WO2014208255A1 - Film miroir et procédé de fabrication de film miroir - Google Patents

Film miroir et procédé de fabrication de film miroir Download PDF

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Publication number
WO2014208255A1
WO2014208255A1 PCT/JP2014/064142 JP2014064142W WO2014208255A1 WO 2014208255 A1 WO2014208255 A1 WO 2014208255A1 JP 2014064142 W JP2014064142 W JP 2014064142W WO 2014208255 A1 WO2014208255 A1 WO 2014208255A1
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Prior art keywords
layer
silver
group
resin
corrosion inhibitor
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PCT/JP2014/064142
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English (en)
Japanese (ja)
Inventor
譲 富永
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富士フイルム株式会社
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Publication of WO2014208255A1 publication Critical patent/WO2014208255A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S40/00—Safety or protection arrangements of solar heat collectors; Preventing malfunction of solar heat collectors
    • F24S40/40—Preventing corrosion; Protecting against dirt or contamination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • the present invention relates to a film mirror and a method for manufacturing the film mirror.
  • glass mirrors have been used for sunlight reflecting devices because they are exposed to ultraviolet rays, heat, wind and rain, and dust from sunlight.
  • a glass mirror when a glass mirror is used, there are problems that it is damaged during transportation and that a high strength is required for the mount on which the mirror is installed, resulting in an increase in construction costs.
  • the use of a lightweight film mirror in which a metal reflective layer is formed on a resin support has been studied, and various developments have been made.
  • a film mirror uses a resin material for a support, its durability is not sufficient compared to a glass mirror. For this reason, the film mirror is required to improve durability and light resistance.
  • a “silver corrosion inhibitor” that prevents corrosion of silver in the binder as an adhesive layer is provided.
  • a configuration using what is included is disclosed (for example, see Patent Document 1).
  • the adhesive layer is formed using a curable resin composition containing glycol dimercaptoacetate as a silver corrosion inhibitor in a polyester resin binder.
  • the silver reflection layer has problems such as a decrease in reflection performance due to silver oxidation with time, and a decrease in adhesion with an adjacent resin layer, and improvement is required.
  • a resin layer adjacent to the silver reflective layer is formed using a curable resin composition containing a silver corrosion inhibitor in a binder as in Patent Document 1, it contacts the silver reflective layer. It has been found that the amount of the silver anticorrosion layer is not sufficient and the desired anticorrosion effect cannot be obtained. Therefore, when the concentration of the silver corrosion prevention layer was improved, the curing of the curable resin composition did not proceed sufficiently due to the presence of the corrosion inhibitor, and the adhesion between adjacent resin layers tended to be inferior. It was.
  • the problems of the present invention made in consideration of the above-mentioned problems of the prior art are that the reflection performance of the reflection layer containing silver and the adhesion between the reflection layer containing silver and the resin layer provided adjacent to the reflection layer are long. It is providing the film mirror excellent in durability maintained over a period. Moreover, the further subject of this invention is providing the simple manufacturing method of the said film mirror excellent in the said durability.
  • the present inventor can solve the above problems by attaching a silver corrosion prevention layer to the surface of the reflective layer containing silver and the vicinity thereof without using a binder.
  • the present invention was completed. That is, the configuration of the present invention is as follows.
  • a support, a resin intermediate layer, a reflective layer containing silver, and a resin protective layer are provided in this order.
  • the surface of the resin intermediate layer on the reflective layer side, on the reflective layer side of the resin intermediate layer A film mirror having a silver corrosion inhibitor on at least one of the surface layer, the surface of the reflective layer on the resin intermediate layer side, and the surface layer of the reflective layer on the resin intermediate layer side.
  • ⁇ 3> The film mirror according to ⁇ 1> or ⁇ 2>, wherein the corrosion inhibitor includes one or more compounds selected from compounds including a triazole structure.
  • ⁇ 4> The film mirror according to any one of ⁇ 1> to ⁇ 3>, which is used for collecting sunlight.
  • ⁇ 5> The step of forming the resin intermediate layer on the support, and the surface of the resin intermediate layer and the surface layer by contacting the surface of the resin intermediate layer with a solution obtained by dissolving or dispersing the silver corrosion inhibitor in a solvent.
  • a step of applying a silver corrosion inhibitor to at least one, a step of forming a reflective layer containing silver on the resin intermediate layer provided with the silver corrosion inhibitor, and resin protection on the surface of the formed reflective layer The method for producing a film mirror according to any one of ⁇ 1> to ⁇ 4>, comprising a step of forming a layer.
  • ⁇ 6> The method for producing a film mirror according to ⁇ 5>, wherein the step of forming the reflective layer includes a step of bringing the plating solution into contact with the resin intermediate layer and forming a layer containing silver by a plating method.
  • a step of forming a reflective layer containing silver on the resin protective layer, and a solution obtained by dissolving or dispersing a silver corrosion inhibitor in a solvent is brought into contact with the surface of the reflective layer to contain at least silver.
  • a step of applying a silver corrosion inhibitor to at least one of the reflective layer surface and the surface layer, a step of forming a resin intermediate layer on the surface of the reflective layer provided with the silver corrosion inhibitor, and the formed resin intermediate layer A method for producing a film mirror according to any one of ⁇ 1> to ⁇ 4>, comprising a step of forming a support on the substrate. ⁇ 8> Contact of a solution obtained by dissolving or dispersing a silver corrosion inhibitor in a solvent is performed by applying this solution to the resin intermediate layer, or by immersing this solution in the resin intermediate layer. ⁇ 5 The method for producing a film mirror according to any one of> to ⁇ 7>.
  • the reflection performance of the reflective layer containing silver, and the adhesion between the reflective layer containing silver and the resin layer provided adjacent thereto are maintained for a long period of time, and have excellent durability.
  • a simple manufacturing method of a film mirror and a film mirror excellent in durability can be provided.
  • the film mirror of the present invention includes a support, a resin intermediate layer, a silver-containing reflective layer (hereinafter, appropriately referred to as “silver reflective layer”), and a resin protective layer in this order.
  • a silver corrosion inhibitor is present at the interface between the silver reflective layer and the silver reflective layer, on at least one of the surface and surface layer of the resin intermediate layer on the silver reflective layer side, and the surface and surface layer of the silver reflective layer on the resin intermediate layer side. That is, the silver corrosion inhibitor includes a surface of the resin intermediate layer on the silver reflective layer side, a surface layer of the resin intermediate layer on the silver reflective layer side, a surface of the silver reflective layer on the resin intermediate layer side, and a resin intermediate layer side of the silver reflective layer Of at least one of the surface layers.
