Film for inkjet printing, laminate sheet, decorative sheet, and number plate

Abstract

To provide a film for inkjet printing excellent in inkjet printability and low-temperature impact resistance.SOLUTION: A film for inkjet printing includes a polyurethane resin, a (meth) acrylic resin, and a pigment. A content of the (meth) acrylic resin is 15-80 pts.mass with respect to 100 pts.mass of the polyurethane resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an inkjet printing film, a laminated sheet, a decorative sheet, and a license plate. [Background technology]

[0002] Films with design layers formed by inkjet printing are used to decorate outdoor signs and two-wheeled and four-wheeled vehicles. For inkjet printing applications, inkjet printing films made primarily from vinyl chloride resin or (meth)acrylic resin are sometimes used (see, for example, Patent Documents 1-3). It is also known that inkjet-printed film is laminated to a substrate (such as a metal plate, a resin plate, or a resin film) and three-dimensionally molded for use as a number plate (also called a "license plate") (see, for example, Patent Document 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-024777 A [Patent Document 2] International Publication No. 2010 / 001664 [Patent Document 3] Japanese Patent Application Publication No. 7-009756 [Patent Document 4] JP 2017-177481 A Summary of the Invention [Problem to be solved by the invention]

[0004] Inkjet printing films made of vinyl chloride resin or (meth)acrylic resin are brittle at low temperatures, and there is concern that they may crack due to impact when used outdoors in cold regions. In addition, films made from urethane resin are known to have excellent low-temperature impact resistance, but they have poor inkjet printability. The present disclosure has been made in consideration of the above-mentioned conventional circumstances, and aims to provide an inkjet printing film that has excellent inkjet printability and low-temperature impact resistance, as well as a laminate sheet, a decorative sheet, and a license plate that use this inkjet printing film. [Means for solving the problem]

[0005] Specific means for achieving the above object are as follows. <1> The composition includes a polyurethane resin, a (meth)acrylic resin, and a pigment, The film for inkjet printing, wherein the content of the (meth)acrylic resin per 100 parts by mass of the polyurethane resin is 15 to 80 parts by mass. <2> The pigment is at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate. <1> 2. The inkjet printing film according to claim 1 . <3> The content of the pigment relative to 100 parts by mass of the polyurethane resin is 10 parts by mass to 70 parts by mass. <1> or <2> 2. The inkjet printing film according to claim 1 . <4> <1> ~ <3> 13. A laminated sheet comprising the film for inkjet printing according to any one of claims 1 to 12, and a pressure-sensitive adhesive layer provided on one surface of the film for inkjet printing. <5> An intermediate layer is provided between the inkjet printing film and the pressure-sensitive adhesive layer. <4> The laminate sheet according to claim 1. <6> The intermediate layer contains a polyurethane resin and a pigment. <5> The laminate sheet according to claim 1. <7> The pigment contained in the intermediate layer is at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate. <6> The laminate sheet according to claim 1. <8> <4> ~ <7> 13. A decorative sheet comprising the laminate sheet according to claim 12, and a surface protective layer disposed on a surface of the inkjet printing film constituting the laminate sheet opposite to the side on which the adhesive layer is provided. <9> A plate base material and a substrate provided on one surface side of the plate base material. <8> A license plate comprising the decorative sheet according to claim 1. Effect of the Invention

[0006] According to the present disclosure, it is possible to provide an inkjet printing film that has excellent inkjet printability and low-temperature impact resistance, as well as a laminate sheet, a decorative sheet, and a license plate that use this inkjet printing film. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a cross-sectional view of a first embodiment of a laminate sheet according to the present disclosure. [Diagram 2] FIG. 2 is a cross-sectional view of a second embodiment of a laminate sheet according to the present disclosure. [Diagram 3] 1 is a cross-sectional view of an embodiment of a decorative sheet according to the present disclosure. [Figure 4] FIG. 1 is a cross-sectional view of one embodiment of the license plate of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, the embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values ​​and their ranges, and do not limit the present disclosure. In the present disclosure, when an embodiment is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. In addition, the size of the members in each drawing is conceptual, and the relative relationship of the size between the members is not limited thereto. In addition, in each drawing, the same reference numerals are given to members having substantially the same functions, and duplicated descriptions may be omitted.

[0009] In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In this disclosure, the term "lamination" refers to stacking layers, where two or more layers may be bonded together or two or more layers may be removable. In the present disclosure, "(meth)acrylic" means at least one of acrylic and methacrylic. In the present disclosure, the average thickness of a layer or film is a value calculated as the arithmetic mean value of thicknesses measured at five points on a target layer or film. The thickness of the layer or film is the value measured using a constant pressure thickness gauge (measuring probe diameter 5 mm).

[0010] In the present disclosure, the term "polyurethane-based resin" refers to a resin obtained as a reaction product of a polyol, an organic polyisocyanate, and an optional chain extender. In the present disclosure, "(meth)acrylic resin" refers to a resin that contains structural units derived from (meth)acrylic monomers, and in which the proportion of structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic resin is 50 mass% or more. In the present disclosure, "methacrylic resin" refers to a resin in which the proportion of structural units derived from methacrylic monomers in the total structural units of the (meth)acrylic resin is 50% by mass or more. In addition, in the present disclosure, "acrylic resin" refers to a resin in which the proportion of structural units derived from acrylic monomers in the total structural units of the (meth)acrylic resin is 50% by mass or more. Note that, in the case where the proportion of structural units derived from methacrylic monomers and the proportion of structural units derived from acrylic monomers in the total structural units of the (meth)acrylic resin are both 50% by mass, the (meth)acrylic resin will be referred to as a methacrylic resin in the present disclosure. In the present disclosure, the term "solid content" refers to components other than the solvent contained in the composition. In this disclosure, "solvent" means water and / or an organic solvent.

