.

[0063] Further, the following acrylic oligomers are known: Beam Set 550B, 575, (Arakawa Chemical Industries, Ltd.), AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (Kyoeisha Chemical Co., Ltd.), CN963, 964, 965NS, 966NS, 969NS, 980NS, 981NS, 982, 983NS, 985, 991NS, 996NS, 8881NS, 8883NS, 9001NS, 9021NS, 9178NS, 9893NS, 929, 989NS, 968NS, 9006NS, 9010NS, 9110NS, 8885NS, 9013NS, 973, 978NS, 9782, 9783, 970, 971, 972, 975NS (manufactured by Sartomer Corporation), U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-33H, UA-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P (manufactured by Shin-Nakamura Chemical Industries), New Frontier R-1235, R-1220, RST-402, R-1304, R-1214, R-1302XT, GX-8801A, R-1603, R-1150D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), EBECRYL210, 220, 230, 270, 280 / 15IB, 284, 294 / 25HD, 1290, 4820, 4858, L5129, 71008210, 8254, 8301R, 8307, 8402, 8405, 8411, 8465, 8800, 8804, 8807, 9260, 9270, 8311, 8701, KRM8200 (manufactured by Daicel-Allnex), UV-1700B, 6300B, 7550B, 7600B, 7605B, 7610B, 7630B, 7640B, 7650B, 6630B, 7000B, 7510B, 3000B, 3200B, 3300B, 3310B, 3700B, 6640B (Mitsubishi Chemical Corporation), Art Resin UN-333, 350, 1255, 2600, 2700, 5590, 6060PTM, 6200, 6202, 6300, 6301, 7600, 7700, 9000PEP, 9200A, 3320HA, 3320HC, 904, 906S (manufactured by Negami Industrial Co., Ltd.), Aronix M-6100, 6250, 6500, 7100, 7300K, 8030, 8060, 8100, 8530, 8560, 9050 (manufactured by Toagosei Co., Ltd.)

[0064] The photopolymerization initiator has the effect of initiating polymerization of the above-mentioned polymerizable compound by irradiation with active energy rays. The amount of the photopolymerization initiator in the ink is preferably 1 to 15% by mass, more preferably 1 to 12% by mass, and even more preferably 1 to 10% by mass. If the content of the polymerization initiator is less than 1% by mass, the film may not be cured properly, and if it exceeds 15% by mass, precipitation may occur at low temperatures, making the ejection of the ink unstable. Furthermore, in order to promote the initiation reaction of the polymerization initiator, it is also possible to use an auxiliary such as a photosensitizer in combination.

[0065] Examples of photopolymerization initiators include benzophenone-based compounds, acetophenone-based compounds, thioxanthone-based compounds, and acylphosphine oxide-based compounds, but from the viewpoint of curability, it is preferable that the wavelength of the irradiated active energy ray overlaps with the absorption wavelength of the photopolymerization initiator as much as possible. In particular, it is preferable that the photopolymerization initiator contains an acylphosphine oxide-based initiator from the viewpoint of coloring during curing and curability in thick films. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0066] Specific examples of the photopolymerization initiator include: 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Benzophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4 -morpholin-4-yl-phenyl)-butan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1-[4-(phenylthiophenyl)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0067] Among these, from the viewpoint of ink curing properties, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 2 From the viewpoints of coloration during curing and curability in the case of a thick film, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferred, with 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide being particularly preferred.

[0068] The active energy ray curable ink composition for the decorative layer contains a colorant. The colorant is appropriately selected depending on the color of the ink. As an example, pigments that can be used in cyan ink, magenta ink, yellow ink, and black ink will be described.

[0069] Pigments used in cyan inks include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 27, 28, 36, 60, 75, and the like. Among these, preferred pigments from the viewpoint of having high coloring properties or weather resistance and increasing the hiding power include CI Pigment Blue 15:3, 15:4, 28, and the like.