  • the silver corrosion inhibitor may contain a slight amount of solvent, but usually, the silver corrosion inhibitor is in a form in direct contact with the silver reflective layer, and the concentration of the silver corrosion inhibitor in contact with the silver reflective layer is high. Therefore, compared with the case where the silver corrosion inhibitor is dispersed and applied in the binder, the corrosion preventing effect of the silver reflection layer is high and the effect is maintained over a long period of time.
  • the adjacent resin intermediate layer is formed as a single film, there is no concern about the decrease in curability caused by the silver corrosion inhibitor, and the adhesiveness between the formed resin intermediate layer and the silver reflective layer is excellent. It will be.
  • the protective function of the silver reflective layer is high, and since it is maintained for a long period of time, the reflectivity is reduced due to silver oxidation, and the adhesion between the silver reflective layer and the resin intermediate layer is reduced due to silver oxidation. All are considered to be suppressed for a long period of time and excellent in durability.
  • the suitable embodiment of the film mirror of this invention and its manufacturing method is demonstrated in detail.
  • FIG. 1 is a schematic sectional view showing an embodiment of the film mirror of the present invention.
  • the film mirror 10 includes a support 12, a plating undercoat polymer layer 14 (hereinafter, appropriately referred to as “polymer layer 14”) that is a resin intermediate layer, a silver reflection layer 16 as a metal reflection layer, and a resin protective layer 18.
  • the corrosion inhibitor 20 is provided on at least one of the surface and the surface layer of the polymer layer 14 on the silver reflective layer 16 side and the surface and the surface layer of the silver reflective layer 16 on the polymer layer 14 side.
  • the film mirror 10 is manufactured by forming the polymer layer 14, the silver reflection layer 16, and the resin protective layer 20 in this order on the support 12.
  • the type of the support 12 is not particularly limited as long as it can reduce the weight of the film mirror 10 and can support the silver reflection layer 16 and the resin protective layer 18.
  • the support body 12 is selected according to the mode and purpose in which the film mirror 10 is installed, and may have flexibility, or may have rigidity.
  • the material of the support 12 is preferably a support using a resin made of polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, liquid crystal polymer, etc. from the viewpoint of weight reduction. These resins can be molded into an arbitrary shape such as a film and used as the support 12. Further, a glass epoxy base material or the like may be used.
  • the support 12 may have a single layer structure made of a base material such as the resin exemplified above, or may have a multilayer structure formed by laminating a plurality of types.
  • the resin include phenol resin, epoxy resin, polyimide resin, BT resin, PPE resin, tetrafluoroethylene resin, liquid crystal resin, polyester resin, PEN, aramid resin, polyamide resin, polyethersulfone, triacetyl cellulose, polyvinyl chloride, Polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, polyacetylene, and the like are suitable, and a resin that can be formed into a film can be used.
  • Particularly suitable support 12 includes a polyester resin film or a polyimide resin film.
  • an aluminum substrate, a SUS substrate, or the like can be used as the support 12.
  • the shape of the support 12 is a planar shape, but the shape is not particularly limited to the form of FIG. 1, and is required as a film substrate in various film mirrors such as a diffusion surface, a concave surface, and a convex surface. Any shape is acceptable.
  • the thickness of the support 12 is preferably about 10 to 5 mm. When the thickness is in this range, the handling during production is good, and it can be easily formed into an arbitrary shape.
  • the thickness of the support 12 is more preferably 20 to 1 mm, still more preferably 25 to 500 ⁇ m.
  • the support 12 may be subjected to a surface treatment for the purpose of improving the adhesion with the polymer layer 14 provided on the support 12 or suppressing the mixing of impurities.
  • Surface treatment includes UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment, and other surface activation treatments, and hydrazine, N-methylpyrrolidone, sodium hydroxide solution, alkaline solution such as potassium hydroxide solution.
  • Treatment with a solution or treatment with an acidic solution such as sulfuric acid, hydrochloric acid or nitric acid can be mentioned.
  • Examples of the treatment to remove and clean the surface of the support 12 include treatment with an organic solvent such as methanol, ethanol, toluene, ethyl acetate, and acetone, and washing with water to remove attached dust. These surface treatments may be performed in combination of a plurality of types.
  • a support 12 having a surface roughness (Ra) of 50 nm or less, and more preferably Ra of 20 nm or less. More preferably, the average roughness (Ra) is 5 nm or less.
  • the film mirror 10 of this embodiment has a resin intermediate layer on the support 12 for the purpose of improving the adhesion between the support 12 and the silver reflective layer 16.
  • the resin intermediate layer include an easy-adhesion layer 28 for facilitating adhesion of metal, a polymer layer 14 useful for forming the silver reflection layer 16 by a plating method, and the like. Also, it may be composed of two or more layers.
  • the film mirror 10 according to the first embodiment includes a polymer layer 14.
  • the polymer layer 14 which is one embodiment of the resin intermediate layer will be described.
  • the polymer layer 14 has at least a plating undercoat polymer.
  • the polymer layer 14 may include reduced metal particles.
  • Examples of the method for forming the polymer layer 14 include a method for forming the polymer layer 14 including the metal precursor on the support 12 by a method such as coating using a composition including the metal precursor and the plating undercoat polymer. It is done. Alternatively, a layer is formed on the support 12 using the polymer layer forming composition, and then the composition containing the metal precursor is brought into contact with the layer provided on the support 12 by a method such as immersion. A method of forming the “polymer layer 14 including a metal precursor” and then reducing the metal precursor included in the “polymer layer 14 including a metal precursor” may be mentioned.
  • the polymer layer 14 containing the reduced metal particles is formed.
  • the content (total amount) of the metal particles contained in the polymer layer 14 is obtained by dissolving the metal particles in the plating undercoat polymer by immersing the resin base material having the polymer layer 14 in concentrated sulfuric acid or the like.
  • the liquid can be measured by elemental analysis using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer) (ICP-1000IV, manufactured by Shimadzu Corporation).
  • ICP-AES Inductively Coupled Plasma Atomic Emission Spectrometer
  • a silver corrosion inhibitor 20 is applied to the polymer layer 14 as described later.
