Metallic Color Film

Abstract

To provide a metallic color film having excellent resistance to moist heat. [Solution] A metallic color film comprising a substrate, a first layer, and a second layer arranged in this order, the first layer being either a color adjusting layer or a metal layer, the second layer being the other of the color adjusting layer and the metal layer different from the layer selected as the first layer, a first protective layer being arranged between the first and second layers, the color adjusting layer containing Si, the metal layer containing at least one of Ag and Al, the first protective layer containing Ti, and the average film thickness of the first protective layer being 1.2 nm or more.

Description

[Technical Field]

[0001] The present invention relates to a metallic color film, and more particularly to a metallic color film having excellent resistance to moist heat. [Background technology]

[0002] Decorative members for achieving specific hues have been developed (for example, Patent Document 1). Patent Document 1 discloses a decorative member including a light-reflecting layer and a light-absorbing layer that is provided on the light-reflecting layer and contains Si. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2020-522006 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the decorative member described in Patent Document 1 leaves room for improvement in terms of moist heat resistance.

[0005] The present invention has been made in view of the above-mentioned conventional inventions, and has as its object to provide a metallic color film having excellent resistance to moist heat. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that a metallic color film that can exhibit excellent moist heat resistance can be obtained by providing a substrate with a color-adjusting layer containing Si, a protective layer containing Ti of a specific thickness, and a metal layer containing Ag or Al, and have completed the present invention. That is, the metallic color film of the present invention that solves the above-mentioned problems mainly includes the following components.

[0007] (1) A metallic color film comprising a substrate, a first layer, and a second layer provided in this order, the first layer being either a color-adjusting layer or a metal layer, the second layer being the other of the color-adjusting layer and the metal layer that is different from the layer selected as the first layer, a first protective layer being provided between the first layer and the second layer, the color-adjusting layer containing Si, the metal layer containing at least one of Ag and Al, the first protective layer containing Ti, and the average film thickness of the first protective layer being 1.2 nm or more.

[0008] With this configuration, the metallic color film has excellent resistance to moisture and heat.

[0009] (2) The metallic color film according to (1), wherein the color-adjusting layer has an average thickness of 2.9 to 100 nm.

[0010] With this configuration, the metallic color film can easily achieve any desired color.

[0011] (3) The metallic color film according to (1) or (2), wherein the first protective layer has an average thickness of 5 nm or less.

[0012] With this configuration, the metallic color film can more easily achieve any desired color with greater brightness.

[0013] (4) A metallic color film described in any one of (1) to (3), further comprising a second protective layer on the surface of the metal layer opposite to the surface in contact with the first protective layer, the second protective layer containing Ti.

[0014] With this configuration, the metallic color film has better resistance to moisture and heat. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a metallic color film having excellent resistance to moist heat. DETAILED DESCRIPTION OF THE INVENTION

[0016] <Metallic color film> The metallic color film of one embodiment of the present invention is a film comprising a substrate, a first layer, and a second layer provided in this order. The first layer is either a color-adjusting layer or a metal layer, and the second layer is the other of the color-adjusting layer and the metal layer, different from the layer selected as the first layer. A first protective layer is provided between the first and second layers. The color-adjusting layer contains Si. The metal layer contains at least one of Ag and Al. The first protective layer contains Ti. The average film thickness of the first protective layer is 1.2 nm or more. Each of these layers will be described below.

[0017] (base material) The substrate is not particularly limited. Preferably, the substrate is a substrate with high light transmittance. For example, the substrate may be made of a poly(meth)acrylic acid ester such as polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, polyimide, polystyrene, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene naphthalate (PEN), cycloolefin polymer (COP), or the like.

[0018] The thickness of the substrate is not particularly limited. For example, the thickness of the substrate is preferably 2 μm or more, more preferably 4 μm or more, and even more preferably 12 μm or more. The thickness of the substrate is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 125 μm or less. When the thickness of the substrate is within the above range, the film can be made lighter and has excellent flexibility.

[0019] The substrate may be subjected to a desired surface treatment. The type of surface treatment is not particularly limited. The surface treatment may be performed on both the surface of the substrate on which the first layer is formed and the surface opposite the surface on which the first layer is formed. Surface treatments performed on the surface on which the first layer is formed include matte finish, satin finish, embossing, hairline finish, various coatings (fluorine finish for imparting antifouling properties, hard coat finish for imparting scratch resistance, antistatic finish for imparting antistatic properties, transfer processing for imparting transferability, lift-off processing for expressing partial design, etc.). On the other hand, surface treatments performed on the surface opposite the surface on which the first layer is formed include matte finish, satin finish, embossing, hairline finish, various coatings (fluorine finish for imparting antifouling properties, hard coat finish for imparting scratch resistance, antistatic finish for imparting antistatic properties, adhesive finish for imparting adhesiveness, etc.). One type of these surface treatments may be performed, or two or more types of treatments may be combined.

