Film mirror laminate and mirror member

Abstract

To provide a film mirror laminate and a mirror member which suppress corrosion of a metal reflection layer and suppress deterioration of adhesion between layers.SOLUTION: The film mirror laminate 1 sequentially includes a substrate film 2, a metal reflective layer 3, a reflection adjusting layer 4, and a water repellent layer 5 toward one side in the thickness direction. The reflection adjusting layer 4 includes a silicon oxide layer 43, and the water repellent layer 5 is disposed on one surface in the thickness direction of the silicon oxide layer 43. The water-repellent layer (5) has a water contact angle of 110 ° or more at one surface thereof in the thickness direction.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film mirror laminate and a mirror member. [Background technology]

[0002] In recent years, AR (Augmented Reality) technology has been attracting attention, and development of head-up display devices using AR technology is progressing. A head-up display device is a device that forms a virtual image in front of the driver of a vehicle such as an automobile, and displays traffic information such as route information and congestion information, as well as vehicle information such as remaining fuel and coolant temperature.

[0003] In a head-up display device, an image from a light source such as a liquid crystal display is reflected by a mirror (reflector), and is visually recognized by the driver as a virtual image. As a reflector used in such a head-up display device, an aluminum surface reflector has been proposed, which has an aluminum layer, an SiO2 layer (first low refractive index layer), a ZrO2 layer (high refractive index layer), and an SiO2 layer (second low refractive index layer) sequentially on a substrate such as glass (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-173005 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the aluminum surface reflector described in Patent Document 1 is susceptible to corrosion of the aluminum layer, which may reduce adhesion between layers.

[0006] The present invention provides a film mirror laminate and a mirror member that suppress corrosion of a metal reflective layer and suppress deterioration of adhesion between layers. [Means for solving the problem]

[0007] The present invention [1] includes a film mirror laminate comprising a substrate film, a metal reflective layer, a reflection adjustment layer, and a water-repellent layer, in that order toward one side in the thickness direction, the reflection adjustment layer comprising a silicon oxide layer, the water-repellent layer being disposed on one side in the thickness direction of the silicon oxide layer, and the water contact angle on one side in the thickness direction of the water-repellent layer being 110° or more.

[0008] The present invention [2] includes the film mirror laminate described in the above [1], which has a reflectance of 95.0% or more for visible light having a wavelength of 360 to 740 nm when irradiated from one side in the thickness direction of the film mirror laminate.

[0009] The present invention [3] includes the film mirror laminate according to the above [1] or [2], wherein the metal reflective layer contains at least one metal selected from the group consisting of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag).

[0010] The present invention [4] includes a film mirror laminate according to any one of the above [1] to [3], wherein the reflection adjustment layer comprises a low refractive index layer, a high refractive index layer, and the silicon oxide layer, in that order toward one side in the thickness direction.

[0011] The present invention [5] includes the film mirror laminate according to any one of the above [1] to [4], wherein the thickness of the silicon oxide layer is 50 nm or less.

[0012] The present invention [6] includes the film mirror laminate according to any one of the above [1] to [5], wherein the water-repellent layer is a dry coating layer.

[0013] The present invention [7] includes a mirror member having, in order toward one side in the thickness direction, a supporting substrate, a pressure-sensitive adhesive layer, and the film mirror laminate described in any one of [1] to [6] above. [Effects of the Invention]

[0014] The film mirror laminate of the present invention comprises a substrate film, a metal reflective layer, a reflection adjustment layer, and a water-repellent layer, arranged in this order toward one side in the thickness direction, the reflection adjustment layer comprises a silicon oxide layer, the water-repellent layer is disposed on one surface in the thickness direction of the silicon oxide layer, and the water contact angle on one surface in the thickness direction of the water-repellent layer is 110° or more. Therefore, corrosion of the metal reflective layer can be suppressed, and a decrease in adhesion between layers can be suppressed.

[0015] The mirror member of the present invention includes a support substrate, a pressure-sensitive adhesive layer, and the above-mentioned film mirror laminate in this order toward one side in the thickness direction. Therefore, corrosion of the metal reflective layer can be suppressed, and a decrease in adhesion between layers can be suppressed. As a result, the reliability of the mirror member is improved. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 shows a cross-sectional view of one embodiment of the film mirror laminate of the present invention. [Figure 2] FIG. 2 shows a cross-sectional view of a mirror member using the film mirror laminate shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0017] 1. Film mirror laminate Referring to FIG. 1, one embodiment of the film mirror laminate of the present invention will be described.

[0018] The film mirror laminate 1 is in the form of a film (including a sheet) having a predetermined thickness, as shown in Fig. 1. The film mirror laminate 1 extends in a plane direction (a first direction and a second direction perpendicular to the first direction) perpendicular to the thickness direction, and one surface and the other surface in the thickness direction of the film mirror laminate 1 are flat.

[0019] The film mirror laminate 1 includes, in this order toward one side in the thickness direction, a substrate film 2, a metal reflective layer 3, a reflection adjustment layer 4, and a water-repellent layer 5. Specifically, as shown in Fig. 1 , the film mirror laminate 1 includes a substrate film 2, a metal reflective layer 3 disposed on one surface in the thickness direction of the substrate film 2, a reflection adjustment layer 4 disposed on one surface in the thickness direction of the metal reflective layer 3, and a water-repellent layer 5 disposed on one surface in the thickness direction of the reflection adjustment layer 4.

[0020] <Base film> The base film 2 is the bottom layer of the film mirror laminate 1 and supports the film mirror laminate 1. The base film 2 includes a transparent resin film 21. Furthermore, the base film 2 further includes a cured resin layer 22 disposed on one surface in the thickness direction and / or the other surface in the thickness direction of the transparent resin film 21, as necessary. In this embodiment, the base film 2 includes the transparent resin film 21 and the cured resin layer 22 disposed on one surface in the thickness direction of the transparent resin film 21.

[0021] The transparent resin film 21 has a film shape (including a sheet shape) and is, for example, a flexible, transparent resin film.

[0022] Examples of materials for the transparent resin film 21 include cellulose resin, polyester resin, (meth)acrylic resin (acrylic resin and / or methacrylic resin), olefin resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, polystyrene resin, norbornene resin, and polyvinyl alcohol resin. Polyester resin, polyolefin resin, and cellulose resin are preferred. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of cellulose resins include triacetyl cellulose (TAC). From the viewpoints of transparency, heat resistance, mechanical strength, and the like, the transparent resin film 21 is preferably at least one selected from the group consisting of a PET film, a COP film, and a TAC film. A PET film is more preferred. The materials for the transparent resin film 21 can be used alone or in combination.

[0023] The transparent resin film 21 has a total light transmittance (JISK-7105) of, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and for example, 100% or less.

[0024] The thickness of the transparent resin film 21 is not particularly limited, but from the viewpoint of strength and ease of handling, it is, for example, 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0025] The thickness of the transparent resin film 21 can be measured using, for example, a film thickness meter.

[0026] The cured resin layer 22 is a layer that improves the mechanical properties of the film mirror laminate 1. The cured resin layer 22 is in contact with one surface of the transparent resin film 21 in the thickness direction, for example.