[0011] <Film for inkjet printing> The film for inkjet printing of the present disclosure contains a polyurethane resin, a (meth)acrylic resin, and a pigment, and the content of the (meth)acrylic resin per 100 parts by mass of the polyurethane resin is 15 parts by mass to 80 parts by mass. The inkjet printing film of the present disclosure has excellent inkjet printability and low-temperature impact resistance. The reason why the inkjet printing film of the present disclosure has excellent inkjet printability and low-temperature impact resistance is not clear, but is presumed to be as follows. It is believed that by further containing a (meth)acrylic resin in an inkjet printing film containing a polyurethane resin, the urethane phase and the (meth)acrylic phase in the inkjet printing film are appropriately separated, and the (meth)acrylic phase existing between the urethane phases is likely to absorb the solvent of the inkjet ink. Therefore, it is presumed that while maintaining the low-temperature impact resistance due to the polyurethane resin, bleeding and uneven shading of the inkjet ink are unlikely to occur, improving the inkjet printability.

[0012] Each component constituting the inkjet printing film of the present disclosure will be described in detail below. The inkjet printing film of the present disclosure contains a polyurethane resin, a (meth)acrylic resin, and a pigment, and may contain other components such as a plasticizer, a softener, an ultraviolet absorber, a light stabilizer, an antifoaming agent, and an antioxidant as necessary.

[0013] (Polyurethane resin) The inkjet printing film of the present disclosure contains a polyurethane resin. The type of polyurethane resin is not particularly limited, and conventionally known polyurethane resins such as polycarbonate polyurethane resin, polyester polyurethane resin, polyether polyurethane resin, etc. may be used. The polyurethane resin may be used alone or in combination of two or more kinds. The polyurethane-based resin preferably contains at least one selected from the group consisting of polycarbonate-based polyurethane resins, polyester-based polyurethane resins, and polyether-based polyurethane resins, and from the viewpoint of improving the weather resistance of the inkjet printing film, polycarbonate-based polyurethane resins are more preferable.

[0014] The elongation of the polyurethane resin at 23°C is preferably 50%GL to 1000%GL, more preferably 75%GL to 750%GL, and even more preferably 100%GL to 500%GL, from the viewpoint of preventing cracking of the film when three-dimensionally molding the film for inkjet printing. When two or more polyurethane resins are used in combination, the elongation of the mixture of polyurethane resins at 23°C is preferably within the above range. preferable.

[0015] The yield point of the polyurethane resin at 23°C is preferably 0.5 N to 20 N, more preferably 0.8 to 15 N, and even more preferably 1.0 N to 10 N, from the viewpoint of preventing cracking of the film when three-dimensionally molding the film for inkjet printing. When two or more polyurethane resins are used in combination, the yield point of the mixture of polyurethane resins at 23°C is preferably within the above range.

[0016] The Young's modulus of the polyurethane resin at 23° C. is preferably 10 MPa to 2000 MPa, more preferably 15 MPa to 1500 MPa, and even more preferably 20 MPa to 1000 MPa, from the viewpoint of preventing cracking of the film when three-dimensionally molding the film for inkjet printing. When two or more polyurethane resins are used in combination, the Young's modulus of the mixture of polyurethane resins at 23° C. is preferably within the above range.

[0017] In the present disclosure, the elongation, yield point and Young's modulus of a polyurethane-based resin at 23°C refer to values ​​determined by conducting a tensile test on a polyurethane-based resin test piece having an average thickness of 35 μm, a length of 150 mm and a width of 10 mm using a tensile tester in a test environment of 23°C, with a gripping distance of 100 mm and a tensile speed of 300 mm / min.

[0018] The proportion of the polyurethane resin in the solid content of the film for inkjet printing is not particularly limited, but from the viewpoint of further improving the low-temperature impact resistance of the film for inkjet printing, it is preferably 40% by mass to 80% by mass, more preferably 58% by mass to 78% by mass, and even more preferably 63% by mass to 76% by mass.

[0019] As the polyurethane resin, commercially available products can be used. Examples of commercially available polyurethane resins include "NE-8836 (polycarbonate-based)", "NE-8811 (polycarbonate-based)", and "NE-8850 (polycarbonate-based)" (all manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), as well as "Superflex 420 (polycarbonate-based)", "Superflex 460 (polycarbonate-based)", and "Superflex 210 (polyester-based)" (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Pandex T-9280 (polycarbonate-based)", "Pandex T-9290 (polycarbonate-based)", "Pandex T-1190 (polyester-based)", and "Pandex T-8190 (polyether-based)" (all manufactured by DIC Covestro Polymer Co., Ltd.).

[0020] The polyurethane resin in the present disclosure also includes the urethane resin contained in the pigment dispersion liquid described below.

[0021] ((Meth)acrylic resin) The inkjet printing film of the present disclosure contains a (meth)acrylic resin. The type of (meth)acrylic resin is not particularly limited, and a conventionally known (meth)acrylic resin can be used. The (meth)acrylic resin may be used alone or in combination of two or more kinds.

[0022] The (meth)acrylic resin may be a homopolymer consisting of structural units derived from a single (meth)acrylic monomer, or a copolymer consisting of structural units derived from two or more types of (meth)acrylic monomers. Here, the (meth)acrylic monomer means at least one of acrylic acid, derivatives of acrylic acid such as acrylic acid alkyl esters, and derivatives of methacrylic acid such as methacrylic acid alkyl esters. The derivatives of acrylic acid and the derivatives of methacrylic acid may have a substituent such as a hydroxyl group, an amino group, a carboxyl group, or a glycidyl group.

[0023] The (meth)acrylic resin may be either a solventless type or a solvent type. From the viewpoint of ease of handling, it is preferable to use a solventless (meth)acrylic resin.

[0024] Examples of the solvent-free (meth)acrylic resin include powdered, pelleted, and beaded (meth)acrylic resins. As the powdered (meth)acrylic resin, a core-shell type having different monomer compositions between the core and shell can also be used.

[0025] As the solvent-free (meth)acrylic resin, commercially available products may be used as they are, but when the (meth)acrylic resin is purchased in a solvent-type state as described below, the resin may be used after being made solvent-free by distilling off the solvent. For example, a powdered (meth)acrylic resin obtained by distilling off the solvent from an emulsion type (aqueous dispersion of a (meth)acrylic resin) may be used.