  • the plating undercoat polymer used for forming the polymer layer 14 will be described.
  • the plating undercoat polymer used to form the polymer layer 14 has at least a polymerizable group and a functional group that interacts with the metal precursor (hereinafter, referred to as “interactive group” as appropriate).
  • an acrylic polymer, polyether, acrylamide, polyamide, polyimide, acrylic polymer, polyester, and the like are preferable, and an acrylic polymer is more preferable.
  • the plating undercoat polymer may contain a constitutional unit other than a constitutional unit containing a polymerizable group and an interaction group depending on the purpose.
  • the composition for forming a polymer layer has excellent solubility in water or an organic solvent and is uniform.
  • a plating undercoat layer can be formed.
  • the “polymer layer forming composition” is a composition for forming the polymer layer 14 including a plating undercoat polymer.
  • an acrylic polymer having an acidic group and a polymerizable group as an interactive group in the side chain can be mentioned.
  • a polymerizable group, an interactive group, and characteristics of the plating undercoat polymer will be described in detail.
  • the polymerizable group of the plating undercoat polymer is chemically bonded between the polymers or between the polymer and the base layer (the support 12 or the easy-adhesion layer 28 or the undercoat layer provided on the support 12) by applying energy. Any functional group can be used.
  • the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity.
  • radical polymerizable group examples include methacryloyl group, acryloyl group, itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group, maleic acid ester group, styryl group, vinyl group, acrylamide group and methacrylamide group. It is done. Of these, a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable.
  • a methacryloyl group, an acryloyl group, an acrylamide group, and a methacrylamide group are preferable from the viewpoint of radical polymerization reactivity and synthetic versatility, and an acrylamide group and a methacrylamide group are more preferable from the viewpoint of alkali resistance.
  • various polymerizable groups such as a (meth) acryl group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester group of a carboxylic acid, a vinyl ether group, and an allyl ether group Is preferred.
  • the interaction group of the plating undercoat polymer is a functional group that interacts with the metal precursor (for example, a coordination group, a metal ion adsorbing group, etc.), and can form an electrostatic interaction with the metal precursor.
  • a functional group, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination with a metal precursor can be used.
  • Nitrogen-containing functional groups such as pyrazole group, group containing alkylamine structure, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, carbonate group, carbonyl group, ester group, Oxygen-containing functional groups such as groups containing N-oxide structures, groups containing S-oxide structures, groups containing N-hydroxy structures; thiophene groups, thiol groups, thiourea groups, sulfoxide groups, sulfonic acid groups, sulfonic acid ester structures Sulfur-containing functional groups such as groups containing phosphine groups; Phosphorus-containing functional groups
  • the plating undercoat polymer support 12 (in the case where the easy-adhesion layer 28 is formed on the support 12, easy adhesion)
  • carboxylic acid group, sulfonic acid group, phosphoric acid group, and boronic acid group can be mentioned, among them, having moderate acidity (not decomposing other functional groups), other functionalities
  • Carboxylic acid groups are particularly preferred from the viewpoint that there are few concerns that affect the group, excellent compatibility with the plating layer, and easy availability of raw materials.
  • An ionic polar group such as a carboxylic acid group can be introduced into the plating undercoat polymer by copolymerizing a radical polymerizable compound having an acidic group.
  • the polymer having an interactive group comprising a radical polymerizable group and a non-dissociable functional group is described in paragraphs [0106] to [0112] of JP-A-2009-007540.
  • Polymers can be used.
  • polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used.
  • Examples of the polymer having a radical polymerizable group, an interactive group composed of a non-dissociative functional group, and an interactive group composed of an ionic polar group include paragraphs [0010] to [0010] of JP 2010-248464 A. [0128] Polymers described in paragraphs [0030] to [0108] of JP 2010-84196 A and US Patent Application Publication No. 2010-080964 may be used.
  • the metal precursor described later may be applied after the polymer layer 14 is formed, or may be contained in the polymer layer forming composition from the beginning.
  • the content of the metal precursor is preferably 0.5 to 100% by mass and more preferably 1 to 50% by mass with respect to the total amount of the composition.
  • the composition for forming a polymer layer preferably contains a radical polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator in order to increase sensitivity to energy application.
  • the radical polymerization initiator is not particularly limited, and generally known ones are used. However, when energy is applied, the plating undercoat polymer can generate active sites that interact with the support 12 and the easy-adhesion layer 28, that is, when a polymer having a polymerization initiation site in the polymer skeleton described above is used. These radical polymerization initiators may not be added.
  • the amount of the radical polymerization initiator to be contained in the polymer layer forming composition is selected according to the configuration of the polymer layer forming composition. In general, the amount of the radical polymerization initiator is preferably about 0.05 to 30% by mass, and preferably about 0.1 to 10.0% by mass in the polymer layer forming composition. More preferred.
  • the polymer layer 14 can be formed by applying a composition for forming a polymer layer on the support 12 or the easy-adhesion layer 28 formed on the surface of the support 12 and applying energy.
  • a composition for forming a polymer layer on the support 12 or the easy-adhesion layer 28 formed on the surface of the support 12 and applying energy.
  • an easy adhesion treatment such as applying energy to the surface of the support 12 in advance.
  • the method for providing the polymer layer 14 on the support 12 is not particularly limited. The method for immersing the support 12 in the composition for forming a polymer layer or the method for applying the composition for forming a polymer layer on the support 12. Etc. From the viewpoint of easily controlling the thickness of the polymer layer 14 to be obtained, a method of coating the polymer layer forming composition on the support 12 is preferable.
  • the coating amount of the polymer layer forming composition is preferably 0.05 to 10 g / m 2 in terms of solid content, particularly 0.3 to 5 g / m 2 from the viewpoint of sufficient interaction formation with the metal precursor described later. m 2 is preferred.
  • the coating solution of the polymer layer forming composition applied to the support 12 or the like is preferably dried at 20 to 60 ° C. for 1 second to 2 hours, and then dried at a temperature exceeding 60 ° C. for 1 second to 2 hours. More preferably, after drying at ⁇ 60 ° C. for 1 second to 20 minutes, drying at a temperature exceeding 60 ° C. for 1 second to 20 minutes.