[0020] The substrate may be subjected to various surface treatments. The surface treatment is not particularly limited. Examples of the surface treatment include corona treatment, plasma treatment, ion bombardment treatment, and ion implantation treatment. This can improve the adhesion of the substrate to a layer formed thereon.

[0021] The substrate may be a substrate on which an anchor layer is formed in order to improve adhesion with the first layer (and the second protective layer, if one is formed) described below. In this case, the substrate is composed of a base sheet made of the above-mentioned material and an anchor layer formed on the base sheet.

[0022] The anchor layer is not particularly limited. For example, the anchor layer may be made of a material that has good adhesion to the base sheet and also to the first layer (or the second protective layer), such as an acrylic resin, a nitrocellulose resin, a polyurethane resin, a polyester resin, a styrene-maleic acid resin, a chlorinated PP resin, a melamine resin, a urea resin, a vinyl chloride resin, a vinyl acetate resin, a siloxane resin, or an epoxy resin.

[0023] The anchor layer may be provided with a design feature by adding a colorant or a metallic pigment. For example, by adding a colorant, the laminate film can easily express a more vivid color appearance. The type and content of the colorant can be appropriately adjusted depending on the desired metallic appearance. Furthermore, the anchor layer may be provided with functionality such as an antistatic effect by adding an antistatic agent or the like.

[0024] The method for forming the anchor layer is not particularly limited. For example, the anchor layer can be formed by an anchor layer forming step of forming an anchor layer on a base sheet, and can be formed by a blade coating method, a bar coating method, a gravure coating method, a reverse roll coating method, a die coating method, screen printing, or the like.

[0025] (1st and 2nd layers) The first layer is either a color adjusting layer or a metal layer, and the second layer is the other layer, either a color adjusting layer or a metal layer, different from the layer selected as the first layer. As will be described later, a first protective layer is provided between the first and second layers. For example, if the first layer is a color adjusting layer, the second layer is a metal layer. In this case, the layers are stacked in the following order: base material, color adjusting layer, first protective layer, and metal layer (first configuration). A viewer can observe from the base material side, and can see the hue of the metal layer adjusted by the color adjusting layer. On the other hand, if the first layer is a metal layer, the second layer is a color adjusting layer. In this case, the layers are stacked in the following order: base material, metal layer, first protective layer, and color adjusting layer (second configuration). A viewer can observe from the color adjusting layer side, and can see the hue of the metal layer adjusted by the color adjusting layer.

[0026] Among these, it is preferable that the metallic color film of this embodiment adopts the first configuration, which provides the metallic color film with better durability.

[0027] Color adjustment layer The color-adjusting layer contains Si. The color-adjusting layer consists essentially of Si. The purity of Si in the color-adjusting layer is preferably 90% by mass or more, more preferably 95% by mass or more, and may be substantially 100% by mass. When the purity of Si is within the above range, the metallic color film tends to exhibit vivid metallic colors. In this embodiment, the color-adjusting layer may contain unavoidable impurities, and may also contain other components as long as they do not impair the effects of this embodiment.

[0028] The average thickness of the color-adjusting layer is preferably 2.9 nm or more, more preferably 3.9 nm or more. The average thickness of the color-adjusting layer is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less. By having the average thickness of the color-adjusting layer within the above range, the metallic color film can easily achieve any color (e.g., gold, deep red-purple metallic, purple metallic, red-purple metallic, green metallic, pink metallic, red metallic, blue metallic, brown metallic, etc.). In this embodiment, the average thickness of the color-adjusting layer can be measured by quantitative analysis using a calibration curve method using a fluorescent X-ray measuring device (e.g., XRF manufactured by Rigaku Corporation).

[0029] The method for forming the color-adjusting layer is not particularly limited. For example, the color-adjusting layer can be formed by appropriately using a conventionally known technique, such as a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method. Among these, the color-adjusting layer of the present embodiment is preferably formed by a sputtering method.

[0030] In the first configuration, the color-adjusting layer is provided on a base material, whereas in the second configuration, the color-adjusting layer is provided on a first protective layer, which will be described later.