[0027] Examples of the cured resin layer 22 include a hard coat layer and an anti-blocking layer. The hard coat layer, for example, makes it difficult for scratches to form on the exposed surface of the transparent resin film 21. The anti-blocking layer, for example, imparts anti-blocking properties to the surfaces of the multiple film mirror laminates 1 that come into contact with each other when the film mirror laminates 1 are stacked in the thickness direction.

[0028] The cured resin layer 22 is, for example, a cured product of a curable resin composition. Specifically, the cured resin layer 22 can be formed by applying a curable resin composition to one surface in the thickness direction of the transparent resin film 21, drying the composition as necessary, and then curing the composition.

[0029] The curable resin composition contains a curable resin. Examples of the curable resin include polyester resin, acrylic urethane resin, acrylic resin (excluding acrylic urethane resin), urethane resin (excluding acrylic urethane resin), amide resin, silicone resin, epoxy resin, and melamine resin. Preferably, acrylic urethane resin is used. The curable resin can be used alone or in combination of two or more kinds.

[0030] Examples of the curable resin composition include an ultraviolet-curable resin composition and a thermosetting resin composition. From the viewpoint of production efficiency, the curable resin composition is preferably an ultraviolet-curable resin composition. The ultraviolet-curable resin composition contains at least one selected from the group consisting of an ultraviolet-curable monomer, an ultraviolet-curable oligomer, and an ultraviolet-curable polymer. A specific example of the ultraviolet-curable resin composition is a composition for forming a hard coat layer described in JP 2016-179686 A.

[0031] The curable resin composition preferably contains particles from the viewpoints of adjusting the hardness, surface roughness, refractive index, and anti-glare properties of the cured resin layer 22. Examples of the particles include inorganic particles and organic particles. Preferably, inorganic particles are used. Examples of the inorganic particles include inorganic oxide particles. Examples of materials for the inorganic oxide particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Preferably, silica is used. Examples of materials for the organic particles include polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate.

[0032] The particles have a number average primary particle diameter of, for example, 5 nm or more, preferably 10 nm or more, and for example, 150 nm or less, preferably 100 nm or less.

[0033] The curable resin composition preferably contains a photopolymerization initiator. The curable resin composition may further contain additives such as a solvent, a leveling agent, a thixotropic agent, and an antistatic agent.

[0034] The thickness of the cured resin layer 22 is, for example, 0.5 μm or more, or preferably 1.0 μm or more, and for example, 10 μm or less, or preferably 5 μm or less.

[0035] When the thickness of the cured resin layer 22 is equal to or greater than the above lower limit, it is possible to fully exhibit the function of the cured resin layer 22. When the thickness of the cured resin layer is equal to or less than the above upper limit, it is possible to reduce the thickness of the film mirror laminate 1.

[0036] One surface in the thickness direction of the substrate film 2 (one surface in the thickness direction of the cured resin layer 22) may be subjected to a surface modification treatment in order to improve adhesion with the metal reflective layer 3 described below. Examples of surface modification treatments include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment. Plasma treatment is preferred. In other words, one surface in the thickness direction of the substrate film 2 (one surface in the thickness direction of the cured resin layer 22) is preferably a plasma-treated surface.

[0037] The total light transmittance (JISK-7105) of the base film 2 is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and for example, 100% or less.

[0038] The thickness of the base film 2 is not particularly limited, but from the viewpoint of strength and handleability, it is, for example, 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0039] <Metal reflective layer> The metal reflective layer 3 is a metal layer having light reflectivity. The metal reflective layer 3 is in contact with one surface in the thickness direction of the base film 2. In this embodiment, the metal reflective layer 3 is in contact with one surface in the thickness direction of the cured resin layer 22.

[0040] Examples of materials for the metal reflective layer 3 include metals with light reflectivity. Specifically, the metal reflective layer 3 contains, for example, at least one metal selected from the group consisting of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), or an alloy of two or more of these metals. Preferably, it contains aluminum or an aluminum alloy. From the viewpoint of light reflectivity, the metal reflective layer 3 is more preferably an aluminum layer. Note that an aluminum alloy is an alloy with an aluminum content of 50 mass % or more.

[0041] The metal reflective layer 3 is, for example, a layer (dry coating layer) formed by a dry coating method. Examples of dry coating methods include sputtering, vacuum deposition, and CVD. Preferably, sputtering is used. That is, the metal reflective layer 3 is preferably a dry coating layer. More preferably, it is a layer (sputter layer) formed by a sputtering method.

[0042] The metal reflective layer 3 has a thickness T1 of, for example, 10 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and for example, 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less.

[0043] When the thickness T1 of the metal reflective layer 3 is equal to or greater than the above-mentioned lower limit, the metal reflective layer 3 can have appropriate light reflectivity. When the thickness T1 of the metal reflective layer 3 is equal to or less than the above-mentioned upper limit, the metal reflective layer 3 can be easily formed with a uniform thickness, and light scattering and the like can be suppressed.

[0044] <Reflection adjustment layer> The reflection adjustment layer 4 is a layer that adjusts the intensity of reflected light, which will be described in detail later. The reflection adjustment layer 4 is in contact with the metal reflective layer 3.

[0045] The reflection adjustment layer 4 includes, on one side in the thickness direction, a silicon oxide layer 43. That is, the silicon oxide layer 43 is disposed at a position in the reflection adjustment layer 4 that is farthest from the metal reflective layer 3 in the thickness direction.

[0046] Reflection adjustment layer 4 has silicon oxide layer 43 on one side in the thickness direction, which can improve adhesion to water-repellent layer 5 described later.

[0047] In this embodiment, the reflection adjustment layer 4 includes a low refractive index layer 41 (first layer), a high refractive index layer 42 (second layer), and a silicon oxide layer 43 (third layer) in this order toward one side in the thickness direction. In other words, the low refractive index layer 41 (first layer) is in contact with the metal reflective layer 3. The high refractive index layer 42 (second layer) is in contact with the low refractive index layer 41 (first layer). The silicon oxide layer 43 (third layer) is in contact with the high refractive index layer 42 (second layer). The low refractive index layer 41 is a layer with a relatively low refractive index, and the high refractive index layer 42 is a layer with a relatively high refractive index.

[0048] The reflection adjustment layer 4 includes a low refractive index layer 41, a high refractive index layer 42, and a silicon oxide layer 43, arranged in this order toward one side in the thickness direction, and by adjusting the thickness of each layer as described below, it is possible to align the phases of the reflected light at multiple interfaces and increase the net reflected light intensity. Therefore, when used as a mirror member 10, the visibility of the image reflected on the mirror member 10 can be improved.

[0049] 1, in this embodiment, reflection adjustment layer 4 has three layers, but is not particularly limited to any number of layers as long as the above-mentioned effect (aligning the phases of reflected light at multiple interfaces and increasing the net reflected light intensity) can be obtained. The number of layers in reflection adjustment layer 4 is, for example, three, four, or five or more. Preferably, it is three layers.

[0050] The low refractive index layer 41 (first layer) is made of a low refractive index material having a refractive index of, for example, 1.6 or less at a wavelength of 550 nm. From the viewpoint of achieving both a low refractive index and low absorption of visible light, examples of the low refractive index material include silicon oxide (SiOx) and magnesium fluoride, and preferably silicon oxide (SiOx).

[0051] Examples of silicon oxides (SiOx) include silicon oxides (silicon dioxide) where X=2 and silicon oxides where X<2. Preferably, silicon dioxide is used.