[0026] Commercially available solvent-free (meth)acrylic resins include "Dianal MB-2593" (manufactured by Mitsubishi Chemical Corporation) and "Parapet GR-F" (manufactured by Kuraray Co., Ltd.), as well as "Dianal BR-50", "Dianal BR-73", "Dianal BR-83", "Dianal BR-101", "Dianal BR-105", "Dianal BR-106", "Dianal BR-113", "Dianal BR-115", "Dianal BR-116", "Dianal BR-117", "Dianal BR-119", "Dianal BR-605", and "Dianal MB-2660". ", "Dianal MB-2952", "Dianal MB-7922", "Dianal LP-3104", "Dianal LP-3106", "Dianal LP-3109", "Dianal LP-3121", "Dianal LP-3130", "Dianal LP-3202", "Dianal LP-3207", "Dianal LP-4100", "Dianal LP-4200", "Dianal LP-5013" (all manufactured by Mitsubishi Chemical Corporation), "Parapet SA-FP", "Parapet SA-NP", and "Parapet SA-CP" (all manufactured by Kuraray Co., Ltd.) are examples thereof.

[0027] The solvent used in the solvent-based (meth)acrylic resin may be an organic solvent or water. The solvent-based (meth)acrylic resin may be an emulsion type (aqueous dispersion of a (meth)acrylic resin).

[0028] The solvent-based (meth)acrylic resin may be a commercially available product. Commercially available solvent-based (meth)acrylic resins include "Dianal SE-5437", "Dianal SE-5102", "Dianal SE-5377", "Dianal SE-5649", "Dianal SE-5466", "Dianal SE-5482", "Dianal HR-169", "Dianal HR-124", "Dianal HR-1127", "Dianal HR-116", "Dianal HR-113", "Dianal HR-1148", "Dianal HR-131", "Dianal HR-470", "Dianal HR-634", "Dianal H" and "Dianal H" are examples of solvent-based (meth)acrylic resins. R-606, "Dianal HR-607", "Dianal LR-1065", "Dianal LR-574", "Dianal LR-143", "Dianal LR-396", "Dianal LR-637", "Dianal LR-162", "Dianal LR-469", "Dianal LR-216", "Dianal LX-1010", "Dianal LX-2011" (all manufactured by Mitsubishi Chemical Corporation), "Nikasol TS-620", "Nissetsu KP-1876E" (all manufactured by Nippon Carbide Industries Co., Ltd.), and "H-4002" (manufactured by Negami Industrial Co., Ltd.).

[0029] The (meth)acrylic resin in the present disclosure also includes the acrylic resin contained in the pigment dispersion liquid described below.

[0030] From the viewpoint of further improving the inkjet printability of the film for inkjet printing, it is preferable that the (meth)acrylic resin contains a methacrylic resin. When a methacrylic resin and an acrylic resin are used in combination as the (meth)acrylic resin, the proportion of structural units derived from methacrylic monomers in the entire methacrylic resin and acrylic resin is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more.

[0031] The content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is 15 to 80 parts by mass. When the content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is 15 parts by mass or more, the inkjet printing performance of the film for inkjet printing is further improved. When the content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is 80 parts by mass or less, the low-temperature impact resistance of the film for inkjet printing is further improved. The content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is preferably 20 parts by mass to 60 parts by mass, more preferably 23 parts by mass to 50 parts by mass, and further preferably 25 parts by mass to 45 parts by mass.

[0032] (Pigments) The inkjet printing film of the present disclosure contains a pigment. The type of pigment is not particularly limited, and any conventionally known pigment can be used. The pigment may be used alone or in combination of two or more types. Examples of the pigment include white pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, etc., color pigments such as iron oxide, chromium oxide, carbon black, ultramarine, etc., and extender pigments such as kaolin, talc, mica, sericite, etc. The pigment preferably contains a color pigment because it is possible to color the inkjet printing film in a predetermined color, and more preferably a white pigment from the viewpoint of further improving the whiteness of the inkjet printing film, and even more preferably at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate. The pigment contained in the inkjet printing film may be in the form of a pigment dispersion in which the above-mentioned pigments are dispersed in a vehicle component. Examples of the vehicle component include resin components such as urethane resins and acrylic resins, and solvent components such as butyl acetate and N,N-dimethylformamide. By using such a pigment dispersion, the pigment can be uniformly dispersed in the inkjet printing film of the present disclosure without agglomeration.

[0033] When the vehicle component is a urethane-based resin or an acrylic-based resin, these resin components are classified as a "polyurethane-based resin" and a "(meth)acrylic resin" in the present disclosure, respectively. For example, when "NX-501 White" (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., pigment: 58% by mass, acrylic resin: 21% by mass, butyl acetate: 21% by mass) is used as the pigment dispersion, the pigment is classified as "pigment" in the present disclosure, and the acrylic resin is classified as "(meth)acrylic resin" in the present disclosure.

[0034] The content of the pigment relative to 100 parts by mass of the polyurethane resin is preferably 10 parts by mass to 70 parts by mass, more preferably 15 parts by mass to 65 parts by mass, further preferably 20 parts by mass to 60 parts by mass, and particularly preferably 20 parts by mass to 40 parts by mass. As described above, when a pigment dispersion is used, the above content means the content of only the pigment, excluding the vehicle component.

[0035] When a white pigment is used as the pigment, the content of the pigment relative to 100 parts by mass of the polyurethane resin is preferably 10 parts by mass to 70 parts by mass. When the content of the pigment relative to 100 parts by mass of the polyurethane resin is 10 parts by mass or more, good whiteness is obtained. When the content of the pigment relative to 100 parts by mass of the polyurethane resin is 70 parts by mass or less, a film having better low-temperature impact resistance and a smooth and good appearance is obtained. The content of the pigment relative to 100 parts by mass of the polyurethane resin is more preferably 15 parts by mass to 65 parts by mass, further preferably 20 parts by mass to 60 parts by mass, and particularly preferably 20 parts by mass to 40 parts by mass.

[0036] (Other Ingredients) The inkjet printing film of the present disclosure may contain other components, such as plasticizers, softeners, UV absorbers, light stabilizers, antifoaming agents, and antioxidants, as necessary. When the inkjet printing film of the present disclosure contains other components, the amount of the other components contained therein is not particularly limited, and may be appropriately set within a range that does not affect the effects of the inkjet printing film of the present disclosure.