[0031] ·Metal layer The metal layer contains at least one of Ag and Al. The metallic color film of this embodiment exhibits any metallic hue by adjusting the hue of Ag or Al with the color-adjusting layer.

[0032] When the metal layer contains Ag, the purity of Ag is preferably 90% by mass or more, more preferably 95% by mass or more, and may be substantially 100% by mass. When the purity of Ag is within the above range, the metallic color film tends to develop a vivid metallic color. In this embodiment, the metal layer may contain unavoidable impurities, and may contain other components as long as they do not impair the effects of this embodiment.

[0033] When the metal layer contains Al, the purity of Al is preferably 90% by mass or more, more preferably 95% by mass or more, and may be substantially 100% by mass. When the purity of Al is within the above range, the metallic color film tends to develop a vivid metallic color. In this embodiment, the metal layer may contain unavoidable impurities, and may contain other components as long as they do not impair the effects of this embodiment.

[0034] The other components contained in the metal layer are not particularly limited. Examples of the other components include palladium, copper, bismuth, gold, platinum, zinc, tin, titanium, nickel, magnesium, lead, and indium. The proportion of the other components contained in the metal layer is preferably 0.1% by mass or more and 10% by mass or less.

[0035] The average thickness of the metal layer is preferably 20 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The average thickness of the metal layer is preferably 150 nm or less, and more preferably 100 nm or less. When the average thickness of the metal layer is within the above range, the metallic color film tends to develop a vivid metallic color. In this embodiment, the average thickness of the metal layer can be measured by quantitative analysis using a calibration curve method using a fluorescent X-ray measuring device (for example, an XRF manufactured by Rigaku Corporation).

[0036] The method for forming the metal layer is not particularly limited. For example, the metal layer can be formed by appropriately using a conventionally known technique, such as a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method.

[0037] In the first configuration, the metal layer is provided on a first protective layer (described later), whereas in the second configuration, the metal layer is provided on the substrate or, if a second protective layer is formed, on the second protective layer, and the first protective layer is provided on the metal layer.

[0038] (First protective layer) The first protective layer is disposed between the first layer and the second layer.

[0039] The first protective layer contains Ti. The first protective layer consists essentially of Ti. The purity of Ti in the first protective layer is preferably 90% by mass or more, more preferably 95% by mass or more, and may be substantially 100% by mass. When the purity of Ti is within the above range, the metallic color film has excellent moist heat resistance. In this embodiment, the first protective layer may contain unavoidable impurities, and may also contain other components as long as they do not impair the effects of this embodiment.

[0040] The average thickness of the first protective layer may be 1.2 nm or more, preferably 1.6 nm or more, and more preferably 2.0 nm or more. The average thickness of the first protective layer is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. If the average thickness of the first protective layer is less than 1.2 nm, the metallic color film will have a metal layer that is prone to corrosion and poor moist heat resistance. By having the average thickness of the first protective layer within the above range, the metallic color film will have a metal layer that is less prone to corrosion and excellent moist heat resistance, allowing the desired color development to be achieved. In this embodiment, the average thickness of the first protective layer can be measured by quantitative analysis using a calibration curve method using a fluorescent X-ray measurement device (for example, an XRF manufactured by Rigaku Corporation).

[0041] The method for forming the first protective layer is not particularly limited. For example, the first protective layer can be formed by appropriately using a conventionally known technique, such as a physical vapor deposition method such as vacuum deposition, sputtering, or ion plating, or a chemical vapor deposition method. Among these, the first protective layer of this embodiment is preferably formed by sputtering.

[0042] In the first configuration, the first protective layer is provided on the color-adjusting layer, whereas in the second configuration, the first protective layer is provided on the metal layer.

[0043] The metallic color film of this embodiment may be provided with other layers as appropriate in addition to the substrate, color-adjusting layer, metal layer, and first protective layer, such as a second protective layer, a scratch-resistant layer, and an adhesive layer.

[0044] (Second protective layer) The second protective layer is preferably provided on the surface of the metal layer opposite to the surface in contact with the first protective layer. By providing the second protective layer, the metallic color film is more likely to prevent corrosion of the metal layer, the color adjusting layer, and the first protective layer.

[0045] The second protective layer is not particularly limited. For example, the second protective layer may be made of an element, oxide, nitride, or alloy of Ti, Cr, Ni, Si, or Al. In this case, the second protective layer is preferably formed by vapor deposition or sputtering.