[0052] That is, the low refractive index layer 41 (first layer) is preferably a first silicon oxide layer, and more preferably a first silicon dioxide layer. The refractive index of the silicon dioxide layer at a wavelength of 550 nm is 1.46.

[0053] The low refractive index layer 41 (first layer) has a thickness t1 of, for example, 10 nm or more, preferably 30 nm or more, and for example, 150 nm or less, preferably 100 nm or less. The low refractive index layer 41 (first layer) has an optical film thickness (product of refractive index and thickness) of, for example, 50 nm or more, and for example, 150 nm or less.

[0054] The high refractive index layer 42 (second layer) is made of a high refractive index material having a refractive index of, for example, 1.9 or more at a wavelength of 550 nm. From the viewpoint of achieving both a high refractive index and low absorption of visible light, examples of high refractive index materials include niobium oxide (NbO), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO), and preferably niobium oxide.

[0055] That is, the high refractive index layer 42 (second layer) is preferably a niobium oxide layer, which has a refractive index of 2.33 at a wavelength of 550 nm.

[0056] The thickness t2 of the high refractive index layer 42 (second layer) is, for example, 10 nm or more, preferably 25 nm or more, and for example, 130 nm or less, preferably 80 nm or less. The optical film thickness (product of refractive index and thickness) of the high refractive index layer 42 (second layer) is, for example, 70 nm or more, and for example, 170 nm or less.

[0057] The silicon oxide layer 43 (third layer) is a layer made of silicon oxide. The silicon oxide layer 43 (third layer) has a refractive index of 1.6 or less at a wavelength of 550 nm. In other words, the silicon oxide layer 43 (third layer) is one of low refractive index layers. When the low refractive index layer 41 (first layer) is a first silicon oxide layer, the silicon oxide layer 43 (third layer) is a second silicon oxide layer.

[0058] Examples of silicon oxides (SiOx) include silicon oxides (silicon dioxide) where X=2 and silicon oxides where X<2. Preferably, silicon dioxide is used.

[0059] That is, the silicon oxide layer 43 (third layer) is preferably a second silicon dioxide layer. The refractive index of the silicon dioxide layer at a wavelength of 550 nm is 1.46.

[0060] The thickness t3 of the silicon oxide layer 43 (third layer) is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, and for example, 50 nm or less, preferably 40 nm or less, more preferably 35 nm or less, even more preferably 30 nm or less.

[0061] The thickness t3 of the silicon oxide layer 43 (third layer) is in the range of, for example, 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 35 nm, and still more preferably 15 nm to 30 nm.

[0062] If the thickness t3 of the silicon oxide layer 43 (third layer) is within the above range, the adhesion to the water-repellent layer 5 can be improved.

[0063] The optical film thickness (product of refractive index and thickness) of the silicon oxide layer 43 (third layer) is, for example, 20 nm or more and, for example, 40 nm or less.

[0064] The reflection adjustment layer 4 is, for example, a layer formed by a dry coating method (dry coating layer). Dry coating methods include sputtering, vacuum deposition, and CVD. Preferably, sputtering is used. That is, the reflection adjustment layer 4 is preferably a dry coating layer. More preferably, it is a layer formed by a sputtering method (sputter layer).

[0065] The total thickness T2 of the reflection adjustment layer 4 (corresponding to t1+t2+t3 in this embodiment) is, for example, 50 nm or more, preferably 80 nm or more, more preferably 100 nm or more, and for example, 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less.

[0066] The ratio (t1 / T2×100) of the thickness t1 of the low refractive index layer 41 (first layer) to the total thickness T2 of the reflection adjustment layer 4 is, for example, 30% or more, preferably 40% or more, and for example, 70% or less, preferably 60% or less.

[0067] The ratio (t2 / T2×100) of the thickness t2 of the high refractive index layer 42 (second layer) to the total thickness T2 of the reflection adjustment layer 4 is, for example, 20% or more, preferably 30% or more, and for example, 60% or less, preferably 50% or less, and more preferably 40% or less.

[0068] The ratio (t3 / T2×100) of the thickness t3 of the silicon oxide layer 43 (third layer) to the total thickness T2 of the reflection adjustment layer 4 is, for example, 5% or more, preferably 10% or more, and for example, 30% or less, preferably 20% or less.

[0069] The thickness t3 of the silicon oxide layer 43 (third layer) is thinner than the thickness t1 of the low refractive index layer 41 (first layer). The thickness t3 of the silicon oxide layer 43 (third layer) is also thinner than the thickness t2 of the high refractive index layer 42 (second layer).

[0070] By adjusting the total thickness T2 of the reflection adjustment layer 4, the thickness t1 of the low refractive index layer 41, the thickness t2 of the high refractive index layer 42, and the thickness t3 of the silicon oxide layer 43 within the above-mentioned ranges, it is possible to align the phases of the reflected light at multiple interfaces and increase the net reflected light intensity. Therefore, when used as the mirror member 10, the visibility of the image reflected on the mirror member 10 can be improved.

[0071] One surface in the thickness direction of the silicon oxide layer 43 (the surface in contact with the water-repellent layer 5) may be subjected to a surface modification treatment. Examples of the surface modification treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.

[0072] <Water-repellent layer> The water-repellent layer 5 has water-repellent properties against water droplets. The water-repellent layer 5 also prevents contamination from the external environment and facilitates the removal of adhered contaminants. The water-repellent layer 5 is disposed on one surface in the thickness direction of the silicon oxide layer 43. The water-repellent layer 5 is in contact with the silicon oxide layer 43. The water-repellent layer 5 is the uppermost layer of the film mirror laminate 1.

[0073] Since the uppermost layer of the film mirror laminate 1 is the water-repellent layer 5, even if the reflection adjustment layer 4 (particularly the silicon oxide layer 43) is relatively thin, corrosion caused by water droplets can be suppressed.

[0074] The material of the water-repellent layer 5 can be an organic fluorine compound having a terminal structure (terminal structure E) represented by the chemical formula CF3OCF2-. That is, the water-repellent layer 5 contains an organic fluorine compound having terminal structure E. A preferred example of such an organic fluorine compound is an alkoxysilane compound having a perfluoropolyether skeleton. An example of an alkoxysilane compound having terminal structure E and a perfluoropolyether skeleton is a compound represented by the following general formula (1):

[0075] CF3-OCF2-R1-X-(CH2) m -Si(OR2)3(1)

[0076] R1 represents a structure containing at least one repeating unit of a perfluoropolyether (PFPE) group, and preferably represents a structure containing two repeating units of a PFPE group. Examples of the repeating unit of a PFPE group include a repeating unit of a linear PFPE group and a repeating unit of a branched PFPE group. Examples of the repeating unit of a linear PFPE group include -(OC n F 2n) p (n represents an integer of 1 or more and 20 or less, and p represents an integer of 1 or more and 100 or less; the same applies hereinafter). Examples of the repeating structure of the branched PFPE group include a structure represented by -(OC(CF3)2) p - and -(OCF2CF(CF3)CF2) p The repeating structure of the PFPE group is preferably a repeating structure of a linear PFPE group. More preferably, it is -(OCF2) p -and-(OC2F4) p -. R2 is, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. X is, for example, an ether group, a carbonyl group, an amino group, or an amide group, and preferably an ether group. m is, for example, an integer of 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

[0077] The alkoxysilane compounds having a perfluoropolyether skeleton can be used alone or in combination of two or more kinds.

