Press-through pack material and press-through pack using the same

Abstract

To provide a press-through pack material to which an anticounterfeit mark is given without depending on a post-fitted hologram seal with possibility of peeling and imitation production; and to provide a press-through pack using the same.SOLUTION: A press-through pack material comprises, laminated on each other in order: a substrate; an opaque underlayer laminated on at least part of a surface of the substrate; and a printing layer containing a coloring metallic pigment formed on at least part of a surface of the opaque underlayer. The coloring metallic pigment contains: a metallic pigment; an amorphous silicon oxide film layer formed on a surface of the metallic pigment; and a plurality of metal particles carried on part or all of a surface of the amorphous silicon oxide film layer. The opaque underlayer has a unit area mass of 0.5 g / m2 or more and 3.0 g / m2 or less, and the printing layer has a unit area mass of 1.0 g / m2 or more and 3.5 g / m2 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a press-through pack material and a press-through pack using the same, and more particularly to a press-through pack material having an anti-counterfeit mark and a press-through pack using the same. [Background technology]

[0002] Press-through packs (also known as PTPs, blister packs, etc.) are commonly used as packaging for individually storing medicines such as tablets. A press-through pack consists of a container that stores the medicine and a lid that covers it, and the medicine is removed by pressing the medicine from the container side to break through the lid.

[0003] In recent years, there has been concern about the distribution of counterfeit medicines, particularly for expensive medicines and medicines that are distributed in large quantities, but because it is difficult to distinguish between genuine and counterfeit medicines from their appearance, press-through packs are equipped with anti-counterfeiting labels, etc. For example, Patent Document 1 discloses a press-through pack in which a hologram seal is attached to the lid of the press-through pack, making it possible to distinguish between genuine and counterfeit medicines. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-212811 Summary of the Invention [Problem to be solved by the invention]

[0005] However, with the technology of Patent Document 1, there are cases where the hologram seal is peeled off and used to package counterfeit medicines, or where users are not fully aware of the real hologram seal and so imitation hologram seals are used to package counterfeit medicines, making it difficult to reliably prevent the distribution of counterfeit medicines.

[0006] Therefore, an object of the present invention is to provide a press-through pack material with an anti-counterfeit mark and a press-through pack using the same, without relying on a post-installed hologram seal that is susceptible to peeling and counterfeiting. [Means for solving the problem]

[0007] As a result of extensive research to achieve the above-mentioned objective, the inventors discovered that the above-mentioned objective can be achieved by using a press-through pack material having a printed layer containing a specific colored metallic pigment, and thus completed the present invention.

[0008] That is, the present invention relates to the following press-through pack material and press-through pack using the same. 1. A substrate, an opaque underlayer laminated on at least a portion of the surface of the substrate, and a printed layer containing a colored metallic pigment formed on at least a portion of the surface of the opaque underlayer are laminated in this order; The color metallic pigment comprises a metallic pigment, an amorphous silicon oxide film layer formed on the surface of the metallic pigment, and a plurality of metal particles supported on a part or the entire surface of the amorphous silicon oxide film layer, The mass per unit area of ​​the opaque underlayer is 0.5 g / m 2 More than 3.0g / m 2 is as follows: The mass per unit area of ​​the printing layer is 1.0 g / m 2 More than 3.5g / m 2 Below is the A press-through pack material characterized by: 2. The press-through pack material according to item 1, wherein the metal particles contain at least one element selected from the group consisting of Cu, Ni, and Ag. 3. The press-through pack material according to item 1 or 2 above, wherein the amorphous silicon oxide film layer has a thickness of 10 nm or more and 1000 nm or less. 4. The press-through pack material according to any one of items 1 to 3 above, wherein the metal particles have an average particle size of 50 nm or less. 5. A press-through pack using the press-through pack material according to any one of items 1 to 4 above as a container and / or a lid for a medicine. [Effects of the Invention]

[0009] The press-through pack material of the present invention cannot be peeled off because the printed layer containing a specific colored metal pigment as an anti-counterfeiting mark is formed by printing, and the color of the printed layer changes significantly (color shift) depending on the viewing angle, so it is a greater deterrent to the distribution of counterfeit drugs than conventional hologram stickers that are added after the fact. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram showing an example of a printed layer in the press-through pack of the present invention. [Figure 2] 1 is a cross-sectional view showing an example of a colored metallic pigment used in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The press-through pack material of the present invention and the press-through pack using the same will be described in detail below. In the following description, the range "A to B" means the range "A or more and B or less" unless otherwise specified.

[0012] The press-through pack material of the present invention comprises a substrate, an opaque underlayer laminated on at least a portion of the surface of the substrate, and a printed layer containing a colored metallic pigment formed on at least a portion of the surface of the opaque underlayer, laminated in this order; The color metallic pigment comprises a metallic pigment, an amorphous silicon oxide film layer formed on the surface of the metallic pigment, and a plurality of metal particles supported on a part or the entire surface of the amorphous silicon oxide film layer, The mass per unit area of ​​the opaque underlayer is 0.5 g / m 2 More than 3.0g / m 2 is as follows: The mass per unit area of ​​the printing layer is 1.0 g / m 2 More than 3.5g / m2 Below is the It is characterized by:

[0013] The press-through pack material of the present invention, which has the above-mentioned characteristics, cannot be peeled off because the printed layer containing a specific colored metal pigment as an anti-counterfeiting mark is formed by printing, and the color of the printed layer changes significantly (color shift) depending on the viewing angle, so it is a greater deterrent to the distribution of counterfeit drugs than conventional hologram stickers that are added after the fact.

[0014] (Press-through pack material) The press-through packing material in the present invention refers to a lid material and / or a storage container that constitutes a press-through pack. When the press-through packing material is a lid material, the substrate described below constitutes the lid material, and it is preferable that the opaque base layer and the printed layer described below are provided on the surface of the substrate opposite to the surface that is bonded to the storage container. When the press-through packing material is a storage container, it is preferable that the substrate described below constitutes the storage container, and it is preferable that the opaque base layer and the printed layer described below are provided on the surface of the substrate opposite to the surface that is bonded to the lid material.

[0015] That is, the authenticity of the press-through pack can be visually confirmed by forming an opaque base layer and a printed layer on the outermost layer side of the press-through pack containing a drug (one and / or the other outer side when the contained drug is positioned on the inside). In particular, when the opaque base layer and the printed layer are formed on the storage container side, it is preferable not to provide an opaque base layer and a printed layer on the pocket containing the drug, but to provide an opaque base layer and a printed layer on the flange portion around it.