[0070] Pigments used in magenta inks include CI Pigment Red 3, 5, 48, 48:1, 48:2, 53:1, 57:1, 101, 122, 146, 166, 170, 177, 185, 202, 207, 209, 254, and the like. Among these, CI Pigment Red 101, 122, and the like are preferred pigments from the viewpoint of having high coloring properties or weather resistance and increasing the hiding power.

[0071] Pigments used in yellow inks include CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 42, 55, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 119, 120, 128, 129, 130, 138, 139, 150, 151, 153, 154, 155, 168, 180, 181, 185, 213, and 214. Among these, preferred pigments from the viewpoint of having high coloring properties or weather resistance and increasing the hiding power include CI Pigment Yellow 42, 120, 138, 150, 151, 155, 213, and the like.

[0072] Pigments used in black inks include CI Pigment Black 1, 6, 7, 9, 10, 11, 20, 26, 28, 31, 32, and 34. Among these, CI Pigment Black 7 is preferred as a pigment from the viewpoint of having high coloring properties or weather resistance and increasing the hiding power.

[0073] In the active energy ray curable ink composition for the decorative layer, the content of the colorant in the ink composition is, for example, 0.5 to 15 mass %. The colorant may be used alone or in combination of two or more kinds.

[0074] The active energy ray curable ink composition for the decorative layer may further contain a dispersant as necessary to disperse the pigment. The content of the dispersant in the active energy ray curable ink composition for the decorative layer is, for example, 0.1 to 5 mass% in the ink composition. The dispersant may be used alone or in combination of two or more.

[0075] Specific examples of pigment dispersants include: ANTI-TERRA-U, U100, 204, 205, DISPERBYK-101N, 102, 103, 106, 108, 109, 110, 111, 130, 140, 142, 145, 161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 180, 182, 184, 185, 2000, 2001, 2008, 2009, 2025, 2050, 2070, 2096, 2013, 2150, 2155, 2163, 2164, BYK-P104, P104S, P105, 9076, 9077, 220SN, BYKJET-9150, 9151 (all manufactured by BYK Japan), Solsperse3000, 9000, 11200, 13240, 13940, 16000, 17000, 20000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 36000, 36600, 37500, 38500, 39000, 41000, 54000, 71000, 76500, J180, J200, X300 (all manufactured by Lubrizol), Disparlon DA-7301, DA-325, DA-375, DA-234 (all manufactured by Kusumoto Chemicals Co., Ltd.), FLORALENE AF-1000, DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, G-700, G-820XF, GW-1500, KDG-2400 (all manufactured by Kyoeisha Chemical Co., Ltd.), TEGO Dispers610, 610S, 630, 650, 652, 655, 662C, 670, 685, 700, 710, 740W, LIPOTIN A, BL, DB, SB (all manufactured by Evonik Degussa), Ajisper PB821, PB822, PN411, PA111 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), BorchiGen0451 (all manufactured by Borchias).

[0076] The active energy ray-curable ink composition may further contain a surface conditioner from the viewpoint of improving wettability, etc. In the present invention, the surface conditioner means a substance that has a hydrophilic moiety and a hydrophobic moiety in its molecular structure and that can adjust the surface tension of the ink by adding it.

[0077] Specific examples of the surface conditioner include anionic surface conditioners such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts, nonionic surface conditioners such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers, cationic surface conditioners such as alkylamine salts and quaternary ammonium salts, acrylic surface conditioners, silicon surface conditioners, and fluorine surface conditioners. Silicon surface conditioners and acrylic surface conditioners are particularly preferred, and commercially available products from BYK, Evonik, Toray Dow Corning, and the like can be used.

[0078] The amount of the surface conditioner can be appropriately selected depending on the purpose of use, but is preferably, for example, 0.01 to 1 mass % in the ink composition. The surface conditioner may be used alone or in combination of two or more kinds.