[0078] If the water-repellent layer 5 contains an alkoxysilane compound having a perfluoropolyether skeleton, the water repellency of the water-repellent layer 5 can be improved.

[0079] The water-repellent layer 5 may be a layer formed by a dry coating method (dry coating layer) or a layer formed by a wet coating method (wet coating layer). Dry coating methods include sputtering, vacuum deposition, and CVD. Vacuum deposition is preferred. That is, the water-repellent layer 5 is preferably a dry coating layer. More preferably, it is a layer formed by a vacuum deposition method (vacuum deposition layer).

[0080] The water contact angle (pure water contact angle) on one surface (exposed surface) in the thickness direction of the water-repellent layer 5 is 110° or more, preferably 111° or more, more preferably 112° or more, even more preferably 115° or more, particularly preferably 117° or more, and, for example, 130° or less.

[0081] The water contact angle (pure water contact angle) on one surface (exposed surface) in the thickness direction of the water-repellent layer 5 is, for example, 110° to 130°, preferably 111° to 130°, more preferably 112° to 130°, even more preferably 115° to 130°, and particularly preferably 117° to 130°.

[0082] If the water contact angle of one surface in the thickness direction of the water-repellent layer 5 is equal to or greater than the above lower limit, the water-repellent layer 5 has high water repellency. Therefore, corrosion of the metal reflective layer 3 due to water droplets (tap water droplets) can be suppressed, and a decrease in adhesion between layers can be suppressed.

[0083] The water contact angle can be determined by the method described in the Examples below. The water contact angle of the outer surface of the water-repellent layer 5 can be adjusted, for example, by the composition of the water-repellent layer 5, the method for forming the water-repellent layer 5, and the composition of other layers.

[0084] The thickness T3 of the water-repellent layer 5 is, for example, 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and for example, 50 nm or less, preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 7 nm or less.

[0085] The ratio (T3 / t3) of the thickness T3 of the water-repellent layer 5 to the thickness t3 of the silicon oxide layer 43 is, for example, 0.10 or more, preferably 0.15 or more, more preferably 0.20 or more, and for example, 0.80 or less, preferably 0.60 or less, more preferably 0.50 or less, and even more preferably 0.40 or less.

[0086] The thickness T3 of the water-repellent layer 5 is preferably smaller than the thickness t3 of the silicon oxide layer 43.

[0087] The water-repellent layer 5 preferably has a small difference in refractive index from the layer (silicon oxide layer 43) that it comes into contact with. The refractive index of the water-repellent layer 5 is, for example, 1.6 or less, or preferably 1.55 or less.

[0088] The thickness of the film mirror laminate 1 is, for example, 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0089] In the film mirror laminate 1, the ratio (T1 / T2) of the thickness T1 of the metal reflective layer 3 to the thickness T2 of the reflection adjustment layer 4 is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, and for example, 0.7 or less, preferably 0.5 or less, more preferably 0.4 or less.

[0090] In the film mirror laminate 1, the ratio (T3 / T2) of the thickness T3 of the water-repellent layer 5 to the thickness T2 of the reflection adjustment layer 4 is, for example, 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, and for example, 0.20 or less, preferably 0.10 or less, more preferably 0.08 or less.

[0091] The reflectance of visible light with a wavelength of 360 to 740 nm irradiated from one side in the thickness direction of the film mirror laminate 1 is, for example, 95.0% or more, preferably 95.5% or more, and more preferably 96.0% or more.

[0092] The reflectance of visible light having a wavelength of 360 to 740 nm irradiated from one side in the thickness direction of the film mirror laminate 1 can be measured by the method described in the examples below.

[0093] The film mirror laminate 1 may have layers other than those described above depending on the intended use. Examples of the other layers include a protective layer and an anti-glare layer.

[0094] <Method of manufacturing film mirror laminate> The above-mentioned film mirror laminate 1 can be manufactured by preparing a substrate film 2 and sequentially forming a metal reflective layer 3, a reflection adjustment layer 4, and a water-repellent layer 5 on the substrate film 2. In this embodiment, the reflection adjustment layer 4 can be formed by sequentially laminating a low refractive index layer 41, a high refractive index layer 42, and a silicon oxide layer 43.

[0095] In other words, the manufacturing method of the film mirror laminate 1 includes, for example, a step of preparing a substrate film 2 (preparation step), a step of forming a metal reflective layer 3 on the substrate film 2 (metal reflective layer formation step), a step of forming a reflection adjustment layer 4 on the metal reflective layer 3 (reflection adjustment layer formation step), and a step of forming a water-repellent layer 5 on the reflection adjustment layer 4 (water-repellent layer formation step).

[0096] The base film 2 can be produced by preparing a transparent resin film 21 and forming a cured resin layer 22 on one surface in the thickness direction of the transparent resin film 21. Specifically, the cured resin layer 22 is formed by applying the above-described curable resin composition to one surface in the thickness direction of the transparent resin film 21 to form a coating film, and then curing this coating film.

[0097] When the curable resin composition contains a solvent, after the curable resin composition is applied, the coating film on the transparent resin film 21 is dried. The drying temperature is, for example, 50° C. to 120° C. The drying time is, for example, 10 seconds to 10 minutes.

[0098] When the curable resin composition contains an ultraviolet-curable resin, the coating film on the transparent resin film 21 is cured by ultraviolet irradiation. Examples of the light source for ultraviolet irradiation include a high-pressure mercury lamp and an LED light. The cumulative irradiation amount of ultraviolet light is, for example, 100 mJ / cm. 2 ~500mJ / cm 2 Furthermore, when the curable resin composition contains a thermosetting resin, the coating film on the transparent resin film 21 is cured by heating.

[0099] One surface in the thickness direction of the substrate film 2 (one surface in the thickness direction of the cured resin layer 22) is subjected to a surface modification treatment as required. When plasma treatment is performed as the surface modification treatment, for example, a sputtering film formation device (magnetron sputtering film formation device) capable of performing a film formation process by a roll-to-roll method is used. Specifically, under vacuum conditions (for example, an ultimate vacuum of 1.5×10 -4 An inert gas (e.g., argon) is introduced under conditions of 0.005 Pa or less (the same applies hereinafter) to plasma-treat one surface in the thickness direction of the substrate film 2. The effective power density of the plasma treatment is, for example, 0.005 W·min / cm. 2 ·m~1.00W·min / cm 2 ·m. Note that the effective power density is the power density of the plasma output (W / cm 2 ) divided by the transport speed (m / min) of the base film 2 in the roll-to-roll system.

[0100] The metal reflective layer 3 can be formed by depositing the material for the metal reflective layer 3 on the substrate film 2. The reflection adjustment layer 4 can be formed by depositing the material for the reflection adjustment layer 4 on the metal reflective layer 3. The reflection adjustment layer 4 can be formed by sequentially laminating a low refractive index layer 41, a high refractive index layer 42, and a silicon oxide layer 43. The metal reflective layer 3 and the reflection adjustment layer 4 (the low refractive index layer 41, the high refractive index layer 42, and the silicon oxide layer 43) are preferably formed continuously.