[0037] (Method of manufacturing film for inkjet printing) The manufacturing method of the film for inkjet printing of the present disclosure is not particularly limited. The film for inkjet printing may be formed, for example, using a resin composition for forming a film for inkjet printing, which contains a polyurethane resin, a (meth)acrylic resin, and a pigment, and the content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is 15 parts by mass to 80 parts by mass. The resin composition for forming a film for inkjet printing may contain other components as necessary. Examples of methods for forming a film for inkjet printing using the resin composition for forming a film for inkjet printing include known methods using a single layer T-die extruder, a multi-layer T-die extruder, a calendar molding machine, and the like. Alternatively, a film for inkjet printing can be formed by applying an organic solvent-containing resin composition for forming a film for inkjet printing to one side of a release-treated temporary support such as a polyethylene terephthalate film, a polypropylene film, or paper, and drying the composition. Examples of such application methods include screen printing, gravure printing, bar coating, knife coating, roll coating, comma coating, blade coating, die coating, spray painting, and methods using an applicator.

[0038] When the resin composition for forming a film for inkjet printing contains an organic solvent, the type of organic solvent is not particularly limited, and is not particularly limited as long as it dissolves or disperses the various components contained in the resin composition for forming a film for inkjet printing. Examples of organic solvents include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane; alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane; aromatic hydrocarbon-based organic solvents such as toluene and xylene; and amide-based organic solvents such as N,N-dimethylformamide. The organic solvents may be used alone or in combination of two or more. The content of the organic solvent is appropriately set in consideration of the coating method of the resin composition for forming a film for ink-jet printing, drying conditions, types of components contained in the composition, and the like.

[0039] (Average thickness) The average thickness of the inkjet printing film of the present disclosure is appropriately set depending on the application. The average thickness of the inkjet printing film is, for example, preferably 20 μm to 120 μm, more preferably 25 μm to 110 μm, and even more preferably 30 μm to 105 μm.

[0040] <Laminated sheet> The laminate sheet of the present disclosure has the inkjet printing film of the present disclosure and a pressure-sensitive adhesive layer provided on one side of the inkjet printing film. Since the laminate sheet of the present disclosure has the inkjet printing film of the present disclosure, it has excellent inkjet printability and low-temperature impact resistance. The laminate sheet of the present disclosure may have layers other than the pressure-sensitive adhesive layer, such as an intermediate layer and a design layer.

[0041] (Adhesive layer) The adhesive layer constituting the laminated sheet is not particularly limited in terms of its components as long as it can be adhered to an adherend such as a resin plate, a metal plate, or a glass plate, and can be formed using a (meth)acrylic adhesive, a silicone adhesive, a synthetic rubber adhesive, or the like. The pressure-sensitive adhesive layer preferably contains a (meth)acrylic resin and an isocyanate-based crosslinking agent from the viewpoint of improving the adhesion and durability of the laminated sheet to the adherend. The pressure-sensitive adhesive layer preferably further contains a pigment from the viewpoint of improving the concealment of the adherend. The pressure-sensitive adhesive layer may contain other components as necessary.

[0042] -(Meth)acrylic resin- The (meth)acrylic resin contained in the pressure-sensitive adhesive layer is preferably an acrylic resin from the viewpoint of improving the adhesion and durability of the laminate sheet to an adherend. When an acrylic resin and a methacrylic resin are used in combination as the (meth)acrylic resin contained in the pressure-sensitive adhesive layer, the proportion of structural units derived from acrylic monomers in the entire methacrylic resin and acrylic resin is preferably 70 mass% or more, more preferably 75 mass% or more, and even more preferably 80 mass% or more.

[0043] In addition, the total ratio of structural units derived from monomers containing a carboxy group in the molecule, such as acrylic acid, methacrylic acid, and other monomers containing a carboxy group, to all structural units of the (meth)acrylic resin contained in the pressure-sensitive adhesive layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of improving the adhesion of the laminated sheet to an adherend and shrink resistance. The total ratio of structural units derived from monomers containing a carboxy group in the molecule to all structural units of the (meth)acrylic resin contained in the pressure-sensitive adhesive layer is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12.5% ​​by mass or less, from the viewpoint of obtaining a good coating appearance of the pressure-sensitive adhesive layer. The total proportion of structural units derived from monomers containing a carboxy group in the molecule in all structural units of the (meth)acrylic resin contained in the pressure-sensitive adhesive layer is preferably 0.1% by mass to 20% by mass.

[0044] The proportion of the (meth)acrylic resin in the solid content of the adhesive layer is not particularly limited, and from the viewpoint of improving the adhesion of the laminated sheet to the adherend, it is preferably 70% by mass to 95% by mass, more preferably 75% by mass to 92% by mass, and even more preferably 80% by mass to 90% by mass.

[0045] -Isocyanate-based crosslinking agent- The type of isocyanate crosslinking agent contained in the pressure-sensitive adhesive layer is not particularly limited, and any conventionally known isocyanate crosslinking agent can be used. The isocyanate crosslinking agent may be used alone or in combination of two or more types. In the present disclosure, the term "isocyanate-based crosslinking agent" refers to a compound having two or more isocyanate groups in one molecule (so-called polyisocyanate compound).

[0046] Examples of the isocyanate crosslinking agent include aromatic polyisocyanate compounds such as xylylene diisocyanate (XDI), diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate (TDI), and aliphatic polyisocyanate compounds or alicyclic polyisocyanate compounds such as hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate, and hydrogenated aromatic polyisocyanate compounds. Further, examples of the isocyanate-based crosslinking agent include dimers, trimers, and pentamers of the above polyisocyanate compounds, adducts of the above polyisocyanate compounds with polyol compounds such as trimethylolpropane, and biuret forms of the above polyisocyanate compounds. Among these, an aromatic polyisocyanate compound or an adduct of an aromatic polyisocyanate compound and a polyol compound such as trimethylolpropane is preferred.