[0079] Specific examples of surface conditioners include: BYK-300, 302, 306, 307, 310, 313, 315N, 320, 322, 323, 325N, 326, 330, 331, 333, 342, 345, 346, 347, 348, 349 , 350, 354, 355, 356, 358N, 361N, 370, 375, 377, 378, 381, 392, 394, 399, 3455, 3550, 3560, 3565, 3760, DYNWET 800N, SILCLEAN 3700, 3701, 3720, UV3500, 3505, 3510, 3530, 3535, 3570, 3575, 3576 (all manufactured by BYK Japan), TEGO Flow 300, 370, 425, ATF 2, ZFS 460, TEGO Glide 100, 110, 130, 406, 410, 411, 415, 432, 435, 440, 450, 482, TEGO GlideA 115, TEGO GlideB 1484, TEGO GlideZG 400 (all manufactured by Evonik Japan), 501W ADDITIVE, FZ-2104 Fluid, 2110, 2123, 2164, 2191 Fluid, 2203, 2215, 2222, 5609 Fluid, L-7001, 7002, 7604, OFX-0193 Fluid, 0309 FLUID, 5211 FLUID, SF 8410 FLUID, SH 3746 FLUID, 8400 FLUID, 8700 FLUID, Y-7006 (all manufactured by Dow Corning Toray Co., Ltd.), Examples of such compounds include KF-351A, 352A, 353, 354L, 355A, 615A, 640, 642, 643, 644, 945, 6004, 6011, 6012, 6015, 6017, 6020, 6204, X-22-2516, and X-22-4515 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0080] The active energy ray curable ink composition may contain an ultraviolet absorbing agent. The ultraviolet absorbing agent has a function of absorbing ultraviolet rays and preventing deterioration caused by ultraviolet rays. Examples of the ultraviolet absorbing agent include cyanoacrylate-based compounds, benzophenone-based compounds, benzoate-based compounds, benzotriazole-based compounds, hydroxyphenyltriazine-based compounds, benzylidene camphor-based compounds, inorganic fine particles, and the like.

[0081] Specific examples of ultraviolet absorbents include: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole 2-[2'-hydroxy-3',5'-bis(α,α-(dimethylbenzyl)phenyl]benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, Examples thereof include hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0082] The amount of the ultraviolet absorbent in the ink composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass. If the amount of the ultraviolet absorbent is too large, the film may not be cured sufficiently. The ultraviolet absorbent may be used alone or in combination of two or more kinds, but it is preferable that the ultraviolet absorbent contains at least two kinds of ultraviolet absorbents. By using multiple kinds of ultraviolet absorbents with different structures, the effect of the ultraviolet absorbent can be further sustained.

[0083] The active energy ray curable ink composition may contain a radical scavenger. The radical scavenger can capture free radicals and improve light stability. In addition, the radical scavenger also includes a substance (so-called polymerization inhibitor) that reacts with free radicals and has a function of preventing a polymerization reaction from occurring.

[0084] Examples of the radical scavenger include hindered amine compounds, hydroquinone compounds, phenol compounds, phenothiazine compounds, nitroso compounds, and N-oxyl compounds, and hindered amine light stabilizers (HALS) are particularly preferred.

[0085] Specific examples of radical scavengers include hindered amine compounds such as bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and 1-{2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl}-2,2,6,6-tetramethylpiperidine, phenol compounds such as phenol, o-, m- or p-cresol, 2-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol, 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, and 2,4-di-t-butylphenol, hydroquinone, and hydroquinone monomethyl. Examples of the hydroquinone compounds include ethers, methylhydroquinone, 2,5-di-t-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, benzoquinone, t-butyl-p-benzoquinone, and 2,5-diphenyl-p-benzoquinone; phenothiazine compounds such as phenothiazine; nitroso compounds such as N-nitroso-N-phenylhydroxylamine ammonium and N-nitroso-N-phenylhydroxylamine aluminum salt; and N-oxyl compounds such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl.