[0016] (base material) In the present invention, the substrate is a material that serves as the base of the press-through pack material.

[0017] The substrate used in the present invention can be a material used in known press-through pack lid materials and / or press-through pack containers. For example, metal foils such as aluminum foil, copper foil, gold foil, and silver foil; papers such as paper and synthetic paper; and resin films such as nylon, polyester film, and polyolefin film can be used alone or in combination of two or more types. Furthermore, colored resin films can also be used as the resin film. Furthermore, commercially available metal foils or resin films with various colored layers, thermal adhesive layers, etc., pre-laminated can also be used as the substrate.

[0018] In addition, in the present invention, a sheet or film containing a metal vapor deposition layer such as an aluminum vapor deposition layer can also be used as the substrate. For example, a laminated film in which a metal vapor deposition layer is formed on the surface of a resin film or the like by a known vapor deposition method (PVD, CVD, etc.) can be used as the substrate. Examples of resin films include polyamide (nylon), polyethylene (especially high-density polyethylene), polypropylene (especially oriented polypropylene), vinyl chloride, ethylene-vinyl alcohol copolymer, polyethylene naphthalate, polyethylene terephthalate, etc.

[0019] The thickness of the metal vapor deposition layer is not limited, but is usually preferably about 200 to 1000 Å. The thickness of the resin film on which metal is vapor deposited is preferably about 9 to 50 μm.

[0020] In the present invention, it is particularly preferable to use aluminum foil as the substrate, as the use of aluminum foil can effectively exhibit the strength, barrier properties, storage stability, etc. required for a packaging material.

[0021] The aluminum foil may be any known or commercially available aluminum foil (including aluminum alloy foil; the same applies hereinafter). The quality of the aluminum foil is not limited, and any of soft foil, hard foil, and semi-hard foil may be used depending on the application or required properties.

[0022] In the present invention, specific examples of aluminum foil include pure aluminum (JIS (AA) 1000 series, for example, 1N30, 1070, 1100, etc.), Al-Mn series (JIS (AA) 3000 series, for example, 3003, 3004, etc.), Al-Mg series (JIS (AA) 5000 series), and Al-Fe series (JIS (AA) 8000 series, for example, 8021, 8079, etc.). Among these, aluminum foils having materials (compositions) such as 1N30, 1070, 1100, 3003, 8021, 8079, etc., as specified by JIS, etc., can be preferably used.

[0023] Furthermore, the aluminum foil may be subjected to shaping, degreasing, cleaning, anchor coating, overcoating, surface treatment, etc., by known methods, if necessary.

[0024] The thickness of the aluminum foil is not particularly limited, but is usually 5 to 200 μm, and preferably 12 to 50 μm. By setting the thickness within this range, better water resistance (moisture resistance), strength, and handleability of the press-through pack can be obtained.

[0025] (opaque base layer) An opaque underlayer is laminated on at least a portion of the surface of the substrate.

[0026] In the present invention, the opaque underlayer is a layer laminated on a substrate, which is a layer that is difficult for visible light to transmit and makes the substrate difficult to visually recognize. It also serves as a layer that serves as a base for a printed layer (described later) and supports the printed layer. The opaque underlayer may be laminated directly on the substrate, or may be laminated with another layer (such as a base layer for facilitating the formation of the opaque underlayer) between the substrate and the opaque underlayer.

[0027] The opaque base layer may have any color as long as it is opaque, but is preferably a white-colored layer or a black (ink)-colored layer. By using a white-colored or black-colored opaque base layer, it becomes easier to visually recognize the color shift caused by the printed layer, as described below.

[0028] The opaque primer layer has a solid mass per unit area of ​​the substrate (also called "unit area mass") of 0.5 g / m 2 More than 3.0g / m 2 The following range (preferably 0.5 g / m 2 More than 2.0g / m 2 The thickness of the printed layer is in the range below. By using this range, the visibility of the color shift caused by the printed layer is improved, as will be described later.

[0029] The white colored layer used as an opaque base layer is also called a solid white layer, and is white due to the use of a pigment such as titanium oxide. The pigment used in the white colored layer can be, for example, a white pigment such as titanium oxide or zinc oxide, but it is particularly preferable to use titanium oxide as the white pigment from the viewpoint of its superiority in terms of the light reflectance of the coating film.

[0030] In addition, in the present invention, colorants other than white pigments can be used in combination within a range that does not impair the effects of the present invention (especially within a range that exhibits a white-like color). Examples of such colorants include phthalocyanine blue, phthalocyanine green, quinacridone-based, quinophthalene-based, perylene-based, dioxazine-based, isoindolinone-based, iron oxide, mica, and color chip pigments thereof. These pigments can also be laminated separately as a single solid colored layer.

[0031] The white colored layer may contain a matrix resin (resin component), that is, the white colored layer preferably has a structure in which a white pigment is dispersed in a matrix resin.

[0032] Therefore, a transparent resin can be preferably used as the matrix resin of the white colored layer to fully utilize the effect of the white pigment. Such a resin is not particularly limited, but at least one of vinyl chloride-vinyl acetate copolymer resin, nitrocellulose-based resin, and polypropylene-based resin can be preferably used in the present invention. In particular, in the present invention, it is preferable to use a vinyl chloride-vinyl acetate copolymer resin as the matrix resin in terms of coating film performance, etc.

[0033] The content of the white pigment (particularly titanium oxide) in the white colored layer can be set depending on, for example, the type of white pigment used. In particular, when the white pigment is dispersed in the matrix resin, the content of the white pigment is usually about 20 to 60 mass %, and particularly preferably 25 to 55 mass %.

[0034] The white colored layer can be formed, for example, by a method including the steps of applying a coating liquid containing a white pigment and drying it.

[0035] The coating liquid can be prepared by a method of mixing a white pigment with a solvent, or by a method of mixing a white pigment, a solvent, and a resin component.

[0036] Examples of the solvent include organic solvents such as aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbon solvents such as methylcyclohexane and cyclohexane, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and acetone, and alcohol solvents such as isopropyl alcohol and denatured ethanol, etc. These can be used alone or in combination of two or more.

[0037] The resin component used may be a resin component that serves as a matrix resin. Therefore, in the present invention, at least one of vinyl chloride-vinyl acetate copolymer resin, nitrocellulose-based resin, and polypropylene-based resin can be suitably used. Other resins that can be used include, for example, polyvinyl butyral resin, phenol-based resin, maleic acid resin, alkyd resin, chlorinated polypropylene resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, and modified olefin-based resin, as long as they do not impair the effects of the present invention. These can be used alone or in combination of two or more. Furthermore, in the present invention, organic binder components contained in known or commercially available inks can also be used.