[0047] As the isocyanate-based crosslinking agent, a commercially available product can be used. Examples of commercially available isocyanate crosslinking agents include "Coronate HX", "Coronate HL-S", "Coronate L", "Coronate L-45E", "Coronate 2031", "Coronate 2037", "Coronate 2234", "Coronate 2785", "Aquanate 200", and "Aquanate 210" (all manufactured by Tosoh Corporation), "Sumidur N3300", "Desmodur N3400", and "Sumidur N75" (all manufactured by Sumika Covestro Urethane Co., Ltd.), "Duranate E-405-80T", "Duranate AE700-100", "Duranate 24A-100", and "Duranate TSE-100" (all manufactured by Asahi Kasei Corporation), "Takenate D-110N", "Takenate D-120N", "Takenate Examples of such additives include "MT-Olestar NP1200," "STABIO D-370N," ​​and "STABIO XD-340N" (all manufactured by Mitsui Chemicals, Inc.), and "Rezamin X-100" (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

[0048] The content of the isocyanate-based crosslinking agent is preferably 1 to 10 parts by mass, more preferably 2 to 9 parts by mass, and even more preferably 3 to 8 parts by mass, per 100 parts by mass of the (meth)acrylic resin (100 parts by mass in total of the (meth)acrylic resins when two or more types of (meth)acrylic resins are used in combination).

[0049] -Pigments- The type of pigment contained in the adhesive layer is not particularly limited, and any conventionally known pigment can be used. The pigment may be used alone or in combination of two or more kinds. The pigment contained in the pressure-sensitive adhesive layer may be the same as or different from the pigment contained in the film for inkjet printing. From the viewpoint of improving the whiteness of the laminated sheet, the pigment contained in the adhesive layer is preferably a white pigment, and more preferably contains at least one pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate. The pigment contained in the pressure-sensitive adhesive layer may be in a state of being dispersed in a vehicle component such as an acrylic resin or a solvent.

[0050] The content of the pigment relative to 100 parts by mass of the (meth)acrylic resin is preferably from 2 to 15 parts by mass, more preferably from 4 to 12 parts by mass, and even more preferably from 6 to 10 parts by mass.

[0051] -Other ingredients- The pressure-sensitive adhesive layer may contain other components such as a plasticizer, a softener, a light stabilizer, a heat stabilizer, and a tackifier, if necessary. When the pressure-sensitive adhesive layer contains other components, the amount of each of the other components is not particularly limited and may be appropriately set within a range that does not affect the function of the pressure-sensitive adhesive layer.

[0052] -Average thickness- The average thickness of the pressure-sensitive adhesive layer is not particularly limited and is, for example, preferably from 10 μm to 70 μm, more preferably from 20 μm to 60 μm, and even more preferably from 30 μm to 50 μm.

[0053] (Middle class) The laminate sheet of the present disclosure may have an intermediate layer between the inkjet printing film and the adhesive layer from the viewpoint of imparting rigidity to improve the handleability of the sheet and from the viewpoint of suppressing migration of the inkjet ink solvent to the adhesive layer. From the viewpoints of further improving the low-temperature impact resistance of the laminate sheet and suppressing color unevenness, the intermediate layer preferably contains a polyurethane resin and a pigment. The intermediate layer may contain other components as necessary.

[0054] -Polyurethane resin- The polyurethane-based resin contained in the intermediate layer may be the same as the polyurethane-based resin contained in the inkjet printing film of the present disclosure. The intermediate layer may contain a resin other than the polyurethane-based resin. The proportion of polyurethane resin in the solid content of the intermediate layer is not particularly limited, but from the viewpoint of further improving the low-temperature impact resistance of the laminate sheet, it is preferably 60% by mass to 90% by mass, more preferably 65% ​​by mass to 88% by mass, and even more preferably 70% by mass to 85% by mass. When the intermediate layer contains a resin other than a polyurethane-based resin, the proportion of the polyurethane-based resin in the resin contained in the intermediate layer is preferably 60% by mass to 99% by mass, more preferably 75% by mass to 99% by mass, and even more preferably 90% by mass to 99% by mass, from the viewpoint of further improving the low-temperature impact resistance of the laminate sheet.

[0055] -Pigments- The type of pigment contained in the intermediate layer is not particularly limited, and any conventionally known pigment can be used. The pigment may be used alone or in combination of two or more kinds. The pigment contained in the intermediate layer may be the same as or different from the pigment contained in the inkjet printing film. The pigment contained in the intermediate layer is preferably a white pigment from the viewpoint of improving the whiteness of the laminate sheet, and more preferably at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate.

[0056] The pigment contained in the intermediate layer may be in the form of a pigment dispersion liquid, dispersed in a vehicle component such as an acrylic resin or a solvent, similar to that used in films for inkjet printing. The content of the pigment relative to 100 parts by mass of the polyurethane resin contained in the intermediate layer is preferably 10 parts by mass to 50 parts by mass, more preferably 15 parts by mass to 45 parts by mass, and even more preferably 20 parts by mass to 40 parts by mass. Note that when a pigment dispersion is used, the above content means the content of only the pigment, excluding the vehicle component.

[0057] -Other ingredients- The intermediate layer may contain other components such as a plasticizer, a softener, an ultraviolet absorber, a light stabilizer, an antioxidant, and an antifoaming agent, if necessary. When the intermediate layer contains other components, the amount of the other components is not particularly limited and may be appropriately set within a range that does not affect the function of the intermediate layer.

[0058] -Average thickness- The average thickness of the intermediate layer is not particularly limited and is, for example, preferably from 10 μm to 40 μm, more preferably from 15 μm to 35 μm, and further preferably from 20 μm to 30 μm. When the laminate sheet has an intermediate layer, the sum of the average thickness of the inkjet printing film and the average thickness of the intermediate layer is preferably 30 μm to 120 μm, more preferably 35 μm to 110 μm, and even more preferably 40 μm to 105 μm.

[0059] (Design layer) The laminate sheet of the present disclosure may have a design layer. The design layer is formed on the surface of the inkjet printing film constituting the laminate sheet opposite to the side on which the adhesive layer is provided. The design layer may be formed on at least a part of the inkjet printing film when the inkjet printing film is viewed in plan. In this case, the design layer is a layer provided to impart design to the decorative sheet described below, and is a layer that expresses a pattern, picture, etc. The design layer is formed by known inkjet printing.