[0086] The amount of the radical scavenger in the ink composition is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less. If the amount of the radical scavenger is too large, it may cause poor curing. The lower limit of the content of the radical scavenger in the ink composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The radical scavenger may be used alone or in combination of two or more kinds.

[0087] The active energy ray-curable ink composition may contain, as other components, additives such as antioxidants, plasticizers, antirust agents, solvents, antibacterial agents, antiviral agents, viscosity adjusters, fillers, defoamers, charge control agents, stress relaxation agents, penetrating agents, light-guiding materials, glittering materials, magnetic materials, and phosphors, as necessary.

[0088] The actinic radiation curable ink composition can be prepared by mixing various components appropriately selected as necessary. In addition, it is preferable to filter the ink using a filter in order to prevent clogging of the nozzles of the head due to impurities, etc.

[0089] The viscosity of the active energy ray curable ink composition at 20°C to 55°C is preferably 5 to 25 mPa·s, and more preferably 5 to 20 mPa·s. Since the temperature during ink ejection is preferably 20°C to 55°C, good ejection stability can be obtained if the ink viscosity is within the above specified range. The ink viscosity can be measured using a cone-plate type viscometer.

[0090] The active energy ray curable ink composition preferably has a surface tension of 20 to 35 mN / m, more preferably 23 to 33 mN / m, at 25° C. When the ink surface tension at 25° C. is within the above specified range, good ejection stability can be obtained. The ink surface tension can be measured by a plate method.

[0091] The active energy ray curable ink composition is preferably an ink for printing with a droplet ejection type printing device, and is particularly preferably an inkjet ink; however, the present invention is not limited thereto, and various printing methods such as gravure printing, offset printing, flexographic printing, screen printing, and coater printing can also be used.

[0092] A droplet ejection type printing device is a printing device that ejects ink droplets from a printing device (particularly a print head) and causes them to land on a substrate, and examples of such a printing device include inkjet printers, etc. In the present invention, inkjet ink refers to ink used in inkjet printers.

[0093] Examples of the inkjet printer include inkjet printers that eject ink by a charge control method or a piezoelectric method. Large-size inkjet printers, specifically inkjet printers intended for printing on products produced on industrial lines, can also be suitably used.

[0094] Next, the paints (undercoat paint and topcoat paint) that can be used to form the undercoat layer and topcoat layer of the laminate of the present invention will be described.

[0095] The undercoat paint may contain, as appropriate, ingredients depending on the purpose, such as resins, solvents, colorants, flexibility-imparting agents, surface conditioners, wetting agents, pigment dispersants, emulsifiers, viscosity modifiers, anti-settling agents, anti-skinning agents, anti-sagging agents, defoamers, anti-color separation agents, leveling agents, drying agents, plasticizers, film-forming aids, neutralizing agents, electrostatic lubricants, antistatic agents, and conductivity-imparting agents.

[0096] The topcoat paint may contain, as appropriate depending on the purpose, for example, resins, solvents, colorants, matting agents, flexibility-imparting agents, surface conditioners, wetting agents, pigment dispersants, emulsifiers, viscosity adjusters, anti-settling agents, anti-skinning agents, anti-sagging agents, defoamers, color separation inhibitors, leveling agents, drying agents, plasticizers, film-forming aids, neutralizing agents, anti-fungal agents, antibacterial agents, insecticides, light stabilizers, ultraviolet absorbing agents, electrostatic lubricants, antistatic agents, and conductivity-imparting agents.

[0097] The undercoat paint and topcoat paint can be prepared by mixing various components appropriately selected as required.

[0098] The undercoat paint and topcoat paint preferably have a viscosity of 1 to 1000 (Pa s, 23°C) at a shear rate of 0.1 (1 / s), and a viscosity of 0.05 to 10 (Pa s, 23°C) at a shear rate of 1000 (1 / s). In the present invention, the viscosity is measured using a rheometer (e.g., ARES rheometer manufactured by TA Instruments) after adjusting the liquid temperature to 23°C.