[0101] The metal reflective layer 3 and the reflection adjustment layer 4 can be formed by depositing the respective materials by, for example, a dry coating method. Examples of the dry coating method include sputtering, vacuum deposition, and CVD. Sputtering is preferred.

[0102] The sputtering method uses a sputtering deposition apparatus (magnetron sputtering deposition apparatus) that can perform a film formation process using a roll-to-roll method. A gas is introduced into a deposition chamber in the sputtering deposition apparatus under vacuum conditions, while a negative voltage is applied to a target placed on a cathode. This generates a glow discharge, ionizing the gas atoms, causing the gas ions to collide with the target surface at high speed, ejecting target material from the target surface and depositing the ejected target material on a predetermined surface. Examples of the gas include inert gases. Examples of the inert gas include argon, krypton, xenon, and mixtures of these gases.

[0103] The target material includes the material of the metal reflective layer 3 and the material of the reflection adjustment layer 4 (the low refractive index layer 41, the high refractive index layer 42, and the silicon oxide layer 43).

[0104] To form a metal (semi-metal) oxide layer, a sintered body of metal (semi-metal) oxide may be used as a target material, or a metal (semi-metal) material may be used as a target material for reactive sputtering. From the viewpoint of film formation speed, reactive sputtering is preferably used for film formation using a metal (semi-metal) material. In this embodiment, the low refractive index layer 41 and the silicon oxide layer 43 are formed by reactive sputtering using silicon (Si) as a material, and the high refractive index layer 42 is formed by reactive sputtering using niobium (Nb) as a material. Note that the semi-metal refers to silicon (Si).

[0105] In reactive sputtering, a mixed gas of an inert gas and oxygen (reactive gas) is used as the gas. The proportion of oxygen contained in the metal oxide layer to be formed can be adjusted by adjusting the mixing ratio (volume ratio) of the inert gas and oxygen. The volume ratio of the inert gas to oxygen (volume of oxygen when the volume of the inert gas is 100) is, for example, 3 to 50.

[0106] Examples of power sources for sputtering include DC power sources, AC power sources, RF power sources, and MF-AC power sources (AC power sources with a frequency band of several tens to several hundreds of MHz). The discharge power in sputtering is, for example, 0.05 kW to 40 kW. The pressure in the film formation chamber when gas (inert gas and / or oxygen) is introduced is, for example, 0.01 Pa to 2 Pa. The film formation temperature is, for example, -20°C to 40°C.

[0107] The water-repellent layer 5 can be formed by depositing a material for the water-repellent layer 5 on the reflection adjustment layer 4. Methods for depositing the water-repellent layer 5 include dry coating and wet coating. Examples of dry coating methods include vacuum deposition, sputtering, and CVD, and preferably vacuum deposition.

[0108] In the vacuum deposition method, the material of the water-repellent layer 5 is dried and solidified and used as a deposition source, and heated to deposit the material of the water-repellent layer 5 on the reflection adjustment layer 4. The heating temperature of the deposition source is not particularly limited as long as it is a temperature at which the material of the water-repellent layer 5 can be evaporated, and is, for example, 150°C to 500°C. When the dry coating method (vacuum deposition method) is used as the method for forming the water-repellent layer 5, a sputtering film-forming apparatus (magnetron sputtering film-forming apparatus) that can perform a film-forming process by a roll-to-roll method can be used. In this case, the metal reflective layer 3, the reflection adjustment layer 4, and the water-repellent layer 5 can be formed consecutively.

[0109] In the wet coating method, a solvent (for example, a fluorine-based solvent) is added to the material for water-repellent layer 5, and the material is diluted to prepare a water-repellent layer composition, which is then applied to one surface in the thickness direction of reflection adjustment layer 4 and dried to form water-repellent layer 5. The drying temperature is, for example, 50°C to 120°C. The drying time is, for example, 10 seconds to 10 minutes.

[0110] In this manner, the film mirror laminate 1 can be manufactured.

[0111] (Action and effect) The above-mentioned film mirror laminate 1 comprises a substrate film 2, a metal reflective layer 3, a reflection adjustment layer 4, and a water-repellent layer 5, arranged in this order toward one side in the thickness direction, the reflection adjustment layer 4 comprises a silicon oxide layer 43, the water-repellent layer 5 is disposed on one surface in the thickness direction of the silicon oxide layer 43, and the water contact angle on one surface in the thickness direction of the water-repellent layer 5 is 110° or more. Therefore, corrosion of the metal reflective layer can be suppressed, and a decrease in adhesion between layers can be suppressed.

[0112] Specifically, the water-repellent layer 5 has a water contact angle of 110° or more on one surface in the thickness direction, and has high water repellency. Therefore, even when water droplets (tap water droplets) adhere to the water-repellent layer 5, corrosion of the metal reflective layer 3 can be suppressed. Consequently, deterioration in interlayer adhesion resulting from corrosion of the metal reflective layer 3 can be suppressed.

[0113] The corrosion of the metal reflective layer 3 can be caused by, for example, chloride ions (Cl ) contained in tap water or the atmosphere. - Specifically, the natural oxide film (Al2O3 film) on the surface of the metal reflective layer 3 is formed by Cl - The area is locally destroyed by Cl, and pitting corrosion progresses from that point. - As a result of the accumulation of chlorides, the chloride concentration increases, dissolving the material (for example, Al) of the metal reflective layer 3. In this way, corrosion of the metal reflective layer 3 progresses.

[0114] 2. Mirror parts Referring to FIG. 2, one embodiment of the mirror member 10 of the present invention will be described.

[0115] The mirror member 10 includes, for example, a support substrate 6, a pressure-sensitive adhesive layer 7, and the above-mentioned film mirror laminate 1, arranged in this order toward one side in the thickness direction. Specifically, as shown in FIG. 2, the mirror member 10 includes a support substrate 6, a pressure-sensitive adhesive layer 7 disposed on one surface in the thickness direction of the support substrate 6, and a film mirror laminate 1 disposed on one surface in the thickness direction of the pressure-sensitive adhesive layer 7. At this time, one surface in the thickness direction of the pressure-sensitive adhesive layer 7 contacts the other surface in the thickness direction of the film mirror laminate 1 (the exposed surface of the substrate film 2). Note that one surface in the thickness direction (uppermost layer) of the mirror member 10 is a water-repellent layer 5.

[0116] The mirror member 10 may be in the form of a film (including a sheet) or a plate, and extends in a plane direction perpendicular to the thickness direction.

[0117] <Supporting base material> The material of the support substrate 6 is not particularly limited and is appropriately selected depending on the application of the mirror member 10. Examples of materials for the support substrate 6 include resin, glass, and metal. From the viewpoint of flexibility, the material for the support substrate 6 is preferably resin. Examples of resins include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; olefin resins such as polyethylene, polypropylene, and cycloolefin polymer; (meth)acrylic resins (acrylic resins and / or methacrylic resins); polycarbonate resins; polyethersulfone resins; polyarylate resins; melamine resins; polyamide resins; polyimide resins; polystyrene resins; norbornene resins; cellulose resins; and polyvinyl alcohol resins.

[0118] The thickness of the supporting substrate 6 is not particularly limited and is appropriately selected depending on the application of the mirror member 10. The thickness of the supporting substrate 6 is, for example, 15 μm to 150 μm.