[0046] The average thickness of the second protective layer formed by vapor deposition or sputtering is not particularly limited. For example, the average thickness of the second protective layer is preferably 0.1 nm or more, more preferably 1 nm or more. Furthermore, the average thickness of the second protective layer is preferably 100 nm or less, more preferably 30 nm or less. By having the average thickness of the second protective layer within the above range, the metallic color film is protected from corrosion and is likely to develop a vivid metallic color. In this embodiment, the average thickness of the second protective layer can be measured by quantitative analysis using a calibration curve method using a fluorescent X-ray measurement device (for example, an XRF manufactured by Rigaku Corporation).

[0047] On the other hand, the second protective layer may be made of a resin such as an acrylic resin, a nitrocellulose resin, a polyurethane resin, a polyester resin, a styrene-maleic acid resin, a chlorinated PP resin, a melamine resin, a urea resin, a vinyl chloride resin, a vinyl acetate resin, a siloxane resin, or an epoxy resin. In this case, the second protective layer is preferably formed by a wet coating method.

[0048] The average thickness of the second protective layer formed by the wet coating method is not particularly limited. For example, the average thickness of the second protective layer is preferably 20 nm or more, more preferably 30 nm or more. Furthermore, the average thickness of the second protective layer is preferably 5 μm or less, more preferably 2 μm or less. When the average thickness of the second protective layer is within the above range, the metallic color film is easily protected from corrosion and develops a vivid metallic color. In this embodiment, the average thickness of the second protective layer can be measured by calculating the optical film thickness equivalent value using an ultraviolet-visible-near-infrared spectrophotometer (e.g., UV3600, manufactured by Shimadzu Corporation).

[0049] Of the above, the second protective layer of this embodiment preferably contains Ti, and may be composed essentially of Ti alone. The purity of Ti in the second protective layer is preferably 90% by mass or more, more preferably 95% by mass or more, and may be essentially 100% by mass. When the purity of Ti is within the above range, the metallic color film has better moist heat resistance. Note that the second protective layer of this embodiment may contain unavoidable impurities, and may also contain other components as long as they do not impair the effects of this embodiment.

[0050] The average thickness of the second protective layer is preferably 1.2 nm or more, more preferably 1.6 nm or more, and even more preferably 2.0 nm or more. The average thickness of the second protective layer is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. When the average thickness of the second protective layer is within the above range, the metallic color film has better moist heat resistance. In this embodiment, the average thickness of the second protective layer can be measured by quantitative analysis using a calibration curve method using a fluorescent X-ray analyzer (for example, an XRF manufactured by Rigaku Corporation).

[0051] In the first configuration, the second protective layer may be provided on the metal layer, while in the second configuration, the second protective layer may be provided on the substrate.

[0052] According to this embodiment, the metallic color film can exhibit a metallic color. The metallic color film is a metallic chromatic color film. In this embodiment, the "color (chromatic color)" can be distinguished from a metallic achromatic color film by satisfying the following formula (1) in the optical reflection characteristic values ​​(a* value, b* value) in the L*a*b* color space. (a* 2 +b* 2 ) 1 / 2 ≧ 3 Equation (1)

[0053] The metallic color film of this embodiment can easily achieve any color (for example, gold, deep red-purple metallic, purple metallic, red-purple metallic, green metallic, pink metallic, red metallic, blue metallic, brown metallic, etc.).

[0054] For example, when the metallic color film of this embodiment exhibits a golden color, it is preferable that a* and b* in the L*a*b* color space of the reflected light of the color adjusting layer on the side opposite to the metal layer satisfy the following (1) to (2). (1) Absolute value of reflection a* < absolute value of reflection b* (2) Reflection b* value ≥ 10

[0055] Furthermore, when the metallic color film of this embodiment exhibits a bluish metallic color, it is preferable that a* and b* in the L*a*b* color space of the reflected light of the color adjusting layer on the side opposite to the metal layer satisfy the following (3) to (4). (3) Absolute value of reflection a* < absolute value of reflection b* (4) Reflection b* value ≦-10

[0056] Furthermore, when the metallic color film of this embodiment exhibits a reddish metallic color, it is preferable that a* and b* in the L*a*b* color space of the reflected light of the color adjusting layer on the side opposite to the metal layer satisfy the following (5) to (6). (5) Absolute value of reflection a* > absolute value of reflection b* (6) Reflection a* value ≥ 10