[0099] The coating means for the undercoat paint and topcoat paint are not particularly limited, and known coating means such as dipping, spin coating, flow coating, roll coating, spray coating, blade coating, and air knife coating can be used.

[0100] The drying means for the undercoat paint is not particularly limited, and may be either natural drying at ambient temperature or forced drying using a dryer, etc. On the other hand, the drying of the topcoat paint is preferably performed by thermal drying (for example, drying at 80 to 180°C). EXAMPLES

[0101] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0102] (Preparation example of ink set 1 for decorative layer) A mixture containing the components shown in Table 1 was stirred and dissolved to make it homogenous, and then filtered to prepare cyan ink 1, magenta ink 1, yellow ink 1, and black ink 1 according to the formulations shown in Table 1, and ink set 1 consisting of these four color inks was prepared.

[0103] [Table 1]

[0104] PB15:4: CI Pigment Blue 15:4 PR122: CI Pigment Red 122 PY150: CI Pigment Yellow 150 PBk7: CI Pigment Black 7 Solsperse32000: Pigment dispersant manufactured by Lubrizol Isobornyl acrylate: Monofunctional polymerizable monomer Phenoxyethyl acrylate: Monofunctional polymerizable monomer BYK-UV3500: Surface conditioner manufactured by BYK Japan 2,4,6-Trimethylbenzoyldiphenylphosphine oxide: Photoinitiator

[0105] In Table 1, "monofunctional ratio [%]" indicates the ratio (mass %) of the monofunctional polymerizable monomer contained in the ink composition.

[0106] (Example of preparation of ink for clear layer) Mixtures containing the components shown in Tables 2-3 were stirred and dissolved to homogenize, and then filtered to prepare clear inks 1-22 according to the formulations shown in Tables 2-3.

[0107] [Table 2]

[0108] [Table 3]

[0109] N-Acryloylmorpholine: Monofunctional polymerizable monomer 1,6-Hexanediol diacrylate: Bifunctional polymerizable monomer Trimethylolpropane triacrylate: Trifunctional polymerizable monomer EBECRYL8402: Difunctional polymerizable urethane acrylate manufactured by Daicel-Allnex Corporation BYK-UV3500: Surface conditioner manufactured by BYK Japan 2,4,6-Trimethylbenzoyldiphenylphosphine oxide: Photoinitiator

[0110] In Tables 2 and 3, "monofunctional ratio [%]" indicates the ratio (mass %) of monofunctional polymerizable monomers contained in the ink composition, and "polyfunctional ratio [%]" indicates the ratio (mass %) of polyfunctional polymerizable monomers contained in the ink composition.

[0111] (Example of preparation of laminate) The undercoat paints shown in Tables 4 to 11 were applied onto a substrate (aluminum plate) and then thoroughly dried to form an undercoat layer. For the undercoat paints shown in Tables 4 to 11, "acrylic" refers to IJ base DMS (manufactured by Dai Nippon Toryo Co., Ltd.), and "polyester melamine" refers to IJ base VNR (manufactured by Dai Nippon Toryo Co., Ltd.). The undercoat layer had a thickness of 15 to 20 μm. After applying the undercoat paint using an air spray, it was baked and dried under the conditions of 160° C. for 20 minutes. Ink set 1 shown in Table 1 was printed on the undercoat layer using a printer (Stage Jet IT-1 manufactured by Tritec Corporation), and then irradiated with an LED light source to sufficiently harden the ink to form a decorative layer. The decorative layer was formed by solid printing of four colors of ink at a print density of 100%, with the thickness of each color layer being 5 μm, and the overall thickness of the decorative layer being 20 μm. Next, each clear ink shown in Tables 4 to 11 was solid printed on the decorative layer with the print density set to the coverage area shown in Tables 4 to 11, and then irradiated with an LED light source to sufficiently harden the ink to form a clear layer. For Examples 61 to 65, the topcoat paint shown in Table 10 was applied onto the decorative layer and the clear layer, and then thoroughly dried to form a topcoat layer. For the topcoat paints shown in Table 10, "acrylic" refers to Duracron CW (manufactured by Dai Nippon Toryo Co., Ltd.), "fluorine-based" refers to V-Flon #2000 (manufactured by Dai Nippon Toryo Co., Ltd.), and "polyester melamine-based" refers to V-Knit #1500 (manufactured by Dai Nippon Toryo Co., Ltd.). The topcoat layer had a thickness of 10 to 20 μm. After applying the topcoat paint using an air spray, it was baked and dried at 160°C for 20 minutes.