[0038] The coating liquid may also contain additives such as dispersants, surfactants, leveling agents, surface conditioners, anti-sagging agents, thickeners, antifoaming agents, and lubricants, as long as the effects of the present invention are not impaired.

[0039] The amount of the white pigment dispersed in the coating liquid may be appropriately set so that the content of the white pigment in the formed white colored layer falls within a predetermined range. That is, when the solid content is the white pigment and a resin component, the amount of the white pigment dispersed may be set while adjusting the ratio of the resin component.

[0040] In the present invention, the coating liquid can be prepared by uniformly mixing these components. A known or commercially available kneader, mixer, or the like can be used for mixing. When a resin component is used, the resin component may be dissolved or dispersed in an organic solvent.

[0041] The method for applying the coating liquid is not particularly limited, and the coating (lamination) can be performed by, for example, a gravure roll coater, offset printing, flexographic printing, UV printing, curtain flow coater, etc. Application by spraying or the like can also be performed.

[0042] After coating, the coating film is dried to obtain a white colored layer. The drying method may be either natural drying or heat drying. When heating, the temperature may be, for example, about 50 to 160°C. In addition, in the present invention, during coating, the above coating and drying may be repeated two or more times to obtain a predetermined thickness.

[0043] The black (ink) colored layer is colored black by a pigment such as carbon black. The pigment used in the black colored layer may be, for example, a black pigment such as carbon black or perylene black, but it is particularly preferable to use carbon black as the black pigment from the viewpoint of superior light reflectance of the coating film.

[0044] In the present invention, colorants other than black pigments can also be used in combination within a range that does not impair the effects of the present invention (especially within a range that provides a black-like color). Examples of such colorants include phthalocyanine blue, phthalocyanine green, quinacridones, quinophthalenes, perylenes, dioxazines, isoindolinones, iron oxides, mica, and color chip pigments thereof. These pigments can also be separately laminated as a single solid color layer.

[0045] The black colored layer may contain a matrix resin (resin component), that is, the black colored layer preferably has a structure in which a black pigment is dispersed in a matrix resin.

[0046] Therefore, a transparent resin can be preferably used as the matrix resin of the black colored layer to fully utilize the effect of the black pigment. Such a resin is not particularly limited, but at least one of vinyl chloride-vinyl acetate copolymer resin, nitrocellulose-based resin, and polypropylene-based resin can be preferably used in the present invention. In particular, in the present invention, it is preferable to use a vinyl chloride-vinyl acetate copolymer resin as the matrix resin in terms of coating film performance, etc.

[0047] The content of black pigment (particularly carbon black) in the black colored layer can be set depending on, for example, the type of black pigment used. In particular, when the black pigment is dispersed in the matrix resin, the content of the black pigment is usually about 10 to 70 mass %, and particularly preferably 15 to 65 mass %. The black colored layer can be formed by the same method as for the white colored layer.

[0048] Furthermore, when an opaque base layer is provided on a press-through pack lid material, it is usually provided on the surface opposite to the surface sealed to the storage container, but it may be provided on both sides of the base material. For example, when a transparent material is used for the storage container, if an opaque base layer is also provided on the surface of the press-through pack lid material that contacts the press-through pack storage container, the opaque base layer will be visible from the press-through pack container side. This also improves the visibility of a character pattern layer formed on the opaque base layer.

[0049] It is also possible to use a colorant other than a white pigment, a black pigment, etc. Examples of such a colorant include phthalocyanine blue, phthalocyanine green, quinacridone-based, quinophthalene-based, perylene-based, dioxazine-based, isoindolinone-based, iron oxide, mica, and color chip pigments thereof. It is also possible to laminate a single solid colored layer using these pigments separately.

[0050] (Printing layer) The printed layer in the present invention is a layer formed on at least a part of the surface of the opaque base layer, and is a layer containing a specific colored metallic pigment described below. The printed layer functions as an anti-counterfeiting mark so that authenticity can be determined, and has a specific color and color shift property that enables consumers to distinguish between authenticity and counterfeit.

[0051] The shape of the printed layer is not particularly limited, and may be polygonal, circular, approximately circular, irregular, or in the shape of letters or symbols. Furthermore, when an opaque base layer is laminated on the entire surface of the substrate, the printed layer may be laminated on the entire surface of the opaque base layer. Furthermore, when opaque base layers are laminated on both surfaces of the substrate, the printed layer may also be laminated on both surfaces.

[0052] The print layer may be composed of only colored metallic pigments, but may also contain inorganic pigments, organic pigments, etc., to the extent that they do not affect color shifting properties.

[0053] The printing layer has a solid mass per unit area of ​​the substrate (mass per unit area) of 1.0 g / m 2 More than 3.5g / m 2 The following range (preferably 1.2 g / m 2 More than 2.7g / m 2 The thickness of the printed layer is in the range below. By using this range, the visibility of the color shift caused by the printed layer is improved, as will be described later.

[0054] colored metallic pigments The color metallic pigment of the present invention contains a core metallic pigment, an amorphous silicon oxide film layer formed on the surface of the metallic pigment, and metal particles supported on part or the entire surface of the amorphous silicon oxide film layer. This structure enables the color shifting properties required for anti-counterfeiting marks to be exhibited.

[0055] In the colored metallic pigment of the present invention, the metal particles are formed so as to completely or partially cover the metallic pigment, so that only the light reflected from the metallic pigment that passes through the metal particle layer or between the particles is perceived as visible light. As a result, the reflected light from the metallic pigment is weakened, resulting in the development of chroma, i.e., color. Furthermore, interference between the light reflected from the surface of the metallic pigment and the light reflected from the surface of the metal particle produces highly saturated interference colors, and when the amorphous silicon oxide film layer is thick, the change in color tone (color shift) depending on the viewing angle becomes extremely large. Even when the metal particles are present in a continuous layer, the above-mentioned interference colors can be produced as long as the metal particle layer is thick enough to transmit light.

[0056] As will be described in detail later, the color metallic pigment may optionally have a base layer formed between the metal pigment core and the amorphous silicon oxide film layer. An intermediate layer (metal layer (intermediate layer A) and / or a metal oxide layer (intermediate layer B) made of a metal oxide other than silicon oxide) may optionally be formed between the amorphous silicon oxide film layer and the metal particle. Furthermore, a weather-resistant coating layer (protective layer) may be formed on the outside of the metal particle. In the cross-sectional view of an example of a color metallic pigment shown in FIG. 2, an amorphous silicon oxide layer 2, an intermediate layer 3, metal particles 4, and a weather-resistant coating layer 5 are sequentially formed on the surface of the metal pigment core 1.