[0057] Furthermore, when the metallic color film of this embodiment exhibits a greenish metallic color, it is preferable that a* and b* in the L*a*b* color space of the reflected light of the color adjusting layer on the side opposite to the metal layer satisfy the following (7) to (8). (7) Absolute value of reflection a* > absolute value of reflection b* (8) Reflection a* value ≦-10 [Example]

[0058] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0059] <Comparative Example 1> A substrate (PET film, 50 μm thick) was prepared, and a color-adjusting layer made of Si was formed on the substrate by sputtering. The sputtering conditions were as follows: A Si target material was used, and the pressure during film formation with Ar gas introduced was 0.2 Pa. The average film thickness of the resulting color-adjusting layer was 4.8 nm. Next, a metal layer made of Ag was formed on the color-adjusting layer by sputtering, thereby producing a metallic color film. The sputtering conditions were as follows: Ag was used as the target, and the pressure during film formation with Ar gas introduced was 0.3 Pa. The average film thickness of the resulting metal layer was 70 nm.

[0060] Example 1 A substrate (PET film, thickness 50 μm) was prepared, and a color-adjusting layer made of Si was formed on the substrate by sputtering. The sputtering conditions were as follows: A Si target material (purity 99.9% by mass) was used as the target, and the pressure during film formation with Ar gas introduced was 0.2 Pa. The average film thickness of the resulting color-adjusting layer was 4.8 nm. Next, a first protective layer made of Ti was formed on the color-adjusting layer by sputtering. The sputtering conditions were as follows: A Ti target material (purity 99.9% by mass) was used as the target, and the pressure during film formation with Ar gas introduced was 0.3 Pa. The average film thickness of the resulting first protective layer was 1.2 nm. Next, a metal layer made of Ag was formed on the first protective layer by sputtering, thereby producing a metallic color film. The sputtering conditions were as follows: The target used was an Ag target material (purity 99.9 mass %), and the pressure during film formation when Ar gas was introduced was 0.3 Pa. The average film thickness of the obtained metal layer was 70 nm.

[0061] <Examples 2 to 8, Comparative Examples 2 to 3> A metallic color film was obtained in the same manner as in Example 1, except that the average thickness of the first protective layer was changed to that shown in Table 1.

[0062] Example 9 As shown in Table 1, a metallic color film was produced in the same manner as in Example 1, except that a second protective layer was formed on the metal layer by the method described below. The second protective layer was a layer made of Ti formed on the metal layer by sputtering. The sputtering conditions were as follows: a Ti target material (purity 99.9% by mass) was used as the target, and the pressure during film formation when Ar gas was introduced was 0.3 Pa. The average film thickness of the obtained second protective layer was 1.2 nm.

[0063] <Examples 10 and 11, Comparative Examples 4 and 5> A metallic color film was obtained in the same manner as in Example 9, except that the average thickness of the first protective layer and the average thickness of the second protective layer were changed as shown in Table 1.

[0064] Example 12 A metallic color film was obtained in the same manner as in Example 1, except that the material and average thickness of the metal layer were changed as shown in Table 1. The metal layer was formed by forming a layer made of Al on the first protective layer by vacuum deposition. The conditions for the vacuum deposition were as follows: Al (purity 99.9% by mass) was used as the deposition material, and the film was formed by resistance heating deposition. The pressure during film formation was 0.03 Pa. The average thickness of the obtained metal layer was 50 nm.

[0065] <Examples 13 and 14> A metallic color film was obtained in the same manner as in Example 12, except that the average film thickness of the color-adjusting layer was changed to that shown in Table 1.

[0066] <Examples 15 to 24> A metallic color film was obtained in the same manner as in Example 1, except that the average film thickness of the color-adjusting layer was changed to that shown in Table 1.

[0067] Example 25 A substrate (PET film, thickness 50 μm) was prepared, and a metal layer made of Ag was formed on the substrate by sputtering. The sputtering conditions were as follows: An Ag target material (purity 99.9% by mass) was used as the target, and the pressure during film formation with Ar gas introduced was 0.3 Pa. The average thickness of the resulting metal layer was 70 nm. Next, a first protective layer made of Ti was formed on the metal layer by sputtering. The sputtering conditions were as follows: A Ti target material (purity 99.9% by mass) was used as the target, and the pressure during film formation with Ar gas introduced was 0.3 Pa. The average thickness of the resulting first protective layer was 1.2 nm. Next, a color-adjusting layer made of Si was formed on the first protective layer by sputtering. The sputtering conditions were as follows: A Si target material (purity 99.9% by mass) was used as the target, and the pressure during film formation with Ar gas introduced was 0.2 Pa. The average thickness of the obtained color-adjusting layer was 4.8 nm.