[0112] The laminates of Examples 1 to 60 and Comparative Examples 1 to 4 are laminates having an undercoat layer, a decorative layer, and a clear layer, and the laminates of Examples 61 to 65 are laminates having an undercoat layer, a decorative layer, a clear layer, and a topcoat layer. These laminates were formed on a substrate, and the substrates with the laminates were used to evaluate blocking resistance, heat resistance, and processability.

[0113] (Clear layer coverage area) The surface of the laminate with the clear layer was photographed using an optical microscope. For Examples 61 to 65, the laminate was photographed before the topcoat layer was formed. Using a digital microscope manufactured by Keyence Corporation, the images were taken at a lens magnification of 500x, allowing the boundaries of the dots to be observed. The dot diameters of 10 clear dots were measured from the captured image, and the average dot radius r was calculated. The number of clear dots printed from the print image data was counted. 3.14×r 2 The area of ​​the decorative layer surface covered by one clear dot was calculated, and this was multiplied by the total number of dot-shaped clear ink pieces on the decorative layer to obtain the "total area of ​​the decorative layer surface covered by dot-shaped clear ink." The image area of ​​the printed image was determined as the area of ​​the entire surface of the decorative layer on the side where the clear layer was present. The coverage area of ​​the clear layer was calculated using the following formula. The results are shown in Tables 4 to 11. Coverage area = (Total area of ​​decorative layer surface covered by dot-shaped clear ink / Total area of ​​decorative layer surface) x 100

[0114] (Pencil hardness of decorative layer) The test plate, the surface of which is the decorative layer, was measured for scratch hardness (pencil hardness method) according to JIS K 5600-5-4 (1999). The hardness of the hardest pencil that does not scratch the surface of the decorative layer was evaluated as the pencil hardness of the decorative layer. The results are shown in Tables 4 to 11. The test plate was made by printing the ink set 1 shown in Table 1 on the substrate (aluminum plate) with a printer (Stage Jet IT-1 manufactured by Tritec), irradiating it with an LED light source to fully harden the decorative layer, and then drying it under baking conditions of 160°C x 20 minutes. The decorative layer was formed by solid printing of four colors of ink at 100% printing density, with each color layer being 5μm thick, and the overall thickness of the decorative layer being 20μm.

[0115] (Pencil hardness of clear layer) The test plate with the clear layer on the surface was measured for scratch hardness (pencil hardness method) according to JIS K 5600-5-4 (1999). The hardness of the hardest pencil that did not scratch the clear layer surface was evaluated as the pencil hardness of the clear layer. The results are shown in Tables 4 to 11. The test plate was prepared by printing each of the clear inks shown in Tables 4 to 11 on the substrate (aluminum plate) at 100% print density using a printer (Stage Jet IT-1 manufactured by Tritec Corporation), irradiating the LED light source to sufficiently harden the clear layer, and then drying it under baking conditions of 160°C x 20 minutes. The thickness of the clear layer was 15 μm.