[0057] When an intermediate layer is formed, the metal particles are adhered to each other to prevent peeling, and it becomes easier to stably obtain a colored metallic pigment that can express a variety of colors and a wide variety of interference colors. The intermediate layer is preferably formed on the entire surface of the amorphous silicon oxide film layer, but even if there is a part of the surface of the amorphous silicon oxide film layer where no intermediate layer is formed, it does not deviate from the scope of the present invention as long as the effect of the present invention is exhibited.

[0058] The intermediate layer is preferably a metal layer (intermediate layer A) and / or a metal oxide layer ((intermediate layer B) also referred to as a "metal oxide layer") made of a metal oxide other than silicon oxide. When the intermediate layer is made of both a metal layer and a metal oxide layer, the order of stacking is not particularly limited. That is, the intermediate layer may be configured such that a metal layer is stacked on the surface of an amorphous silicon oxide film layer, and a metal oxide layer is stacked on the surface of that metal layer, or such that a metal oxide layer is stacked on the surface of an amorphous silicon oxide film layer, and a metal layer is stacked on the surface of that metal oxide layer. The intermediate layer may also include two or more metal layers and two or more metal oxide layers, and in that case the order of stacking is not particularly limited.

[0059] The composition of the colored metallic pigment will be described in detail below.

[0060] metallic pigments Preferred examples of metal pigments as cores include aluminum, copper, zinc, titanium, iron, nickel, chromium, and alloys thereof, as well as metal-coated glass flakes and other metal-coated inorganic pigments, and among these, aluminum is particularly preferred from the viewpoint of design. When aluminum is used, it is advantageous in that a variety of colored metal pigments exhibiting interference colors can be obtained by forming an amorphous silicon oxide film layer and further supporting metal particles.

[0061] The preferred average particle size of the metallic pigment is, for example, in the range of 2 to 300 μm. When the average particle size is 2 μm or more, it is possible to obtain a color metallic pigment that imparts a good finished appearance and good hiding power to the coating film for forming the printing layer. Furthermore, when the average particle size is 300 μm or less, it is possible to obtain a color metallic pigment that can prevent deterioration in the finished appearance of the coating film due to poor dispersion of the color metallic pigment. It is more preferable that the average particle size is in the range of 5 to 100 μm. Note that the average particle size of the metallic pigment in this specification means the average major axis, and such average particle size can be measured by laser diffraction.

[0062] The shape of the metal pigment is not particularly limited and may be various shapes such as spherical, granular, polygonal, irregular, lumpy, or flaky. However, from the viewpoint of obtaining good design properties and a wide variety of colors, the flake shape is preferred.

[0063] When the metallic pigment is in the form of flakes, the preferred thickness (average thickness) is, for example, within the range of 0.01 to 5 μm. A thickness of 0.01 μm or more can provide a colored metallic pigment that can maintain a good finished appearance without impairing the lightfastness and weather resistance of the coating film. Furthermore, a thickness of 5 μm or less can provide a colored metallic pigment that imparts good design properties and a variety of colors to the coating film. The thickness is more preferably within the range of 0.02 to 1 μm. Such a thickness can be calculated from the water surface diffusion area and the specific gravity of the metallic pigment used as the core.

[0064] As described above, the preferred shape of the metallic pigment is preferably flake-like (i.e., scale-like), and a preferred example is one in which the ratio A / B of the average particle diameter A to the average thickness B is within the range of 5 to 1000. When the ratio A / B is 5 or more, the design properties of the coating film are good and a wider variety of colors can be expressed. Furthermore, when the ratio A / B is 1000 or less, deformation of the metallic pigment during production and a decrease in dispersibility of the color metallic pigment in the resin composition are less likely to occur, which is preferable. The ratio A / B is more preferably within the range of 15 to 500. As for the shape of the metallic pigment, among flake-like shapes, a coin-like shape with a smooth surface and rounded end faces, known as the silver dollar type, is particularly preferred.

[0065] The metallic pigments used in the present invention can be obtained, for example, as atomized powders or powders obtained by pulverizing metal flakes using a wet ball mill (i.e., the Hall method) or a dry ball mill. Alternatively, they can be obtained by depositing a thin metal film onto a film or the like, followed by peeling and pulverization. Metal-coated glass flakes and other metal-coated pigments can be obtained by forming layers of elements or alloys of Ag, Cu, Ni, Fe, Co, Cr, Sn, etc. on a flake or granular inorganic substrate such as glass flakes, mica, alumina, silica, or titanium oxide using techniques such as electroless plating, vapor deposition, or sputtering.

[0066] base layer A base layer may be formed on the surface of the metal pigment before the amorphous silicon oxide film layer is formed. Examples of the base layer include, but are not limited to, a layer consisting of a single film or a mixture film of any of oxides, hydroxides, and hydrates containing at least one element selected from the group consisting of molybdenum, phosphorus, and aluminum. Even when a base layer is formed on the surface of the metal pigment in this way, the present invention will still refer to the amorphous silicon oxide film layer being formed on the surface of the metal pigment.

[0067] Amorphous silicon oxide layer The color metallic pigment has an amorphous silicon oxide film layer laminated on the surface of the metallic pigment. This amorphous silicon oxide film layer is preferably formed on the entire surface of the metallic pigment, but even if there is a portion of the surface of the metallic pigment where the amorphous silicon oxide film layer is not formed, it does not deviate from the scope of the present invention as long as the effect of the present invention is exhibited. Such an amorphous silicon oxide film layer may be formed directly on the surface of the metallic pigment, but from the viewpoint of ensuring the water resistance of the metallic pigment and improving the adhesion of the amorphous silicon oxide film layer, it is preferable to interpose the above-mentioned underlayer between the metallic pigment and the amorphous silicon oxide film layer.

[0068] The thickness of the amorphous silicon oxide film layer is not particularly limited, but is preferably in the range of more than 150 nm to 1000 nm. A layer thickness exceeding 150 nm increases the optical path difference required for interference, resulting in the formation of a coating film exhibiting high saturation and significant color change. A thickness exceeding 1000 nm may require a long time to form the amorphous silicon oxide film layer, resulting in poor productivity, or may increase the overall thickness of the color metal pigment, potentially impairing the smoothness of the amorphous silicon oxide film layer. The thickness of the amorphous silicon oxide film layer can be measured by cross-sectional observation using a scanning electron microscope. In this case, such measurements are performed on 50 random color metal pigments, and the average value is taken as the thickness of the amorphous silicon oxide film layer.