  • the composition for forming a polymer layer is formed by bringing the polymer in the energy application region into contact with the support 12 or the easy-adhesion layer 28 provided on the support 12 and then applying energy. Alternatively, an interaction is formed between the polymerizable group of the polymer and the support 12 or the easy-adhesion layer 28 provided on the support 12. And the polymer layer 14 fixed on the support body 12 (or on the support body 12 through the easily bonding layer 28) is formed. Thereby, the support body 12 and the polymer layer 14 adhere
  • Examples of the energy application method include heating and exposure.
  • As an energy application method by exposure specifically, light irradiation by a UV lamp, visible light, or the like is possible.
  • Examples of the light source used for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
  • the exposure power is preferably in the range of 10 to 8000 mJ / cm 2 from the viewpoint of facilitating the polymerization, suppressing the decomposition of the polymer, or forming a good interaction of the polymer, A range of 100 to 3000 mJ / cm 2 is more preferable. Note that exposure may be performed in an atmosphere in which substitution with an inert gas such as nitrogen, helium, or carbon dioxide is performed, and the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less.
  • an inert gas such as nitrogen, helium, or carbon dioxide
  • Energy application by heating can be performed by, for example, a general heat heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like.
  • the temperature is preferably in the range of 20 to 200 ° C., in order to facilitate the polymerization or to suppress thermal denaturation of the support, and in the range of 40 to 120 ° C. It is more preferable that
  • the film thickness of the polymer layer 14 is not particularly limited, but is preferably 0.05 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m from the viewpoint of adhesion to the support 12 and the like. Further, the surface roughness (Ra) of the polymer layer 14 obtained by the above method is preferably 20 nm or less, and more preferably 10 nm or less, from the viewpoint of reflection performance.
  • the polymer layer 14 preferably includes reduced metal particles.
  • the reduced metal particles contained in the polymer layer 14 are obtained by applying a metal precursor to the polymer layer 14 and reducing the metal precursor to make the metal precursor reduced metal particles. When the metal precursor is applied to the polymer layer 14, the metal precursor adheres to the interactive group by interaction.
  • the amount of reduced metal particles contained in the polymer layer 14 is preferably 0.01 to 5 g / m 2 , and more preferably 0.05 to 1 g / m 2 .
  • a metal precursor will not be specifically limited if it functions as an electrode by changing to a metal by a reduction reaction. Moreover, as a metal precursor, what functions as an electrode of plating in formation of a metal reflective layer is mentioned preferably. Therefore, what functions as an electrode by reducing a metal precursor to a metal is preferable. Specifically, metal ions such as Au, Pt, Pd, Ag, Cu, Ni, Al, Fe, and Co are used as the metal precursor. When the metal ion which is a metal precursor is contained in the composition for forming a polymer layer, after forming a layer on the support 12, it becomes zero-valent metal particles by a reduction reaction.
  • the metal ion which is a metal precursor is contained in the composition for polymer layer formation as a metal salt.
  • the metal ion Ag ion, Cu ion, and Pd ion are preferable in terms of the type and number of functional groups capable of coordination, and catalytic ability.
  • the Ag ions those obtained by dissociating the silver compounds shown below can be suitably used.
  • the silver compound examples include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate.
  • silver nitrate is preferable from the viewpoint of water solubility.
  • Cu ions those obtained by dissociating the following copper compounds can be suitably used.
  • copper compounds include copper nitrate, copper acetate, copper sulfate, copper cyanide, copper thiocyanate, copper chloride, copper bromide, copper chromate, copper chloranilate, copper salicylate, copper diethyldithiocarbamate, diethyldithiol.
  • copper carbamate and copper p-toluenesulfonate examples include copper carbamate and copper p-toluenesulfonate.
  • copper sulfate is preferable from the viewpoint of water solubility.
  • the metal precursor is preferably applied to the polymer layer 14 as a dispersion or solution (metal precursor liquid).
  • the particle diameter of the metal precursor in the dispersion or solution is preferably 1 to 200 nm, more preferably 1 to 100 nm, and still more preferably 1 to 60 nm.
  • the particle size of the reduced metal particles can be controlled to a desired size.
  • the particle diameter means an average primary particle diameter (volume conversion), and is measured by reading from an image of SEM (S-5200, manufactured by Hitachi High-Tech Manufacturing & Service Co., Ltd.).
  • Metal ions that are metal precursors applied to the polymer layer 14 are reduced by a metal activation liquid (reducing liquid).
  • the metal activation liquid is composed of a reducing agent that can reduce a metal precursor (mainly metal ions) to a zero-valent metal and a pH adjuster for activating the reducing agent.
  • concentration of the reducing agent with respect to the entire metal activation liquid is preferably 0.05 to 50% by mass, and more preferably 0.1 to 30% by mass.
  • boron-based reducing agents such as sodium borohydride and dimethylamine borane
  • reducing agents such as formaldehyde and hypophosphorous acid
  • reduction with an aqueous alkaline solution containing formaldehyde is preferred.
  • the concentration of the pH adjusting agent with respect to the entire metal activation liquid is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass.
  • As the pH adjuster acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen carbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and the like can be used.
  • the temperature during the reduction is preferably 10 to 100 ° C, more preferably 20 to 70 ° C. These concentrations and temperatures are preferably in this range from the viewpoints of the particle diameter of the metal precursor, the surface roughness of the polymer layer 14, the conductivity (surface resistance value), and the deterioration of the reducing solution during reduction.
  • the particle diameter of the reduced metal particles contained in the polymer layer 14 is preferably 1 to 200 nm, more preferably 1 to 100 nm, and further preferably 1 to 60 nm from the viewpoint of reflection performance. By being in this range, the reflectance after plating becomes good.
  • the particle size is measured by reading from an SEM (S-5200 manufactured by Hitachi High-Tech Manufacturing & Service) image.
  • the surface resistance value of the polymer layer 14 containing the reduced metal particles is preferably 0.001 ⁇ / ⁇ or more and 100 ⁇ / ⁇ or less, and more preferably 0.03 ⁇ / ⁇ or more and 50 ⁇ / ⁇ or less. Within this range, the plated surface is formed uniformly and smoothly and the reflectance is good. Further, the surface roughness (Ra) of the polymer layer 14 containing the reduced metal particles is preferably 20 nm or less, and more preferably 10 nm or less, from the viewpoint of reflection performance.
  • the polymer layer 14 containing the metal particles thus obtained is suitably used when the silver reflecting layer 16 described in detail below is formed by a plating method that is a wet method.
  • the silver reflective layer 16 formed by plating using the polymer layer 14 is excellent in adhesion to the resin substrate and surface smoothness.