[0116] <Blocking resistance> A substrate with a laminate was prepared as a test plate according to the above (Laminate Preparation Example). The same aluminum plate as used as the substrate (or the substrate side surface of another substrate with a laminate prepared in the same manner) was placed on the laminate side surface of the test plate, and a pressure of 10 kgf / cm 2 After applying a load of 10 ... When the blocking resistance is evaluated as ⊚ or ◯, the laminate has excellent blocking resistance. Evaluation criteria ◎: Can be peeled off smoothly, no color transfer to the back side 〇: Peels off with some noise, but no color transfer to the back side △: It takes some force to peel off, and there is slight color transfer on the back side. ×: Requires force to peel off, and color transfer occurs across the entire back surface

[0117] <Heat resistance> The substrate with the laminate was baked for 20 minutes in a drying oven set at 160° C., and then the state of the laminate was observed and the heat resistance of the laminate was evaluated according to the following criteria. The results are shown in Tables 4 to 11. Evaluation criteria ◯: No cracking or peeling occurs. ×: Cracks or peeling occurs.

[0118] <Workability> The substrate with the laminate was prepared as a test plate. The substrate surface on which the laminate was formed was placed on the outside, and a plate of the same thickness as the test plate (the same aluminum plate as the substrate of the test plate was used) was sandwiched on the inside of the bent plate, and the plate was bent 180 degrees. The bent portion was visually observed for cracks, and further, cellophane tape was applied to the bent portion and quickly peeled off to check for the presence or absence of peeling. The processability of the laminate was evaluated according to the following criteria. The results are shown in Tables 4 to 11. When the processability is evaluated as ⊚ or ◯, the laminate has excellent processability. Evaluation criteria ⊚: There are no cracks in the bent portion, and no peeling occurs even when tape is peeled off. ◯: Fine cracks occur at the bent portion, but no peeling occurs even when tape is peeled off. △: Fine cracks were generated at the bent portion, and peeling occurred when the tape was peeled off. ×: Cracks and spontaneous peeling occurred at the bent portion, and the laminate was turned up.

[0119] [Table 4]

[0120] [Table 5]

[0121] [Table 6]

[0122] [Table 7]

[0123] [Table 8]

[0124] [Table 9]

[0125] [Table 10]

[0126] [Table 11]

[0127] In Tables 4 to 6, "Clear ink formulation" shows details of the clear ink used. Specifically, "monofunctional" in "clear ink formulation" indicates the monofunctional polymerizable monomer contained in the clear ink, "polyfunctional" indicates the polyfunctional polymerizable monomer contained in the clear ink, "(ratio in ink)" indicates the proportion (mass %) of the polyfunctional polymerizable monomer contained in the clear ink, and "urethane acrylate" indicates the proportion (mass %) of urethane acrylate contained in the clear ink.

Claims

1. A laminate including a decorative layer and a clear layer, the decorative layer is formed from an active energy ray-curable ink composition containing a colorant, and the clear layer is formed from an active energy ray-curable ink composition that does not contain a colorant, and a ratio of a polyfunctional polymerizable monomer in the ink composition is less than 50 mass%, The pencil hardness of the decorative layer is B or less, and the pencil hardness of the clear layer is H or more; A laminate characterized in that the clear layer is scattered on the decorative layer and covers 60 area % or more and 90 area % or less of the surface of the decorative layer.

2. The laminate according to claim 1 , wherein the active energy ray curable ink composition constituting the decorative layer contains a monofunctional polymerizable monomer in a proportion of 70% by mass or more in the ink composition.

3. 3. The laminate according to claim 1, wherein the active energy ray curable ink composition constituting the clear layer contains urethane acrylate in an amount of 3% by mass or more and 8% by mass or less in the ink composition.

4. The laminate according to claim 1 or 2, further comprising an undercoat layer, and the decorative layer is located on the undercoat layer.

5. 3. The laminate according to claim 1 or 2, further comprising a topcoat layer, the topcoat layer being located on the clear layer and on the decorative layer where the clear layer is not present.

Images