[0069] As a method for forming an amorphous silicon oxide film layer, for example, a method can be employed in which a metal pigment and a solution containing an organic silicon compound are stirred or kneaded in a slurry or paste state while being kept basic or acidic, thereby forming an amorphous silicon oxide film layer on the surface of the metal pigment or on the surface of a metal pigment having a base layer formed on its surface.

[0070] Examples of the organosilicon compound include methyltriethoxysilane, methyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, and condensates thereof, γ-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, and N-2-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0071] As a solvent for dissolving the silicon compound to prepare a solution containing the organosilicon compound, it is preferable to use a hydrophilic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone, etc. It is also preferable to further add water sufficient to hydrolyze the alkoxysilane to the solvent.

[0072] In this way, an amorphous silicon oxide film layer can be formed on the surface of a metal pigment by hydrolyzing an organic silicon compound in a solvent containing a hydrophilic solvent as its main component and dispersing the metal pigment, thereby precipitating amorphous silicon oxide onto the metal pigment.

[0073] The term "amorphous" in the amorphous silicon oxide film layer refers to a state in which no clear diffraction peaks derived from silicon oxide are detected in a crystal structure analysis by X-ray diffraction method.

[0074] Intermediate layer A (especially the metal layer as an electroless plating catalyst layer) When metal particles are formed by electroless plating using a water-soluble metal salt, the metal layer can be used as the intermediate layer A and formed using a method used as a pretreatment for electroless plating. Pretreatment for electroless plating generally includes a catalyst (also called catalyzing)-accelerator (also called accelerating) method and a sensitizing-activating method, and either method may be used. Alternatively, only catalyst or only sensitizing may be performed.

[0075] The catalyst-accelerator method is a method in which a mixed solution containing Sn (tin) and either Pd (palladium), Pt (platinum), or Au (gold) is used as a catalyst, and a metal pigment on which an amorphous silicon oxide film layer has been formed is immersed in the catalyst to adsorb a complex compound of Sn and either Pd, Pt, or Au on the surface of the amorphous silicon oxide film layer, and then an acid solution such as sulfuric acid or hydrochloric acid, or an alkaline solution such as sodium hydroxide or ammonia, is used as an accelerator, and the metal pigment is immersed in the accelerator to remove the Sn and activate either Pd, Pt, or Au.

[0076] The sensitizing-activating method is a method in which a Sn solution is used as a sensitizing liquid, a metal pigment on which an amorphous silicon oxide film layer has been formed is immersed in the sensitizing liquid to allow the Sn compound to be adsorbed onto the surface of the amorphous silicon oxide film layer, and then a solution containing either Pd, Pt, or Au is used as an activating liquid to support either Pd, Pt, or Au on the surface of the amorphous silicon oxide film layer.

[0077] The sensitizing method is a method in which a Sn solution is used as a sensitizing liquid, a metal pigment on which an amorphous silicon oxide film layer has been formed is immersed in the sensitizing liquid, and the Sn compound is adsorbed onto the surface of the amorphous silicon oxide film layer, thereby supporting the Sn compound on the surface of the amorphous silicon oxide film layer.

[0078] The metal source for the intermediate layer A formed by a method used as a pretreatment for electroless plating can be a water-soluble metal salt containing any of Sn, Pd, Pt, and Au. Specific examples of the metal salt include tin chloride, tin oxalate, tin sulfate, tin bromide, tin acetate, tin borofluoride, tin fluoride, sodium stannate, potassium stannate, tin methanesulfonate, tin sulfide, tin silicofluoride, palladium chloride, palladium acetate, palladium bromide, palladium hydroxide, palladium nitrate, palladium oxide, palladium sulfate, gold bromide, gold chloride, platinum chloride, and platinum oxide.

[0079] Using the method described above, an electroless plating catalyst layer of Sn, Pd, Pt, Au, or the like is formed as intermediate layer A. Metal particles can then be formed on the surface of intermediate layer A by electroless plating. When the metal pigment with intermediate layer A formed thereon is immersed in an electroless plating solution, the catalytic activity of intermediate layer A oxidizes the reducing agent in the plating solution on the surface of intermediate layer A. The electrons released at this time reduce metal ions in the electroless plating solution, causing the metal to precipitate on the surface of intermediate layer A and producing metal particles.

[0080] As described above, such intermediate layer A preferably contains at least one element selected from the group consisting of Sn, Pd, Pt, and Au.

[0081] The thickness of the intermediate layer A is preferably 30 nm or less. In this case, the resulting colored metallic pigment imparts good saturation and interference color. The thickness of the intermediate layer A is more preferably within the range of 0.1 to 10 nm. The thickness of the intermediate layer A can be confirmed as a metal layer formed between the amorphous silicon oxide film layer and the metal particles, for example, when observed at a high magnification of about 3,000,000 times using a transmission electron microscope (TEM). The presence of elements can also be confirmed by local EDS (energy-dispersive X-ray spectroscopy). The intermediate layer A is typically formed as a continuous layer of particle aggregates.

[0082] The intermediate layer A may be deposited uniformly or non-uniformly on the surface of the amorphous silicon oxide film layer (or intermediate layer B (metal oxide layer) described below). Even if the thickness of the intermediate layer A is so thin that it cannot be observed by TEM, for example, it is possible to deposit metal particles densely and uniformly when the intermediate layer A is deposited.

[0083] Intermediate layer B (especially the metal oxide layer) When a metal oxide layer (metal oxide layer) made of a metal oxide other than silicon oxide is used as intermediate layer B, this metal oxide layer is preferably formed on the entire surface of the amorphous silicon oxide film layer, but even if the amorphous silicon oxide film layer includes a portion on the surface where the metal oxide layer is not formed, this does not deviate from the scope of the present invention as long as the effects of the present invention are exhibited. By forming such a metal oxide layer, the metal particles can be densely and uniformly precipitated at regular intervals due to the good adsorption state between the metal particles and the metal oxide layer described below, and highly saturated interference colors can be expressed.

[0084] Such a metal oxide layer preferably contains an oxide of at least one element selected from the group consisting of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr (zirconium), Ti (titanium), and Ce (cerium), and in particular, it is preferable that the metal oxide layer contains an oxide of any one of Sn, Zn, Ti, and Ce.

[0085] The method for forming the metal oxide layer is not particularly limited, but suitable examples include a method in which an alkoxide of a metal constituting the metal oxide layer is hydrolyzed by a sol-gel method to precipitate it on an amorphous silicon oxide film layer, a method in which an alkali is added to a metal salt solution of the metal constituting the metal oxide layer to neutralize and precipitate the metal oxide, and a method in which a metal pigment on which an amorphous silicon oxide film layer has been formed is brought into contact with a solution in which an organometallic compound is dissolved in an organic solvent, and the resulting solution is oxidized by heat treatment to form a metal oxide layer on an amorphous silicon oxide film layer.