[0119] The dimensions of the supporting substrate 6 (length in the first direction and length in the second direction) are not particularly limited and are selected appropriately depending on the application of the mirror member 10. The length in the first direction of the supporting substrate 6 is, for example, equal to or greater than the length in the first direction of the film mirror laminate 1. Furthermore, the length in the second direction of the supporting substrate 6 is, for example, equal to or greater than the length in the second direction of the film mirror laminate 1.

[0120] <Adhesive layer> Examples of materials for the pressure-sensitive adhesive layer 7 include the pressure-sensitive adhesive composition described in JP-A-2023-110548.

[0121] The thickness of the adhesive layer 7 is not particularly limited as long as it can bond the supporting substrate 6 and the film mirror laminate 1, and is, for example, 5 μm to 100 μm.

[0122] <Method of manufacturing mirror member> The mirror member 10 can be manufactured by preparing an adhesive layer 7 (adhesive sheet) and bonding the supporting substrate 6 and the film mirror laminate 1 with the adhesive layer 7 interposed therebetween.

[0123] That is, the manufacturing method of the mirror member 10 includes, for example, a step of preparing the adhesive layer 7 (adhesive sheet) and a step of bonding the supporting substrate 6 and the film mirror laminate 1 via the adhesive layer 7.

[0124] The pressure-sensitive adhesive layer 7 is prepared, for example, by the method described in JP 2023-110548 A. Specifically, it is prepared by the method described in the Examples below. In this case, the pressure-sensitive adhesive layer 7 is prepared as a laminate sandwiched between a first release liner and a second release liner (first release liner / pressure-sensitive adhesive layer / second release liner).

[0125] The support substrate 6 and the film mirror laminate 1 are bonded via the adhesive layer 7 obtained by peeling off the first release liner and the second release liner from the above laminate. Specifically, one thickness-wise surface of the support substrate 6 is bonded to the other thickness-wise surface of the film mirror laminate 1 (the exposed surface of the transparent resin film 21) via the adhesive layer 7.

[0126] In this manner, the mirror member 10 can be manufactured.

[0127] (Action and effect) The mirror member 10 includes the film mirror laminate 1. This can prevent corrosion of the metal reflective layer 3 and prevent a decrease in adhesion between layers. As a result, the reliability of the mirror member 10 is improved.

[0128] (Application) The film mirror laminate 1 and the mirror member 10 can be used for, for example, vehicle structural parts, vehicle-mounted items such as head-up displays, housings for electronic devices, housings for home appliances, structural parts, machine parts, various automobile parts, electronic device parts, household goods such as furniture and kitchen utensils, medical equipment, building material parts, and exterior parts. The film mirror laminate 1 and the mirror member 10 are particularly suitable for head-up display applications. [Example]

[0129] The present invention will be described in more detail below with reference to examples, comparative examples, and reference examples. It should be noted that the present invention is not limited to the examples, comparative examples, and reference examples. The specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit (a numerical value defined as "equal to or less than") or lower limit (a numerical value defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0130] Example 1 (Preparation process) A curable resin composition with a solids concentration of 30 wt% was prepared by mixing 100 parts by weight (solids equivalent) of an acrylic urethane resin (product name: Beamset 577, UV-curable resin, manufactured by Arakawa Chemical Industries, Ltd.) containing silica particles with a number-average primary particle diameter of 50 nm, 3.0 parts by weight of a photopolymerization initiator (product name: Omnirad 127, manufactured by IGM Resins), and 0.15 parts by weight of a silicone-based leveling agent (product name: Polyflow LE303, manufactured by Kyoeisha Chemical Co., Ltd.) and diluting with butyl acetate. This curable resin composition was applied to one side of a 50 μm-thick polyethylene terephthalate (PET) film (product name: Lumirror® #50-U48, manufactured by Toray Industries, Inc.) in the thickness direction to a thickness of 1.5 μm after drying to form a coating. The coating was then dried by heating at 60°C for 60 seconds. The composition was then irradiated with a high-pressure mercury lamp at a wavelength of 365 nm and an integrated light dose of 300 mJ / cm. 2 The coating film was cured by irradiating it with ultraviolet light, thereby forming a hard coat layer (HC layer). In this way, a substrate film having an HC layer (cured resin layer) on a PET film (transparent resin film) was obtained.

[0131] (Metal reflective layer formation process) First, one surface in the thickness direction of the substrate film (one surface in the thickness direction of the HC layer) was plasma treated. For the plasma treatment, a roll-to-roll sputtering deposition device (magnetron sputtering deposition device) was used. Note that this sputtering deposition device is equipped with a deposition chamber in which the deposition process can be carried out while the work film (substrate film) is running in the roll-to-roll method. The ultimate vacuum in the deposition chamber of the sputtering deposition device was 1.0 x 10 -4 After evacuating the chamber to a vacuum of 2.0 Pa, argon was introduced as a sputtering gas (inert gas) into the chamber, and the pressure in the chamber was set to 2.0 Pa. The effective power density was set to 0.50 W·min / cm. 2 The effective power density is the power density of the plasma output (W / cm 2 ) divided by the work film transport speed (m / min) using the roll-to-roll method.

[0132] Next, a 50 nm thick aluminum layer (Al layer) was formed by sputtering on one surface of the substrate film in the thickness direction (one surface of the HC layer in the thickness direction). A roll-to-roll sputtering deposition apparatus (magnetron sputtering deposition apparatus) was used to form the Al layer (metal reflective layer). This sputtering deposition apparatus is equipped with a deposition chamber that can perform the deposition process while running the workpiece film (substrate film) using the roll-to-roll method. The sputtering deposition conditions for forming the Al layer are detailed below.

[0133] The ultimate vacuum level in the deposition chamber of the sputter deposition equipment is 1.0 x 10 -4 After evacuating the chamber to a vacuum of 0.3 Pa, argon was introduced as a sputtering gas into the chamber, and the pressure in the chamber was set to 0.3 Pa. Aluminum was used as the target of the sputtering film formation device. An MF-AC power supply was used as the power source for applying voltage to the target, with a discharge power of 14 kW and a film formation temperature of 25°C.

[0134] In this way, an Al layer was formed on one surface in the thickness direction of the substrate film (one surface in the thickness direction of the HC layer).

[0135] (Reflection adjustment layer formation process) Next, a sputtering method (reactive sputtering method) was used to form a reflection adjustment layer on one thickness surface of the Al layer, which included a 68 nm thick first silicon oxide layer (first layer), a 53 nm thick niobium oxide layer (second layer), and a 20 nm thick second silicon oxide layer (third layer) in that order toward one thickness direction. A roll-to-roll sputtering deposition apparatus (magnetron sputtering deposition apparatus) was used to form the reflection adjustment layer. Note that this sputtering deposition apparatus is equipped with a deposition chamber that can perform the deposition process while running a workpiece film (a substrate film with a metal reflective layer) using the roll-to-roll method. Details of the sputtering deposition conditions for forming the reflection adjustment layer are shown below.