  • the corrosion inhibitor 20 is a state in which the silver corrosion inhibitor 20 is dissolved directly in the polymer layer 14 (preferably, a polymer layer containing reduced metal particles) or dissolved in a suitable solvent. It is given by making it contact with.
  • a mode in which the silver corrosion inhibitor 20 is applied is shown in FIGS. 2 and 3 show another example of the first embodiment.
  • the silver corrosion inhibitor 20 may adhere over the entire surface of the polymer layer 14.
  • the silver corrosion inhibitor 20 may adhere to at least a part of the surface of the polymer layer 14 in an island shape.
  • the mirror film of this embodiment is in another example of the first mode shown in FIG. In No. 24, the silver corrosion inhibitor 20 is applied to the surface layer of the plating undercoat polymer layer 14, that is, from the surface of the plating undercoat polymer layer 14 to a region having a depth of about 200 nm.
  • the silver corrosion inhibitor 20 may be distributed in an island shape on at least a part of the interface between the polymer layer 14 and the silver reflective layer 16.
  • voids open cells are formed in the polymer layer 14 due to permeation of the plating catalyst or the plating solution.
  • the silver corrosion inhibitor 20 may be scattered not only on the surface and the surface layer of the polymer layer 14 but also in deeper portions in the polymer layer 14.
  • the silver corrosion inhibitor 20 may be attached to at least one of the surface of the polymer layer 14 and the surface layer, and the silver corrosion inhibitor 20 may further exist in a deeper portion of the polymer layer 14. 1 to 3, when the silver reflective layer 16 is formed by plating, the silver reflective layer 16 and the silver corrosion inhibitor 20 come into contact with each other. For this reason, corrosion of the silver reflective layer 16 is effectively suppressed.
  • the silver reflection layer 16 has a micro gap.
  • the silver corrosion inhibitor 20 adhered to the surface of the polymer layer 14 may not only contact the surface of the silver reflective layer 16 but also penetrate and adhere to the surface layer of the silver reflective layer 16 (16A: see FIG. 6). sell.
  • the silver corrosion inhibitor 20 is in contact with the silver constituting the silver reflective layer 16, so that the silver corrosion of the silver reflective layer 16 is effectively prevented.
  • the silver corrosion inhibitor 20 is preferably present in an amount that satisfies the adhesion amount described below. Even if the surface of the resin intermediate layer 14 or the silver reflective layer 16 is uneven, if the silver corrosion inhibitor 20 is given a sufficient amount for preventing corrosion, for example, the silver corrosive recesses on the surface of the silver reflective layer 16 are corroded. The aspect which the inhibitor 20 adheres may be sufficient, and the aspect which the silver corrosion inhibitor 20 adheres to a convex part conversely may be sufficient. Moreover, when the silver corrosion inhibitor 20 is arrange
  • “corrosion” refers to a phenomenon in which silver is chemically or electrochemically eroded or deteriorated by an environmental material surrounding it (see JIS Z0103-2004).
  • the silver corrosion inhibitor 20 is disposed in a part of the surface of the polymer layer 14 as the resin intermediate layer and inside the polymer layer 14 .
  • the component (for example, silver) constituting the silver reflecting layer 16 and the silver corrosion inhibitor 20 may be mixed and present. That is, when the reduced silver particles and the silver corrosion inhibitor 20 are mixed in the polymer layer 14 and the silver reflective layer 16 is formed by plating with the reduced silver particles as a starting point, in the polymer layer 14, It is also possible to include a state in which granular silver is included and a corrosion inhibitor is included in a gap between the granular silvers.
  • the “surface layer” is a region close to the surface from the surface on the polymer layer 14 side as the resin intermediate layer of the silver reflective layer 16 to a position of 50 nm in the depth direction, or on the silver reflective layer 16 side of the polymer layer 14. It means a region close to the surface from the surface to the position of 200 nm in the depth direction.
  • the silver corrosion inhibitor 20 is included in the surface layer of the silver reflective layer 16, the silver corrosion inhibitor 20 is on the polymer layer 14 side of the silver reflective layer 16 from the viewpoint of hardly affecting the reflection characteristics of the silver reflective layer 16. It is preferable to exist only in a region from the surface to a position in the depth direction of 30 nm.
  • the content of the silver corrosion inhibitor 20 is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of silver contained in the silver reflection layer 16. Especially, from a viewpoint that the adhesiveness of the polymer layer 14 and the silver reflective layer 16 and the light resistance of the film mirror 10 become more favorable, it is 0.03 with respect to 100 mass parts of silver contained in the silver reflective layer 16.
  • the range is preferably from 0.8 to 0.8 parts by mass, and more preferably from 0.05 to 0.6 parts by mass.
  • the content of the silver corrosion inhibitor 20 means the total amount of the silver corrosion inhibitor 20 contained in the entire film mirror 10.
  • the silver corrosion inhibitor 20 when the silver corrosion inhibitor 20 is present only on the surface of the silver reflective layer 16 and when the silver corrosion inhibitor 20 is present only on the surface layer 16A of the silver reflective layer 16, the silver corrosion inhibitor 20 present on the surface or each surface layer. It is sufficient that the amount (attachment amount) is within the above range. When the silver corrosion inhibitor 20 is present on both the surface and the surface layer, the total amount of the silver corrosion inhibitor 20 on the surface and the amount of the silver corrosion inhibitor 20 in the surface layer of the silver reflection layer 16 is in the above range. If it is in.
  • the amount of the silver corrosion inhibitor 20 is measured by elution of the surface and surface corrosion inhibitors with an acid solution of 25% hydrochloric acid or the like and measuring the absorbance of the UV-Vis absorption spectrum, or by surface element analysis such as XPS. It can be measured by the method used. Whether the silver corrosion inhibitor 20 exists up to the depth of the polymer layer 14 or the silver reflection layer 16 is obtained by obliquely cutting with SAICAS (registered trademark, manufactured by Daipura Wintes Co., Ltd.), It is measured by analyzing the cut section by the TOF-SIMS method (time-of-flight secondary ion mass spectrometry).
  • SAICAS registered trademark, manufactured by Daipura Wintes Co., Ltd.
  • the silver corrosion inhibitor 20 is applied after the formation of the polymer layer 14 that is a resin intermediate layer, so that the silver corrosion inhibitor 20 is present on at least one of the surface and the surface layer of the polymer layer 14 and is in contact with the silver reflective layer 16 at a high density. It will be.