[0086] Examples of metal alkoxides used in the hydrolysis and precipitation method include tetraethoxytin and tetrabutoxytitanium, and a colloidal solution of the metal alkoxide dispersed therein is preferably used. Examples of catalysts for hydrolysis of metal alkoxides include aqueous ammonia, ethylenediamine, monoethanolamine, diethanolamine, hydrazine, and urea.

[0087] Examples of metal salts used in the neutralization precipitation method include tin chloride, tin fluoride, zinc chloride, titanyl sulfate, cerium nitrate, and cerium acetate. Examples of neutralizing agents for metal salts include aqueous ammonia, sodium hydroxide, monoethanolamine, and diethanolamine. Examples of reaction solvents include water, ethanol, isopropyl alcohol, methylpropylene glycol, and butyl cellosolve.

[0088] Examples of organometallic compounds used in methods using organometallic compounds include fatty acid metal salts such as cobalt naphthenate, nickel stearate, zirconium stearate, and dibutyltin dilaurate. As a solvent for dissolving the organometallic compound, any organic solvent capable of dissolving the organometallic compound can be used, such as toluene, xylene, dimethylformamide, acetone, ethyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and butyl cellosolve. The heat treatment temperature for decomposing and oxidizing the organometallic compound is preferably 200 to 500°C. At temperatures below 200°C, it may be difficult to oxidize the organometallic compound. At temperatures above 500°C, the metal pigment is likely to aggregate, increasing the risk of fire.

[0089] Furthermore, when metal particles described later are formed by electroless plating using a water-soluble metal salt, a layer containing Sn, Pt, Au, Pd, Zn, etc. (the aforementioned intermediate layer A), which is generally used as a pretreatment for the electroless plating, may be formed on the metal oxide layer (intermediate layer B). In the color metallic pigment of the present invention, even when such an intermediate layer is formed, it is expressed as the metal particles being formed so as to cover the amorphous silicon oxide film layer.

[0090] In the present invention, by providing a metal layer (intermediate layer A) or a metal oxide layer (intermediate layer B) on the amorphous silicon oxide film layer as a pretreatment for electroless plating, metal particles can be selectively attached to the amorphous silicon oxide film layer. When intermediate layer A and intermediate layer B are formed, the interface between the two layers may not be clearly distinguishable, and in that case, the intermediate layer A and intermediate layer B may be in a mixed state.

[0091] In the present invention, the thickness of the intermediate layer B is preferably 30 nm or less. In this case, the resulting color metallic pigment imparts good saturation and interference color. The thickness of the intermediate layer B is more preferably within the range of 0.1 to 10 nm. The intermediate layer B may be deposited uniformly or unevenly on the surface of the amorphous silicon oxide film layer. If the intermediate layer B is too thick, the thickness of the resulting color metallic pigment will also be large, resulting in a decrease in hiding power. If the intermediate layer B is too thin, sufficient effect will not be obtained and the color tone will be unstable. If the thickness of the intermediate layer B is large, it can be measured by cross-sectional observation using a transmission electron microscope (TEM). If the thickness of the intermediate layer B is small, the presence of the metallic pigment can be confirmed by surface analysis using X-ray photoelectron spectroscopy (XPS).

[0092] metal particles In the case of a colored metallic pigment, metal particles are supported on a part or the whole of the surface of the amorphous silicon oxide film layer. When an intermediate layer is formed, the metal particles are formed so as to cover a part or the whole of the surface of the intermediate layer.

[0093] In the present invention, interference occurs between light reflected from the surface of the metal particle and light reflected from the surface of the metal pigment, which is the core, that passes through the amorphous silicon oxide film layer and the metal particle layer, resulting in a colored metal pigment that exhibits a highly saturated interference color.

[0094] Preferred examples of metal particles include particles containing at least one of Al (aluminum), Ti (titanium), Cr (chromium), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Sn (tin), Pt (platinum), Au (gold), and alloys thereof. When the metal particles contain one or more metals selected from these metals and metal alloys, a colored metallic pigment exhibiting a highly saturated interference color can be obtained. Particularly preferred metal particles include particles containing at least one element selected from the group consisting of Cu, Ni, and Ag.

[0095] The metal particles preferably have an average particle size of 50 nm or less. In this case, even in the case of a color metallic pigment having both areas where the metal particles are formed and areas where the metal particles are not formed, the surface morphology is relatively smooth, and a color metallic pigment that can exhibit a metallic feel with an excellent finished appearance can be obtained. The average particle size of the metal particles is more preferably 30 nm or less.

[0096] Although there is no particular lower limit for the average particle size of the metal particles, it is preferably 1 nm or more. If it is less than 1 nm, light passes through the metal particles, resulting in less light reflected from the metal particle layer and a weaker coloring effect due to light interference, which may result in a decrease in the saturation of the resulting color metallic pigment. Even if the metal particles are present in a continuous layer, the aforementioned interference color can be expressed as long as the thickness is sufficient to transmit light.

[0097] The metal particles formed in the color metallic pigment of the present invention are preferably formed so as to cover only a portion of the amorphous silicon oxide film layer, rather than completely covering it. However, in order to obtain a color metallic pigment with higher saturation, it is preferable that the spacing between the metal particles be 10 nm or less. In this case, the spacing between the metal particles of 10 nm or less corresponds to the portion not covered by the metal particles as described above. In this case, the lower limit of the spacing is preferably 0.1 nm or more.

[0098] Although two or more metal particles may be deposited on the amorphous silicon oxide film layer in an overlapping state, it is preferable that the metal particles are deposited as a single layer. In this case, interference between the light reflected from the metal particles and the light reflected from the core metal pigment and passing through between the metal particles imparts a highly saturated interference color. Furthermore, it is preferable that the metal particles are deposited on the metal particle support layer without contacting each other. Most typically, it is preferable that the metal particles are deposited on the amorphous silicon oxide film layer in a single layer without contacting each other and with the distance between the metal particles being 10 nm or less.

[0099] The deposition state of the metal particles, the average particle diameter, and the spacing between the metal particles can be evaluated by, for example, cross-sectional observation using a transmission electron microscope (TEM). In this case, a preferred method for preparing a sample for observation is to process the cross section of a colored metallic pigment on which metal particles have been formed using a focused ion beam (FIB). This method allows the processing location to be determined while viewing a scanning ion microscope (SIM) image, making it possible to process specific locations within the sample. After processing using the above method, the cross section of the metal particles is observed using a transmission electron microscope (TEM) at 300,000 to 3,000,000 magnifications.