[0136] In the deposition of the first layer, the ultimate vacuum in the deposition chamber of the sputtering deposition equipment was 1.0 × 10 -4 After evacuating the chamber to a vacuum of 0.3 Pa, argon as a sputtering gas (inert gas) and oxygen as a reactive gas were introduced into the chamber, and the pressure inside the chamber was set to 0.3 Pa. The argon and oxygen were introduced into the chamber so that the volume ratio between them was 100:11. Niobium (Nb) was used as the target for the sputtering film formation device. An MF-AC power supply was used as the power source for applying voltage to the target, with a discharge power of 20 kW and a film formation temperature of 25°C.

[0137] In the deposition of the second layer, the ultimate vacuum in the deposition chamber of the sputtering deposition equipment was 1.0 × 10 -4 After evacuating the chamber to a vacuum of 0.3 Pa, argon as a sputtering gas (inert gas) and oxygen as a reactive gas were introduced into the chamber, and the pressure inside the chamber was set to 0.3 Pa. The argon and oxygen were introduced into the chamber so that the volume ratio between them was 100:33. Silicon (Si) was used as the target for the sputtering film formation device. An MF-AC power supply was used as the power source for applying voltage to the target, with a discharge power of 17 kW and a film formation temperature of 25°C.

[0138] The third layer was formed under the same conditions as those for the first layer described above.

[0139] In this way, a reflection adjustment layer was formed on one thickness-wise surface of the metal reflective layer, which had a first silicon oxide layer (first layer), a niobium oxide layer (second layer), and a second silicon oxide layer (third layer) arranged in that order toward one thickness-wise side.

[0140] (Water-repellent layer formation process) Then, a 5-nm-thick water-repellent layer was formed on one thickness-wise surface of the reflection adjustment layer (one thickness-wise surface of the second silicon oxide layer (third layer)) using vacuum deposition, a type of dry coating method (DC method). A dried water-repellent layer material (product name: SHIN-ETSU SUBELYN KY1903-1, active ingredient: alkoxysilane compound containing a perfluoropolyether skeleton, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the evaporation source for the water-repellent layer, and the heating temperature of the evaporation source was set to 260°C.

[0141] In this way, a water-repellent layer having a thickness of 5 nm was formed on one surface in the thickness direction of the reflection adjustment layer (one surface in the thickness direction of the second silicon oxide layer (third layer)).

[0142] In this manner, a film mirror laminate of Example 1 was produced in which the outermost layer (layer disposed on one surface of the reflection adjustment layer in the thickness direction) was a water-repellent layer.

[0143] The thickness of the water-repellent layer formed by the DC method, such as in Example 1 and Examples 2 and 3 described later, was measured using the following procedure. The fluorine fluorescent X-ray intensity of the water-repellent layer to be measured (Examples 1 to 3) was measured using an X-ray fluorescence analyzer (product name: ZSX-PRIMUS II, measuring diameter: ψ30 mm, manufactured by Rigaku Corporation). The water-repellent layer formed in Example 4 described later was used as the measurement standard. The thickness of the water-repellent layer to be measured was calculated using the following formula from the fluorine fluorescent X-ray intensity I1 of the water-repellent layer to be measured, the fluorine fluorescent X-ray intensity I2 of the measurement standard water-repellent layer (Example 4), and the thickness (7 nm) of the measurement standard water-repellent layer (Example 4). Thickness of the water-repellent layer to be measured = Thickness of the water-repellent layer to be measured × I1 / I2

[0144] Examples 2 and 3 As shown in Table 1, film mirror laminates of Examples 2 and 3 were produced in the same manner as the film mirror laminate of Example 1, except that the thickness of the water-repellent layer was changed.

[0145] Example 4 A film mirror laminate of Example 4 was produced in the same manner as the film mirror laminate of Example 1, except that the water-repellent layer forming step was changed as follows.

[0146] (Water-repellent layer formation process) A 7-nm-thick water-repellent layer was formed on one thickness-wise surface of the reflection adjustment layer (one thickness-wise surface of the second silicon oxide layer (third layer)) using a wet coating method (WC method). Specifically, a fluorine-based solvent (Fluorinert, 3M Company) was added to a water-repellent layer material (product name: SHIN-ETSU SUBELYN KY1903-1, active ingredient: an alkoxysilane compound containing a perfluoropolyether skeleton, manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a water-repellent layer composition with a solids concentration of 0.10% by volume. This water-repellent layer composition was applied to one thickness-wise surface of the reflection adjustment layer (one thickness-wise surface of the silicon oxide layer (third layer)) using a wire bar and dried at 60°C for 2 minutes to form a water-repellent layer with a calculated thickness of 7 nm.

[0147] In addition, for the water-repellent layers formed by the WC method such as in Examples 4 and 5 and Comparative Example 3, the wet thickness (thickness before drying) was measured using a spectroscopic film thickness meter (product name: MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.), and the thickness after drying was calculated from the wet thickness using the following formula. Thickness after drying = Wet thickness x solid content (volume%)

[0148] Example 5 As shown in Table 1, a film mirror laminate of Example 5 was produced in the same manner as the film mirror laminate of Example 4, except that the thickness of the water-repellent layer was changed.

[0149] Comparative Example 1 Except for not forming a water-repellent layer, the film mirror laminate of Comparative Example 1 was produced in the same manner as the film mirror laminate of Example 1. That is, in Comparative Example 1, no other layer was provided on one side of the reflection adjustment layer in the thickness direction.

[0150] Comparative Example 2 A film mirror laminate of Comparative Example 2 was produced in the same manner as the film mirror laminate of Example 1, except that a 5 μm thick HC layer was formed instead of the water-repellent layer. The HC layer was the same as that formed on the transparent resin film. The outermost surface layer of Comparative Example 2 was an HC layer.

[0151] Comparative Example 3 A film mirror laminate of Comparative Example 3 was produced in the same manner as the film mirror laminate of Example 1, except that the water-repellent layer forming step was changed as follows.

[0152] (Water-repellent layer formation process) A 9-nm-thick water-repellent layer was formed on one thickness-wise surface of the reflection adjustment layer (one thickness-wise surface of the second silicon oxide layer (third layer)) using a wet coating method (WC method). Specifically, a fluorine-based solvent (Novec 7300, 3M Company) was added to a water-repellent layer material (product name: Optool DSX, active ingredients: fluorine-based compound and perfluorohexane, manufactured by Shin-Etsu Chemical Co., Ltd.) and diluted 1 / 400 to prepare a water-repellent layer composition with a solids concentration of 0.05%. This water-repellent layer composition was applied to one thickness-wise surface of the reflection adjustment layer (one thickness-wise surface of the silicon oxide layer (third layer)) using a wire bar and dried at 60°C for 2 minutes to form a 9-nm-thick water-repellent layer. The outermost layer of Comparative Example 3 was a water-repellent layer.

[0153] [Water contact angle] The water contact angle on one surface in the thickness direction of the water-repellent layer was measured for the film mirror laminates of each Example and Comparative Example 3. Specifically, 4.0 μL of water was dropped onto one surface in the thickness direction of the water-repellent layer, and 2 seconds after the drop, the angle between the water-repellent layer surface and the tangent to the edge of the droplet was measured using a contact angle measuring device (product name: DMo-701, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1. Note that the water contact angle was not measured for Comparative Examples 1 and 2 because they did not have a water-repellent layer.