[0068] <Examples 26 to 27> A metallic color film was obtained in the same manner as in Example 25, except that the average film thickness of the color-adjusting layer was changed to that shown in Table 1.

[0069] <Comparative Example 6> A substrate (PET film, thickness 50 μm) was prepared, and a metal layer made of Ag was formed on the substrate by sputtering. The sputtering conditions were as follows: an Ag target material (purity 99.9 mass%) was used as the target, and the pressure during film formation when Ar gas was introduced was 0.3 Pa. The average film thickness of the obtained metal layer was 80 nm.

[0070] <Comparative Example 7> A substrate (PET film, thickness 50 μm) was prepared, and a metal layer made of Al was formed on the substrate by vacuum deposition. The conditions for the vacuum deposition were as follows: Al (purity 99.9 mass%) was used as the deposition material, and the film was formed by resistance heating deposition. The pressure during film formation was 0.03 Pa. The average film thickness of the obtained metal layer was 50 nm.

[0071] [Table 1]

[0072] The films obtained in Examples 1 to 27 and Comparative Examples 1 to 7 were evaluated for optical properties, visual color tone, and moist heat resistance by the following evaluation methods. The results are shown in Table 1.

[0073] <Optical property evaluation> The optical characteristic values ​​(a*, b*, L*) and total light reflectance (Y) in the L*a*b* color space of the light reflected from the color-adjusting layer on the side opposite the metal layer were measured using an ultraviolet-visible-near-infrared spectrophotometer (UV3600, manufactured by Shimadzu Corporation) in the wavelength range of 300 nm to 800 nm. After measuring a baseline using a standard white plate made of barium sulfate, the total light reflectance spectrum of each metallic color film was then measured. For metallic color films employing the first configuration (Examples 1 to 24, Comparative Examples 1 to 7), light was incident from the substrate side to measure the reflected light. On the other hand, for metallic color films employing the second configuration (Examples 25 to 27), light was incident from the color-adjusting layer side to measure the reflected light.

[0074] <Visual color evaluation> The tint of the metallic color film was evaluated visually. In this evaluation, the metallic color films employing the first configuration (Examples 1 to 24, Comparative Examples 1 to 7) were observed from the substrate side. On the other hand, the metallic color films employing the second configuration (Examples 25 to 27) were observed from the color-adjusting layer side.

[0075] <Heat and humidity resistance evaluation> A 5 cm x 5 cm metallic color film was prepared and tested using a thermo-hygrostat (PR-1ST, manufactured by Espec Corporation). The test was conducted under conditions of a temperature of 60°C, a humidity of 95% RH, and a test time of 168 hours. The color change before and after the test was visually observed and evaluated according to the following evaluation criteria. In this case, for metallic color films employing the first configuration (Examples 1 to 24, Comparative Examples 1 to 7), the color change was observed from the substrate side. On the other hand, for metallic color films employing the second configuration (Examples 25 to 27), the color change was observed from the color-adjusting layer side. (Evaluation criteria) ⊚: The discolored area was less than 10% of the test piece. ○: The discolored area was 10% or more and less than 30% of the test piece. △: The discolored area was 30% or more and less than 50% of the test piece. ×: The discolored area was 50% or more of the test piece.

[0076] As shown in Table 1, the metallic color films of Examples 1 to 27 of the present invention developed vivid metallic colors and had excellent resistance to moist heat.

Claims

1. a substrate, a first layer, and a second layer are provided in this order; the first layer is either a color adjusting layer or a metal layer, the second layer is a color-adjusting layer or a metal layer, which is the other layer different from the layer selected as the first layer, a first protective layer is provided between the first layer and the second layer; the color-adjusting layer contains Si, the metal layer contains at least one of Ag and Al, the first protective layer contains Ti; A metallic color film, wherein the average thickness of the first protective layer is 1.2 nm or more.

2. 2. The metallic color film according to claim 1, wherein the color-adjusting layer has an average film thickness of 2.9 to 100 nm.

3. 3. The metallic color film according to claim 1, wherein the first protective layer has an average thickness of 5 nm or less.

4. a second protective layer is further provided on a surface of the metal layer opposite to a surface in contact with the first protective layer; 3. The metallic color film according to claim 1, wherein the second protective layer contains Ti.

Images