[0100] The method for forming the metal particles is not particularly limited, but suitable methods include vacuum deposition, sputtering, electroless plating, etc. Among these methods, the electroless plating method is particularly suitable because it can deposit the metal particles uniformly at the predetermined intervals as described above and can provide good color saturation.

[0101] Weather-resistant coating layer (protective layer) The color metallic pigment of the present invention may further have a weather-resistant coating layer formed on the metal particles. Examples of the weather-resistant coating layer include a single film or a mixture film of an oxide, hydroxide, or hydrate containing at least one element selected from the group consisting of aluminum, silicon, and cerium, or a resin coating layer. The thickness of the weather-resistant coating layer is not limited, but is preferably within the range of 1 to 200 nm.

[0102] The main structure of the colored metallic pigment has been described above, but it is sufficient for the colored metallic pigment to have metal particles supported on part or the entire surface of the amorphous silicon oxide film layer, and it is also acceptable for the colored metallic pigment to have additional layers, granular materials, etc. other than those described above formed within the scope that does not impair the effects of the present invention.

[0103] (thermal adhesive layer) The press-through pack material may further comprise a thermal adhesive layer on at least a portion of the outermost surface. In the press-through pack material, the thermal adhesive layer is also called a heat seal layer, and it is possible to produce a press-through pack package in which the contents are sealed by thermally bonding the lid material and the storage container. The thermal adhesive layer may be formed on the adhesive surface of either (or both) the lid material or the storage container.

[0104] The thermal adhesive layer is not particularly limited, and materials containing various thermoplastic resins can be used as heat-sealable resins. Examples of resin components constituting the thermal adhesive layer include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear polyethylene, saturated polyester, linear saturated polyester, unstretched polypropylene, chlorinated polypropylene, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ionomer, ethylene-ethyl acrylate-maleic anhydride terpolymer, vinyl chloride-vinyl acetate copolymer, polyolefin, carboxylic acid-modified polyethylene, carboxylic acid-modified polypropylene, carboxylic acid-modified ethylene-vinyl acetate copolymer, vinyl chloride, and polystyrene. Commercially available products can also be used. For example, commercially available products such as "Bondine" manufactured by Sumitomo Chemical Co., Ltd. and "Mersen M" manufactured by Tosoh Corporation can be used.

[0105] The thickness of the thermal adhesive layer is not limited, but is preferably about 1 to 100 μm, more preferably 2 to 50 μm. The amount of the thermal adhesive layer formed is 1 to 30 g / m2 in terms of mass after drying. 2 It is preferable to set it to about this level.

[0106] The thermal adhesive layer can be formed, for example, by 1) a method including a step of applying a coating liquid containing a resin component and drying it, or by 2) a method including a step of laminating a sealant film that has been preformed using a resin component.

[0107] In the above method 1), the coating liquid can be a solution or dispersion of the resin component. As the solvent for this, one or more of the various solvents listed above can be used. In this case, the coating amount after drying is 2 to 15 g / m. 2 It should be about that level.

[0108] The coating method can be, for example, coating (laminating) by a gravure roll coater, offset printing, flexographic printing, UV printing, curtain flow coater, etc. Coating by spraying or the like can also be carried out.

[0109] As the sealant film of 2) above, for example, a resin film such as polyamide (nylon), polyethylene (particularly high-density polyethylene), polypropylene (particularly oriented polypropylene), vinyl chloride, ethylene-vinyl alcohol copolymer, polyethylene naphthalate, polyethylene terephthalate, etc. In this case, the thickness of the resin film is preferably about 9 to 50 μm. These sealant films themselves can also be commercially available products. [Example]

[0110] Example 1 A black ink (vinyl chloride-vinyl acetate copolymer resin as the matrix resin, containing 5% by mass of carbon black on a solids basis) was applied to the entire glossy side of a 20 μm thick aluminum foil (1N30 hard material, manufactured by Toyo Aluminum Co., Ltd.) to form a black colored layer. The black ink was applied by gravure printing using a gravure plate to a mass of 1.2 g / m after drying. 2 It was set to be.

[0111] Next, a color-shifting ink layer (containing 34.2% by mass of Chromashine CPK-20X manufactured by Toyo Aluminum Co., Ltd., consisting of a vinyl chloride-vinyl acetate copolymer resin as the matrix resin, a metal pigment, an amorphous silicon oxide film layer formed on the surface of the metal pigment, and metal particles supported on part of the surface of the amorphous silicon oxide film layer, on a solid content basis) was gravure printed on a gravure plate to form a color-shifting ink layer so that it would be approximately 2 μm thick after drying.

[0112] Next, a protective layer varnish containing an epoxy resin as a matrix resin was applied using a gravure plate so as to cover the color-shifting ink layer, and after drying, the varnish was applied to a thickness of 2 g / m 2 A protective layer was provided so that

[0113] After that, the ink was dried at a surface temperature of approximately 180°C for a drying time of approximately 10 seconds. 2 The color shifting ink layer was laminated.

[0114] In this way, a PTP lid material was produced in which aluminum foil (substrate), black colored layer (opaque base layer), color shifting ink layer (printed layer), and protective layer were laminated in this order.

[0115] When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black colored layer was completely shielded, and that the color tone changed from yellow to pale pink by changing the viewing angle from 45 degrees to 90 degrees relative to the coated surface.

[0116] Example 2 1.5g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the black ink layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0117] Example 3 1.8g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the black ink layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0118] Example 4 2.7g / m on black ink 2A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the black ink layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0119] Example 5 3.0 g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the black ink layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0120] Example 6 The coating conditions for black ink are 0.5 g / m after drying. 2 The ink density was set to 2.7 g / m on black ink. 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the black ink layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0121] Example 7 White ink (vinyl chloride-vinyl acetate copolymer resin as matrix resin, containing 51.2 mass% titanium oxide on a solids basis) was applied to the entire glossy surface of the aluminum foil at a density of 2.0 g / m after drying. 2 The white ink was applied so that a white colored layer (opaque base layer) was formed, and the white ink was applied at a density of 2.7 g / m 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated on the white-colored layer. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the white-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0122] Example 8 An embodiment in which a printing layer is provided on a storage container is shown in Figure 1. Similar to Example 1, a black-colored layer and a color-shifting ink layer were provided on the glossy side of a 45 μm-thick aluminum foil (a hard material conforming to JIS-H4160, manufactured by Toyo Aluminum Co., Ltd.).