[0154] [Water drop corrosion test] An adhesive layer obtained by the following method was attached to the other thickness-wise surface (exposed surface of the transparent resin film) of the film mirror laminate of each Example and Comparative Example. The film mirror laminate was then attached to a 165 mm × 65 mm glass (product name: S200423, manufactured by Matsunami Glass Co., Ltd.) via the adhesive layer. Next, 5 mL of tap water was dropped onto one thickness-wise surface of the film mirror laminate (the exposed surface opposite the surface attached to the glass) using a dropper, and the film mirror laminate was placed in a thermo-hygrostat (manufactured by Espec Corporation) with the water-dropped surface facing directly upward and left to stand for 500 hours under conditions of 60°C and 95% RH. After 500 hours, the one thickness-wise surface of the film mirror laminate (the surface onto which the water was dropped) was visually inspected and evaluated according to the following criteria. The results are shown in Table 1. {standard} A: No corrosion (base film not exposed) B: Corrosion present (The metal reflective layer has corroded and peeled off, exposing the base film)

[0155] (Preparation of adhesive sheet) [Preparation of oligomer composition] 60 parts by weight of dicyclopentanyl methacrylate and 40 parts by weight of methyl methacrylate as monomer components, 3.5 parts by weight of α-thioglycerol as a chain transfer agent, and 100 parts by weight of toluene as a polymerization solvent were mixed and stirred at 70°C for 1 hour under a nitrogen atmosphere. Next, 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was added, and the mixture was reacted at 70°C for 2 hours, then heated to 80°C and reacted for 2 hours. The reaction solution was then heated to 130°C, and the toluene, chain transfer agent, and unreacted monomer components were dried and removed to obtain a solid acrylic oligomer. The acrylic oligomer had a weight-average molecular weight of 5100 and a glass transition temperature (Tg) of 130°C.

[0156] [Preparation of Prepolymer Composition] 67 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of N-vinyl-2-pyrrolidone, 3 parts by mass of hydroxyethyl acrylate, and 15 parts by mass of 4-hydroxybutyl acrylate as monomer components were mixed with 0.05 parts by mass of Irgacure 651 (trade name, manufactured by BASF) and 0.05 parts by mass of Irgacure 184 (trade name, manufactured by BASF) as photopolymerization initiators, and then this monomer mixture was exposed to ultraviolet light in a nitrogen atmosphere to partially photopolymerize, thereby obtaining a prepolymer composition (polymerization rate: approximately 10%).

[0157] [Preparation of Pressure-Sensitive Adhesive Composition] To 100 parts by mass of the obtained prepolymer composition, 5 parts by mass of the oligomer composition, 0.3 parts by mass of 1,6-hexanediol diacrylate (trade name "A-HD-N", manufactured by Shin-Nakamura Chemical Co., Ltd.), and 0.3 parts by mass of a silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed uniformly to obtain a pressure-sensitive adhesive composition. The gel fraction of the pressure-sensitive adhesive composition was 82%.

[0158] [Preparation of adhesive sheet] A 75 μm-thick first release liner (trade name: Diafoil MRF75, a PET film with a silicone-based release layer on its surface, manufactured by Mitsubishi Chemical Corporation) was prepared, and a pressure-sensitive adhesive composition was applied to the release layer side of the first release liner so that the thickness after drying was 25 μm to form a coating layer. A 75 μm-thick second release liner (trade name: Diafoil MRE75, a PET film with one side treated with silicone release, manufactured by Mitsubishi Chemical Corporation) was attached to this coating layer so that the release-treated surface was in contact with it. The laminate (first release liner / pressure-sensitive adhesive composition layer / second release liner) thus obtained was exposed to light from the second release liner side at an irradiation intensity of 5 mW / cm on the irradiated surface directly below the lamp. 2 The adhesive was photocured by irradiating it with ultraviolet light using a black light positioned so that the adhesive was cured. By peeling off the first and second release liners, it can be used as a 25 μm thick adhesive layer (adhesive sheet).

[0159] [Reflectance] The reflectance of the film mirror laminate in each example and comparative example was measured using a spectrophotometer (product name: CM-26d, manufactured by Konica Minolta, Inc.). A 45 mm × 50 mm black acrylic plate was attached to the other thickness-wise surface of the film mirror laminate (the exposed surface of the transparent resin film) via the adhesive layer obtained by the above method, to prepare a measurement sample. Measurement was performed by irradiating the film mirror laminate with visible light having a wavelength of 360 nm to 740 nm at an incident angle of 2° from one thickness-wise side. The results are shown in Table 1.

[0160] [Adhesion] The adhesion of the film mirror laminates of each Example and Comparative Example was evaluated by a cross-cut test method based on the JIS K 5400 cross-cut tape test. Specifically, the other thickness-wise surface of the film mirror laminate (the exposed surface of the transparent resin film) was attached to a 45 mm x 50 mm glass (product name: S200200, manufactured by Matsunami Glass Co., Ltd.) via the adhesive layer obtained by the above method. Next, 11 vertical and horizontal cuts were made at 10 mm intervals on one thickness-wise surface of the film mirror laminate (the exposed surface of the water-repellent layer) to create a total of 100 grid-like squares. Tape (product name: Sekisui Cellotape No. 252, manufactured by Sekisui Chemical Co., Ltd.) cut to a length of approximately 15 mm was pressed onto the grid-like squares. The edge of the tape was then grasped and peeled at a 90° angle for 0 to 0.2 seconds. The same procedure (applying and peeling the tape) was repeated at a 90° angle. The adhesion between the layers was evaluated according to the following criteria. The results are shown in Table 1. The area of ​​one square (1 cm 2 ) A square is considered to have peeled off when more than 50% of it has peeled off. {standard} A: The number of peeled squares is 0 B: The number of peeled squares is 1 or more

[0161] [Table 1] [Explanation of symbols]

[0162] 1. Film mirror laminate 2. Base film 3 Metal reflective layer 4 Reflection adjustment layer 5. Water-repellent layer 21 Transparent resin film 22 Cured resin layer 41 Low refractive index layer 42 High refractive index layer 43 Silicon oxide layer

Claims

1. a substrate film, a metal reflective layer, a reflection adjustment layer, and a water-repellent layer arranged in this order toward one side in a thickness direction; the reflection adjustment layer comprises a silicon oxide layer; the water-repellent layer is disposed on one surface of the silicon oxide layer in a thickness direction; A film mirror laminate, wherein the water contact angle on one surface in the thickness direction of the water-repellent layer is 110° or more.

2. 2. The film mirror laminate according to claim 1, wherein the reflectance of visible light having a wavelength of 360 to 740 nm irradiated from one side in the thickness direction of the film mirror laminate is 95.0% or more.

3. The film mirror laminate according to claim 1, wherein the metal reflective layer comprises at least one metal selected from the group consisting of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag).

4. The film mirror laminate according to claim 1 , wherein the reflection adjustment layer includes a low refractive index layer, a high refractive index layer, and the silicon oxide layer in this order toward one side in the thickness direction.

5. The film mirror laminate according to claim 1 , wherein the silicon oxide layer has a thickness of 50 nm or less.

6. The film mirror laminate according to claim 1 , wherein the water-repellent layer is a dry coating layer.

7. A mirror member comprising, in order toward one side in a thickness direction, a supporting substrate, a pressure-sensitive adhesive layer, and the film mirror laminate according to any one of claims 1 to 6.

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