[0060] Fig. 1 is a cross-sectional view of a first embodiment of a laminate sheet of the present disclosure. The laminate sheet 10 of Fig. 1 has an inkjet printing film 20 of the present disclosure and an adhesive layer 30 provided on one side of the inkjet printing film 20. A design layer 40 is provided on the side of the inkjet printing film 20 opposite to the side on which the adhesive layer 30 is provided. Fig. 2 is a cross-sectional view of a second embodiment of the laminate sheet of the present disclosure. The laminate sheet 50 of Fig. 2 has an intermediate layer 60 between the inkjet printing film 20 of the present disclosure and the pressure-sensitive adhesive layer 30. A design layer 40 is provided on the surface of the inkjet printing film 20 opposite to the surface on which the intermediate layer 60 is provided. The details of the inkjet printing film 20, the adhesive layer 30, the design layer 40 and the intermediate layer 60 are as described above.

[0061] <Decorative sheet> The decorative sheet of the present disclosure comprises the laminate sheet of the present disclosure and a surface protective layer disposed on the side of the inkjet printing film constituting the laminate sheet opposite to the side on which the adhesive layer is provided. By providing the surface protective layer in the decorative sheet, the printed surface of the inkjet printing film (the surface on which the design layer is formed) can be protected from external impact. The decorative sheet may have layers other than the surface protective layer as necessary, such as a pressure-sensitive adhesive layer for laminating the surface protective layer on the laminate sheet, and an easy-adhesion layer provided between the surface protective layer and the pressure-sensitive adhesive layer.

[0062] (Surface protective layer) The material of the surface protective layer is not particularly limited. Examples of the surface protective layer include layers made of films containing resins such as polyolefin resins (e.g., polyethylene (PE) and polypropylene (PP)), polyester resins (e.g., polyethylene terephthalate (PET)), acetate resins (e.g., triacetyl cellulose), polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyurethane resins, (meth)acrylic resins, vinyl chloride resins, ABS (Acrylonitrile Butadiene Styrene) resins, and fluorine-based resins. From the viewpoint of further improving the low-temperature impact resistance of the decorative sheet, the surface protective layer preferably contains a polyurethane resin. The surface protective layer may contain various additives such as a crosslinking agent, a crosslinking catalyst, a plasticizer, a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, an antioxidant, a filler, an antifoaming agent, and a surfactant.

[0063] -Average thickness- The average thickness of the surface protective layer is not particularly limited and is, for example, preferably from 20 μm to 100 μm, more preferably from 20 μm to 90 μm, and further preferably from 30 μm to 70 μm.

[0064] The decorative sheet of the present disclosure can be used as a constituent member of the license plate of the present disclosure described below. In addition to license plates, the decorative sheet of the present disclosure can be used for the interior or exterior of vehicles such as automobiles, and for interior use in buildings such as walls, floors, and ceilings.

[0065] Fig. 3 is a cross-sectional view of one embodiment of the decorative sheet of the present disclosure. Hereinafter, in the decorative sheet of the present disclosure, the "adhesive layer" constituting the laminate sheet is also referred to as the "first adhesive layer". The decorative sheet 70 of Fig. 3 has the laminate sheet 10 of the present disclosure having the inkjet printing film 20 and the first adhesive layer 30 in this order, and a surface protection layer 80 arranged on the side of the inkjet printing film 20 constituting the laminate sheet 10 opposite to the side on which the first adhesive layer 30 is provided. Between the film for inkjet printing 20 and the surface protective layer 80 , a second adhesive layer 90 is disposed, which adheres the surface protective layer 80 onto the surface of the film for inkjet printing 20 . A design layer 40 is provided on the surface of the inkjet printing film 20 opposite to the surface on which the first pressure-sensitive adhesive layer 30 is provided. The first pressure-sensitive adhesive layer 30 and the second pressure-sensitive adhesive layer 90 may have the same configuration or may have different configurations. The details of the inkjet printing film 20, the first adhesive layer 30, the second adhesive layer 90, the design layer 40 and the surface protection layer 80 are as described above. By providing the surface protective layer 80 on the design layer 40, the durability of the design layer 40 is improved.

[0066] <License plate> The license plate of the present disclosure comprises a plate substrate and a decorative sheet of the present disclosure provided on one side of the plate substrate. The configuration of the license plate of the present disclosure may be, for example, a configuration in which an adhesive layer of the decorative sheet of the present disclosure is adhered to one side of a plate substrate, and a design layer (e.g., license plate characters) may be provided on the side of the surface protection layer constituting the decorative sheet opposite the side on which the laminate sheet is arranged. The method for forming the design layer on the surface of the surface protection layer opposite to the side on which the adhesive layer is provided is not particularly limited, and the design layer can be formed by a known printing method such as inkjet printing, screen printing, gravure printing, hot stamp printing, letterpress printing, etc. In particular, when forming the characters on the license plate, it is preferable to form the characters by printing a heat-curable ink by a known printing method and then baking the ink (so-called baked coating).

[0067] 4 is a cross-sectional view of one embodiment of the license plate of the present disclosure. Hereinafter, in the license plate of the present disclosure, the "adhesive layer" constituting the laminate sheet is also referred to as the "first adhesive layer." 4 has, in this order, a plate substrate 110, a first adhesive layer 30, an inkjet printing film 20, a second adhesive layer 90, and a surface protective layer 80. The inkjet printing film 20 and the first adhesive layer 30 constitute a laminate sheet 10 of the present disclosure. The laminate sheet 10, the second adhesive layer 90, and the surface protective layer 80 constitute a decorative sheet 70 of the present disclosure. In the license plate 100, a second design layer 120 is provided on the surface protective layer 80. In addition, a design layer 40 is provided on the surface of the inkjet printing film 20 opposite to the surface on which the first adhesive layer 30 is provided. The details of the plate substrate 110 will be described later. The details of the laminate sheet 10, the decorative sheet 70, and the second design layer 120 are as described above.