  • the binder resin added with the silver corrosion inhibitor 20 is used as the resin intermediate layer, the effects of the present invention cannot be achieved. Specifically, when the silver corrosion inhibitor 20 is added before the resin intermediate layer is formed (that is, in the coating liquid for forming the polymer layer) and then the energy is applied to form the polymer layer 14, the silver corrosion prevention The agent 20 is uniformly dispersed throughout the resin intermediate layer. For this reason, the quantity of the silver corrosion inhibitor 20 which contacts the adjacent silver reflection layer 16 decreases. Therefore, a sufficient corrosion prevention effect cannot be obtained.
  • the kind in particular of the silver corrosion inhibitor 20 is not restrict
  • examples of the silver corrosion inhibitor having an adsorptive group for silver include amines and derivatives thereof, Compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, compounds having an indazole ring, copper chelate compounds, thioureas, mercapto It is desirable to select from at least one of a group-containing compound, a thioether (a compound having a sul
  • amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, o-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate , Diisopropylammonium benzoate, diisopropylammonium nitrite , Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohex
  • Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, and N-phenyl-3. , 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.
  • Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy) -5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy3'5'-di-tert-butylphenyl) benzotriazole, 2-
  • Examples of the compound having a pyrazole ring include pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole, 4-aminopyrazole, and a mixture thereof.
  • Examples of the compound having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or mixtures thereof.
  • Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4 Formylimidazole, 4-methyl-5-formylimidazole, 2-ethy
  • Examples of the compound having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.
  • copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and the like, or a mixture thereof.
  • thioureas examples include thiourea, guanylthiourea, and the like, or a mixture thereof.
  • mercaptoacetic acid thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto
  • thioethers examples include didodecyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, ditridecyl 3,3′-thiobispropionate, and bis [3- (dodecylthio) propionic acid] 2.
  • naphthalene compounds examples include thionalide.
  • a more specific example of the silver corrosion inhibitor 20 includes compounds represented by the following formulas (D) to (J).
  • R 41 to R 45 each independently represents a hydrogen atom or a substituent.
  • substituents include a halogen atom (eg, fluorine atom, chlorine atom), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl).
  • cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • aralkyl group eg, benzyl group, 2-phenethyl group, etc.
  • aryl group eg, phenyl group, naphthyl group, p-tolyl group, p) -Chlorophenyl group etc.
  • alkoxy group eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.
  • aryloxy group eg phenoxy group etc.
  • acylamino group eg acetylamino group, propionylamino group etc.
  • Alkylthio group for example, methylthio group, ethylthio group, butylthio group
  • arylthio group eg, phenylthio group, etc.
  • sulfonylamino group eg, methanesul
  • Q represents a nitrogen atom or CR 46.
  • R 46 represents a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 46 is preferably a hydrogen atom.
  • R 51 to R 53 each independently represents a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 51 to R 53 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an amino group, and a mercapto group, in that light resistance is more excellent.
  • R 61 to R 63 each independently represents a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 61 to R 63 are each independently preferably selected from the group consisting of a hydrogen atom, an alkyl group, an amino group, and a mercapto group from the viewpoint that light resistance is more excellent.
  • R 71 to R 72 each independently represents a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 71 to R 72 are each independently preferably selected from the group consisting of a hydrogen atom, an alkyl group, an amino group, a mercapto group, and an alkyl sulfide group from the viewpoint of more excellent light resistance.
  • R 81 to R 84 each independently represents a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 81 to R 84 are independently selected from the group consisting of a hydrogen atom and an alkyl group from the viewpoint of more excellent light resistance.
  • A represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms.
  • La represents an alkylene group, —S—, —CO—, —O—, or a combination thereof (for example, —alkylene group—S-alkylene group—, —COO-alkylene group).
  • n represents an integer of 2 to 4.
  • R 101 and R 102 each independently represent a hydrogen atom or a substituent.
  • the substituent is synonymous with the substituent represented by R 41 to R 45 in the formula (D).
  • R 101 is preferably selected from the group consisting of hydrogen atom and alkyl group.
  • R 102 is preferably selected from the group consisting of a hydrogen atom, a mercapto group, an amino group, and an alkyl group.
  • Lb represents an alkylene group.
  • m represents an integer of 1 to 5
  • l represents an integer of 0 to 4
  • the method for applying the silver corrosion inhibitor 20 is not particularly limited, but the silver corrosion inhibitor 20 may be brought into direct contact with the polymer layer 14, or a solution dissolved or dispersed in an appropriate solvent may be brought into contact with the polymer layer 14. Good.
  • the silver corrosion inhibitor 20 adheres to the surface of the polymer layer 14 or penetrates into the surface layer of the polymer layer 14 and adheres to the interaction group of the plating undercoat polymer. (Adsorption).
  • the silver corrosion inhibitor 20 has an adsorptive group for silver, the silver corrosion inhibitor 20 comes into close contact with the silver reflective layer 16 formed by plating through the adsorptive group.
  • a contact condition will not be restrict
  • the contact is preferably performed at 10 ° C. to 50 ° C. for 0.2 minutes to 60 minutes.
  • the type of the solvent used for dissolving and dispersing the silver corrosion inhibitor 20 is not particularly limited, but a solvent that can dissolve the silver corrosion inhibitor 20 is preferable.
  • the solvent solvent or dispersion medium
  • examples of the solvent include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone.
  • Amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, benzene Aromatic hydrocarbon solvents such as toluene and xylene, and other solvents such as ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents. Further, the content of the silver corrosion inhibitor 20 when the silver corrosion inhibitor 20 is dissolved and dispersed in the solvent is not particularly limited.
  • the silver corrosion inhibitor 20 with respect to 100 parts by mass of the solvent. Is preferably 0.0001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass.
  • the resin support body 12 which has the polymer layer 14 to which the silver corrosion inhibitor 20 was given as needed. You may implement the process of wash
  • the type of solvent used for cleaning is not particularly limited, and is selected according to the type of silver corrosion inhibitor 20 used. For example, the solvent used for melt
  • the method of washing with a solvent is not particularly limited, and a method of applying a solvent on the support 12 with the polymer layer 14 provided with the silver corrosion inhibitor 20 or a support 12 with the polymer layer 14 provided with the silver corrosion inhibitor 20 is used.
  • the method of immersing in a solvent is mentioned.