[0123] Next, a polyurethane dry laminating adhesive (mass after drying: 3 g / m) was applied to the glossy side of the aluminum foil. 2 A 25 μm thick nylon film (Bonyl RX, manufactured by Kohjin Co., Ltd.) was laminated onto the other side of the aluminum foil using a polyurethane dry lamination adhesive (mass after drying: 3 g / m 2 ) was used to laminate a 60 μm thick polyvinyl chloride sealant film.

[0124] In this way, a PTP container material was produced in which a polyvinyl chloride sealant film / aluminum foil (substrate) / black colored layer (opaque base layer) / color shifting ink layer (printed layer) / nylon film layer were laminated in that order.

[0125] When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black colored layer was completely shielded, and that the color tone changed by changing the viewing angle, as in Example 1.

[0126] Example 9 1.5g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0127] Example 10 1.8g / m on black ink 2A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0128] Example 11 2.7g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0129] Example 12 3.0 g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0130] Example 13 The coating conditions for black ink are 0.5 g / m after drying. 2 The ink density was set to 2.7 g / m on black ink. 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the black-colored layer was completely shielded and that the color tone changed by changing the viewing angle, as in Example 1.

[0131] Example 14 White ink (vinyl chloride-vinyl acetate copolymer resin as matrix resin, containing 51.2 mass% titanium oxide on a solids basis) was applied to the entire glossy surface of the aluminum foil at a density of 2.0 g / m after drying. 2The white ink was applied so that a white colored layer (opaque base layer) was formed, and the white ink was applied at a density of 2.7 g / m 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was confirmed that the white colored layer was completely shielded, and that the color tone changed by changing the viewing angle, as in Example 1.

[0132] Comparative Example 1 0.2g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0133] Comparative Example 2 0.6g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0134] Comparative Example 3 0.8g / m on black ink 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0135] Comparative Example 4 1.2 g / m on aluminum foil excluding the ink coloring layer 2A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0136] Comparative Example 5 2.7g / m on aluminum foil excluding the ink coloring layer 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0137] Comparative Example 6 The coating conditions for black ink are 0.2 g / m2 after drying. 2 The ink density was set to 0.8 g / m on black ink. 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0138] Comparative Example 7 The coating conditions for black ink are 0.2 g / m2 after drying. 2 The ink density was set to 2.7 g / m on black ink. 2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0139] Comparative Example 8 White ink (vinyl chloride-vinyl acetate copolymer resin as matrix resin, containing 51.2 mass% titanium oxide on a solids basis) was applied to the entire glossy surface of the aluminum foil at a density of 2.0 g / m after drying. 2 The white ink was applied so that a white colored layer (opaque base layer) was formed, and the white ink was applied at a density of 0.8 g / m2 A PTP lid material was produced in the same manner as in Example 1, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0140] Comparative Example 9 0.2g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was found that the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0141] Comparative Example 10 0.6g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was found that the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0142] Comparative Example 11 0.8g / m on black ink 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, it was found that the black-colored layer was not completely shielded, and no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0143] Comparative Example 12 1.2 g / m on aluminum foil excluding the ink coloring layer 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0144] Comparative Example 13 2.7g / m on aluminum foil excluding the ink coloring layer 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0145] Comparative Example 14 The coating conditions for black ink are 0.2 g / m2 after drying. 2 The ink density was set to 0.8 g / m on black ink. 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0146] Comparative Example 15 The coating conditions for black ink are 0.2 g / m2 after drying. 2 The ink density was set to 2.7 g / m on black ink. 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0147] Comparative Example 16 White ink (vinyl chloride-vinyl acetate copolymer resin as matrix resin, containing 51.2 mass% titanium oxide on a solids basis) was applied to the entire glossy surface of the aluminum foil at a density of 2.0 g / m after drying. 2 The white ink was applied so that a white colored layer (opaque base layer) was formed, and the white ink was applied at a density of 0.8 g / m 2 A PTP container material was produced in the same manner as in Example 8, except that the color-shifting ink layer was laminated. When the color-shifting ink layer was observed with the naked eye, no change in color tone was observed even when the viewing angle was changed, as in Example 1.

[0148] Test Example 1 The press-through pack materials obtained in the examples and comparative examples were visually evaluated for appearance, and the results are shown in Table 1.

[0149] [Table 1]

[0150] As shown by the above results, the press-through pack material of the present invention can be equipped with an anti-counterfeit marking without using a hologram seal, making it easy to determine whether it is genuine or not. Furthermore, unlike hologram seals, the material cannot be removed from the press-through pack and therefore cannot be reused. Furthermore, the color of the metal pigment used as the anti-counterfeit marking changes significantly depending on the manufacturing conditions, making it difficult to reproduce the same product. Therefore, it is a significant deterrent to the distribution of counterfeit medicines. [Explanation of symbols]

[0151] 1. Core metallic pigments 2. Amorphous silicon oxide film layer 3. Intermediate layer (metal layer and / or metal oxide layer made of a metal oxide other than silicon oxide) 4. Metal particles 5.Weather-resistant coating layer (protective layer)

Claims

1. a substrate, an opaque underlayer laminated on at least a portion of the surface of the substrate, and a printed layer containing a colored metallic pigment formed on at least a portion of the surface of the opaque underlayer, laminated in this order; The color metallic pigment comprises a metallic pigment, an amorphous silicon oxide film layer formed on the surface of the metallic pigment, and a plurality of metal particles supported on a part or the entire surface of the amorphous silicon oxide film layer, The opaque underlayer is a black colored layer, the black colored layer has a structure in which a black pigment is dispersed in a matrix resin, the matrix resin is at least one of a vinyl chloride-vinyl acetate copolymer resin, a nitrocellulose-based resin, and a polypropylene-based resin; The mass per unit area of ​​the opaque underlayer is 0.5 g / m ２ 2.0g / m or more ２ is as follows: The mass per unit area of ​​the printing layer is 1.2 g / m ２ 3.0g / m or more ２ Below is the A press-through pack material characterized by:

2. 2. The press-through pack material according to claim 1, wherein the metal particles contain at least one element selected from the group consisting of Cu, Ni, and Ag.

3. 3. The press-through pack material according to claim 1, wherein the amorphous silicon oxide film layer has a thickness of 10 nm or more and 1000 nm or less.

4. The press-through pack material according to any one of claims 1 to 3, wherein the metal particles have an average particle size of 50 nm or less.

5. A press-through pack using the press-through pack material according to any one of claims 1 to 4 as a container and / or a lid for a medicine.

Images