[0068] As the plate substrate, a metal plate or a resin plate can be used. Examples of the metal plate include an aluminum plate, a stainless steel plate, and an iron plate. Examples of the resin plate include a polycarbonate plate, a polyester plate, a polyvinyl chloride plate, an acrylic plate, an ABS plate, and a PP plate. If necessary, these plate materials may be molded into a shape such as a frame. EXAMPLES

[0069] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

[0070] <Preparation of Resin Composition for Forming Film for Inkjet Printing> A resin composition for forming a film for inkjet printing was prepared by stirring and mixing the polyurethane resin, (meth)acrylic resin, and pigment dispersion with a 1:1 (by mass) mixed solvent of isopropanol and toluene as a dilution solvent using a disper at 23° C. for 10 minutes. The blending amounts of the polyurethane resin, (meth)acrylic resin, and pigment dispersion calculated as solid content are as shown in Table 1. The dilution solvent was added so that the proportion of solids in the resin composition for forming a film for inkjet printing was 23 mass %. The contents of "acrylic resin" and "pigment" derived from the pigment dispersion in the resin composition for forming a film for inkjet printing are also shown separately in Table 1. Additionally, the total amount of the (meth)acrylic resin in the resin composition for forming a film for inkjet printing and the acrylic resin derived from the pigment dispersion is shown in the "Total (meth)acrylic resin" column in Table 1.

[0071] <Preparation of film for inkjet printing> [Examples 1-12, Comparative Examples 1-2] Next, the resin composition for forming a film for inkjet printing was applied using an applicator to a polyethylene terephthalate film (manufactured by Lintec Corporation, thickness: 75 μm, product name P756050) that had been subjected to a release treatment so that the average thickness after drying would be as shown in Table 1, and the film was heated and dried in an atmosphere of 100°C for 3 minutes and in an atmosphere of 160°C for 3 minutes to obtain films for inkjet printing of Examples 1-12 and Comparative Example 1-2. In Table 1, the details of each component contained in the resin composition for forming a film for inkjet printing are as follows. NE-8836: "Rezamin NE-8836" [manufactured by Dainichi Seika Chemicals Co., Ltd., one-component non-yellowing polycarbonate-based urethane resin], elongation at 23°C: 166% GL, yield point at 23°C: 8.7N, Young's modulus at 23°C: 431.7MPa NE-8811: "Rezamin NE-8811" [manufactured by Dainichi Seikagaku Kogyo Co., Ltd., one-component non-yellowing polycarbonate-based urethane resin], elongation at 23°C: 278% GL, yield point at 23°C: 1.7N, Young's modulus at 23°C: 65.0MPa NE-8850: "Rezamin NE-8850" [manufactured by Dainichi Seikagaku Kogyo Co., Ltd., one-component non-yellowing polycarbonate-based urethane resin], elongation at 23°C: 172% GL, yield point at 23°C: 1.0 N, Young's modulus at 23°C: 24.3 MPa ·MB-2593: "Dianal MB-2593" [Mitsubishi Chemical Corporation, methacrylic resin, solvent-free (powder)] GR-F: "Parapet GR-F" [Kuraray Co., Ltd., methacrylic resin, solvent-free type (powder, core-shell type)] NX-501: "NX-501 White" [manufactured by Dainichiseika Chemicals Mfg. Co., Ltd., titanium oxide dispersion (pigment: 58% by mass, acrylic resin: 21% by mass, butyl acetate: 21% by mass (solid content 79% by mass)]

[0072] Comparative Example 3 29.5 parts by mass of ethyl acrylate, 62.5 parts by mass of methyl methacrylate, 7.0 parts by mass of 2-hydroxyethyl methacrylate, and 1.0 parts by mass of acrylic acid were polymerized by a standard method to obtain 62.5 parts by mass of acrylic copolymer A, 65.0 parts by mass of ethyl acrylate, 20 parts by mass of methyl methacrylate, 14.0 parts by mass of 2-hydroxyethyl methacrylate, and 1.0 parts by mass of acrylic acid were polymerized by a standard method to obtain 37.5 parts by mass of acrylic copolymer B, 24.6 parts by mass of NX-501, and ethyl acetate as a dilution solvent were stirred and mixed at 23 ° C. for 10 minutes using a disper, and the mixture was applied to a peel-treated polyethylene terephthalate film so that the average thickness after drying was 55 μm, and the mixture was heated and dried in a 100 ° C. atmosphere for 1 minute to obtain an inkjet printing film (acrylic film) of Comparative Example 3.

[0073] Comparative Example 4 As a film for inkjet printing of Comparative Example 4, a vinyl chloride film (00W5M [manufactured by Nippon Carbide Industries Co., Ltd.] was prepared.

[0074] The elongation, yield point and Young's modulus at 23° C. for each polyurethane resin (NE-8836, NE-8811 and NE-8850) were measured as follows. The polyurethane resin and N,N-dimethylformamide as a dilution solvent were mixed and stirred for 10 minutes at 23°C using a disper, and the resulting solution was applied to an untreated polyethylene terephthalate film using an applicator to an average thickness of 35 μm, and the film was formed by heating and drying for 3 minutes at 80°C and then for 3 minutes at 140°C. The dilution solvent was blended so that the solid content in the solution was 23% by mass. The film thus obtained was cut into a length of 150 mm and a width of 10 mm, and a tensile test was carried out using a tensile tester (manufactured by A&D Co., Ltd., product name RTG-1310) at a gripping distance of 100 mm and a tensile speed of 300 mm / min to determine the elongation, yield point, and Young's modulus. The measurement temperature was 23°C.

[0075] <Preparation of laminated sheet> A mixture of 100 parts by mass of an acrylic copolymer obtained by polymerizing 90 parts by mass of butyl acrylate and 10.0 parts by mass of acrylic acid by a standard method, 8.34 parts by mass of white pigment DAD-100 [manufactured by DIC Corporation, titanium oxide pigment] (pigment: 75% by mass, resin: 25% by mass), 5.0 parts by mass of an isocyanate-based crosslinking agent Coronate L-45E [manufactured by Mitsubishi Gas Chemical Co., Ltd.], and ethyl acetate was applied to a peel-treated polyethylene terephthalate film [manufactured by Lintec Corporation, thickness: 75 μm, PET75GS (product name)] so that the thickness after drying was 40 μm, and the adhesive layer was obtained by heating and drying for 1 minute in a 100 ° C. atmosphere. The obtained adhesive layer was attached to one side of the inkjet printing film produced or prepared as described above to produce an evaluation sheet (laminate sheet).