  • the washing conditions are not particularly limited, but it is preferable to contact with a solvent at 10 to 50 ° C. for 0.1 to 5 minutes from the viewpoint that the excess silver corrosion inhibitor 20 can be removed more efficiently.
  • the silver reflection layer 16 is a layer provided on the polymer layer 14 and has a function of reflecting incident light. Silver or an alloy containing silver can increase the reflectance in the visible light region of the film mirror 10 and reduce the dependency of the reflectance on the incident angle.
  • the visible light region means a wavelength region of 400 to 700 nm.
  • the incident angle means an angle with respect to a line perpendicular to the film surface.
  • the silver content in the silver reflecting layer 16 is preferably 90 atomic% to 99.8 atomic% in the total of silver and other metals (100 atomic%). Further, the content of other metals is preferably 0.2 atomic% to 10 atomic% from the viewpoint of durability.
  • the silver reflection layer 16 may contain other metals other than silver to the extent that the reflection characteristics of the silver reflection layer 16 are not affected, from the viewpoint of improving durability. Gold, copper, nickel, iron, palladium, etc. are mentioned.
  • the silver corrosion inhibitor 20 may be contained in at least one of the surface of the silver reflective layer 16 on the polymer layer 14 side and the surface layer 16A of the silver reflective layer.
  • a conventionally known method can be used as the electroplating method.
  • the metal particles contained in the polymer layer 14 have a function as an electrode, by performing electroplating on the polymer layer 14, the silver reflective layer 16 having excellent adhesion to the resin support.
  • metal compounds used for plating include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver methanesulfonate, silver ammonia, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, and chloranil.
  • silver compounds such as silver oxide, silver salicylate, silver diethyldithiocarbamate, silver diethyldithiocarbamate, and silver p-toluenesulfonate.
  • silver methanesulfonate is preferable from the viewpoint of environmental impact and smoothness.
  • the film thickness of the silver reflecting layer 16 obtained by the electroplating method can be controlled by adjusting the metal concentration or the current density contained in the plating bath. By adding a base metal layer having an appropriate thickness, it is possible to improve reflectance and reduce pinholes by smoothing the surface.
  • the silver reflective layer 16 may be formed by performing dry plating such as vacuum deposition using the polymer layer 14 containing the reduced metal particles. According to this method, since the surface of the polymer layer 14 is covered with a metal, it is possible to form the silver reflective layer 16 that has better adhesion than ordinary vapor deposition or the like and is strong against heat.
  • the silver reflective layer 16 may be treated with a strong acid or a strong alkali in order to improve the reflection performance and durability of the silver reflective layer 16. Further, an inorganic film or a metal oxide film may be formed on the metal surface.
  • the thickness of the silver reflective layer 16 is not particularly limited, but is preferably 50 to 500 nm, more preferably 80 to 300 nm from the viewpoint of reflectivity.
  • the method for forming the silver reflective layer 16 is not particularly limited, and either a wet method or a dry method can be employed.
  • the wet method include a known method as a so-called metal plating method (electroless plating or electroplating).
  • the dry method include a vacuum deposition method, a sputtering method, and an ion plating method.
  • the content (total amount) of silver contained in the silver reflective layer 16 is determined by immersing the silver reflective layer 16 in concentrated sulfuric acid or the like to dissolve the silver in the silver reflective layer 16, and then dissolving the obtained solution with ICP-AES ( It can be measured by elemental analysis using an inductively coupled plasma emission spectrometer (ICP-1000IV, manufactured by Shimadzu Corporation).
  • the resin protective layer 18 is a layer disposed on the silver reflection layer 16 and is provided on the surface of the silver reflection layer 16 on the incident light side.
  • the resin protective layer 18 prevents the silver reflecting layer 16, the support 12, the polymer layer 14, or the like from being deteriorated or damaged by sunlight, rainwater, dust, or the like, and stabilizes the specularity.
  • the resin material used for forming the resin protective layer 18 is a resin that can form a film or layer, and the strength or durability of the formed film or layer, air and moisture blocking properties, and further this resin In addition to the adhesion between the protective layer 18 and the adjacent layer (for example, the silver reflection layer 16 or the surface coating layer), a resin having excellent transparency is preferable.
  • As the resin protective layer 18, a resin having high transparency with respect to light having a wavelength required by the film mirror 10 is particularly preferable.
  • cellulose ester resins for example, cellulose ester resins, polyester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyether sulfone) resins, polyethylene terephthalate, polyester resins such as polyethylene naphthalate, polyethylene, Polypropylene, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl alcohol resin, ethylene vinyl acetate resin, and ethylene acrylate copolymer, polycarbonate , Norbornene resin, polymethylpentene resin, polyamide, fluorine resin, polymethyl methacrylate, acrylic resin , Olefin resin, polyurethane resin, and silicone resin.
  • polyester resins such as polyethylene naphthalate, polyethylene, Polypropylene, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose
  • the resin contained in the resin protective layer 18 includes acrylic resin, polyvinyl butyral, ethylene vinyl acetate resin, and ethylene acrylate ester.
  • One or more resins selected from copolymers are preferred.
  • the resin protective layer 18 preferably further contains a crosslinking agent.
  • a crosslinking agent By containing a crosslinking agent, a crosslinked structure is formed in the resin protective layer 18. Thereby, while the intensity
  • a crosslinking agent it can select according to correlation with resin which comprises the resin protective layer 18.
  • the crosslinking agent include a carbodiimide compound, an isocyanate compound, an epoxy compound, an oxetane compound, a melamine compound, a bisvinylsulfone compound, and the like.
  • the resin protective layer 18 contains additives such as an ultraviolet absorber, a photopolymerization initiator, an antistatic agent, a coating aid (leveling agent), an antioxidant, and an antifoaming agent. May be.
  • a composition for forming the resin protective layer 18 (hereinafter referred to as “protective image forming composition” as appropriate) is dissolved in a solvent and coated on the silver reflective layer 16, and then the solvent is reduced to reduce the resin protective layer.
  • a method of forming the resin protective layer 18 by heating to a temperature at which the resin contained in the protective layer forming composition melts, and casting on the silver reflective layer 16.
  • the protective layer forming composition is formed into a film in advance, and the obtained film is bonded to the silver reflective layer 16 via an adhesive, or the silver reflective layer 16 is formed by a method such as thermal lamination.
  • the solid content concentration of the protective layer-forming coating solution composition is preferably in the range of 1 to 30% by mass.