[0076] The laminate sheet of Example 10 was separately produced as follows. The polyurethane resin and the pigment dispersion were mixed with a 1:1 (by weight) mixed solvent of isopropanol and toluene as a dilution solvent by stirring for 10 minutes at 23° C. using a disper to prepare a resin composition for forming an intermediate layer. The blending amounts of the polyurethane resin and the pigment dispersion calculated as solid content are as shown in Table 1. The dilution solvent was added so that the proportion of solids in the intermediate layer-forming resin composition was 25% by mass. Next, the obtained intermediate layer-forming resin composition was applied to one side of the inkjet printing film of Example 10 using an applicator so that the average thickness after drying would be as shown in Table 1, and heat drying was performed in a 100°C atmosphere for 3 minutes and in a 160°C atmosphere for 3 minutes to obtain a laminate having an intermediate layer on one side of the inkjet printing film. An adhesive layer was attached to the side of this laminate on which the intermediate layer was provided as described above to produce an evaluation sheet (laminate sheet) of Example 10.

[0077] [Low temperature impact resistance evaluation] The release-treated polyethylene terephthalate film was removed from the evaluation sheet, and the sheet was attached to an aluminum plate in an environment of 23° C. and 50% RH, and then treated at 120° C. for 1 hour to prepare a test piece. The prepared test pieces were subjected to an evaluation test for impact resistance in a low-temperature chamber (product name: constant temperature and humidity chamber, built-in chamber E series, manufactured by Espec Corp.) with the ambient temperature set to -30°C. Specifically, in the low-temperature chamber, the test pieces were subjected to an impact test under the following conditions using a DuPont impact tester (product name: DuPont impact tester, manufactured by TP Giken Corp.) in accordance with the method of JIS K 5600-5-3:1999. The obtained results are shown in Table 2. Weight: 500g Die tip radius: 6.35mm The evaluation criteria were as follows: "A" and "B" are practically acceptable levels, with "A" being the most preferable. A: The film does not crack when tested from a drop height of 100 cm. B: The film does not crack when tested from a drop height of 50 cm, but cracks occur when tested from a drop height of 100 cm. C: The film cracks when tested from a drop height of 50 cm.

[0078] [Inkjet printability evaluation] Using an inkjet printer JV-300 (manufactured by MIMAKI), a 100% M (magenta) solid print was printed in a size of 150 mm x 150 mm on the side of the evaluation sheet where the inkjet printing film was provided, and the appearance of the printed area was visually evaluated. The evaluation criteria for printability are as follows. The obtained results are shown in Table 2. "A" and "B" are practical levels, with "A" being the most preferable. A: There are no uneven shades and it looks uniform. B: Slight unevenness in shading is visible C: Print bleeding and uneven shading are clearly visible

[0079] [Whiteness rating] The release-treated polyethylene terephthalate film was removed from the evaluation sheet, and the sheet was attached to an aluminum plate in an environment of 23° C. and 50% RH, and then treated at 120° C. for 1 hour to prepare a test piece. Using a colorimeter (manufactured by Konica Minolta, Inc., product name: CM-3600A), the L value of the SCE (Specular Component Exclude) method was measured in accordance with geometric condition C of JIS Z 8722:2009, and the whiteness was evaluated. The evaluation criteria are as shown below. The obtained results are shown in Table 2. "A" and "B" are practically acceptable levels, with "A" being the most preferable. A:L value > 90 B: 85≦L value≦90 C:L value < 85

[0080] [Table 1]

[0081] [Table 2]

[0082] The film used in Comparative Example 1, in which the content of the (meth)acrylic resin was less than 15 parts by mass per 100 parts by mass of the polyurethane resin, was poor in inkjet printability. The film used as Comparative Example 2, in which the content of the (meth)acrylic resin exceeded 80 parts by mass per 100 parts by mass of the polyurethane resin, was poor in low-temperature impact resistance. The acrylic film containing no polyurethane resin used in Comparative Example 3 was poor in low-temperature impact resistance. The vinyl chloride film used in Comparative Example 4 was poor in low-temperature impact resistance. On the other hand, the films of the Examples were superior in ink jet printability and low-temperature impact resistance to the films of the Comparative Examples, and were capable of achieving both of these properties. Among the films of the Examples, the films of Examples 10 and 12 were excellent in inkjet printability and low-temperature impact resistance, and also in whiteness. In particular, the film of Example 10 having an intermediate layer (average total thickness of the inkjet printing film and intermediate layer: 55 μm) exhibited higher whiteness than the film of Example 12 not having an intermediate layer (average thickness: 105 μm) despite its thinner average thickness. [Explanation of symbols]

[0083] 10, 50 laminated sheet 20 Inkjet printing film 30 Adhesive layer (first adhesive layer) 40, 120 Design layer 60 Middle Class 70 Decorative Sheet 80 Surface protective layer 90 Second adhesive layer 100 Number Plate 110 Plate substrate

Claims

1. The ink contains a polyurethane resin, a (meth)acrylic resin, and a pigment, The content of the (meth)acrylic resin relative to 100 parts by mass of the polyurethane resin is 15 parts by mass to 80 parts by mass.

2. 2. The film for ink-jet printing according to claim 1, wherein the pigment is at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate.

3. 3. The film for inkjet printing according to claim 2, wherein the content of the pigment is 10 parts by mass to 70 parts by mass based on 100 parts by mass of the polyurethane resin.

4. 4. A laminated sheet comprising the film for inkjet printing according to claim 1 and a pressure-sensitive adhesive layer provided on one surface of the film for inkjet printing.

5. The laminate sheet according to claim 4 , further comprising an intermediate layer between the inkjet printing film and the pressure-sensitive adhesive layer.

6. The laminate sheet according to claim 5 , wherein the intermediate layer contains a polyurethane resin and a pigment.

7. 7. The laminate sheet according to claim 6, wherein the pigment contained in the intermediate layer is at least one kind of white pigment selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, and barium sulfate.

8. A decorative sheet comprising the laminate sheet according to claim 4 and a surface protective layer disposed on a surface of the inkjet printing film constituting the laminate sheet opposite to the surface on which the pressure-sensitive adhesive layer is provided.

9. A license plate comprising a plate substrate and the decorative sheet according to claim 8 provided on one surface side of the plate substrate.

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