  • the method of curing the resin film applied to the surface of the silver reflective layer 16 is not particularly limited, and a method corresponding to the resin material used for forming the resin protective layer 18 such as heating or UV irradiation can be appropriately selected. That's fine.
  • the film thickness of the resin protective layer 18 is preferably in the range of 3 to 30 ⁇ m from the viewpoint of achieving the necessary protective function and durability and suppressing the reduction in light reflectivity, and in the range of 5 to 10 ⁇ m. It is more preferable that
  • the resin protective layer 18 is preferably substantially free of the silver corrosion inhibitor 20.
  • the resin protective layer 18 is formed of a curable resin composition, if the silver corrosion inhibitor 20 is included, curing may be hindered.
  • substantially not contained means that the content of the silver corrosion inhibitor 20 is 0.02 mass% or less with respect to the total amount of the resin protective layer 18 and is 0.01 mass% or less. It is preferable.
  • the resin protective layer 18 may contain an ultraviolet absorber.
  • the ultraviolet absorber By including the ultraviolet absorber, the light resistance of the film mirror 10 is further improved.
  • the type of the ultraviolet absorber is not particularly limited, but examples of the organic system include benzophenone system, benzotriazole system, phenyl salicylate system, triazine system, benzoate system, etc., and inorganic systems include titanium oxide, zinc oxide, cerium oxide, Examples include iron oxide.
  • a polymeric ultraviolet absorber having a molecular weight of 1000 or more.
  • the molecular weight is 1000 or more and 3000 or less.
  • the film mirror 10 may further have a surface coating layer on the resin protective layer 18.
  • the weather resistance and scratch resistance of the film mirror 10 are further improved.
  • the surface coating layer may be a soft layer having a hardness of 100 N / mm 2 or less and an elastic recovery rate of 60% or more, or may be a so-called hard coat layer having a hard surface. .
  • the thickness in the case of forming a soft surface coating layer is not particularly limited, but is 1 to 50 ⁇ m because the scratch resistance of the film mirror 10 becomes better and the maintenance ratio of the haze value and the reflectance becomes higher. It is preferably 3 to 30 ⁇ m. Further, the thickness in the case of forming a hard surface coating layer is preferably from 0.1 to 50 ⁇ m, more preferably from 0.1 to 10 ⁇ m, from the viewpoint of antifouling properties and scratch resistance.
  • the use of the film mirror 10 is not particularly limited, it can be preferably used for the purpose of collecting sunlight (for collecting sunlight) because of its excellent durability. That is, it can be suitably used as a solar member such as a solar cell or solar thermal power generation.
  • the film mirror 26 of the present embodiment includes a support 12, an easy adhesion layer 28 that is a resin intermediate layer, a silver corrosion inhibitor 20, a silver reflection layer 16, and a resin protective layer 18. In this order.
  • the film mirror 26 has the same configuration as the film mirror 10 except that the film mirror 10 shown in FIG. 1 includes an easy-adhesion layer 28 instead of the polymer layer 14 as a resin intermediate layer.
  • the easily bonding layer 28 is formed on the support body 12, and the silver corrosion inhibitor 20 is provided to this easily bonding layer 28.
  • the silver reflection layer 16 may be formed by a plating method or a vapor phase method, and the resin protective layer 18 may be formed on the surface thereof.
  • the silver reflective layer 16 is formed on the resin protective layer 18, the silver corrosion inhibitor 20 is contacted, and then the support 14 is pasted via the easy-adhesion layer 28. May be.
  • the same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.
  • the aspect manufactured with the manufacturing method different from 1st embodiment among the said manufacturing methods is explained in full detail.
  • the resin protective layer 18 is formed.
  • the aspect of the resin protective layer 18 is as described in the first embodiment.
  • the silver reflective layer 16 is formed on the surface of the resin protective layer 18.
  • the manufacturing method of the silver reflective layer 16 in this embodiment is not specifically limited, Either a wet method or a dry method may be employ
  • the wet method include an electroplating method.
  • Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method.
  • the silver reflective layer 16 is the same as that described in the first embodiment, and the preferred embodiment is also the same.
  • the surface of the silver reflection layer 16 and / or the surface layer of the silver reflection layer 16 is prevented by bringing a silver corrosion inhibitor 20 into contact therewith.
  • Agent 20 is applied.
  • the silver corrosion inhibitor 20 may be provided over the entire surface of the silver reflecting layer 16 as in the film mirror 26 shown in FIG. 4, but as another example, as in the film mirror 30 shown in FIG.
  • the silver corrosion inhibitor 20 may be in an island shape on a part of the surface of the silver reflective layer 16.
  • the silver reflection layer 16 has many fine voids regardless of the formation method. For this reason, like the film mirror 32 shown in FIG.
  • the silver corrosion inhibitor 20 is directly or directly dissolved or dissolved or dispersed in the appropriate solvent and brought into contact with the silver reflective layer 16A to prevent silver corrosion.
  • the agent 20 may be included, but such a state may be used.
  • a component (for example, silver) constituting the silver reflective layer 16 and the silver corrosion inhibitor 20 are mixed and present in the surface 16A of the silver reflective layer shown in FIG.
  • the mixed state is not particularly limited, and examples thereof include an aspect in which the silver reflection layer surface layer 16A is included in a state where granular silver is filled, and the silver corrosion inhibitor 20 is included in the granular silver gap.
  • the silver reflective layer surface layer 16A means a region from the surface on the easy adhesion layer 28 side of the silver reflective layer 16 to a position in the depth direction of 50 nm.
  • the silver corrosion inhibitor 20 is included in the surface 16A of the silver reflection layer, the silver corrosion inhibitor 20 is a surface of the silver reflection layer 16 on the easy adhesion layer 28 side in that the surface reflection characteristics of the silver reflection layer 16 are more excellent. It is preferable to exist only in a region from the top to a position in the depth direction of 30 nm. As described above, the presence of the silver corrosion inhibitor 20 not only on the surface of the silver reflective layer 16 but also on the surface 16A of the silver reflective layer prevents the silver reflective layer 16 from being corroded more effectively.
  • the silver reflective layer 16 to which the silver corrosion inhibitor 20 was provided as needed after giving the silver corrosion inhibitor 20 to the silver reflective layer 16, before the process of forming the easily bonding layer 28 which is a resin intermediate
  • the cleaning step may be performed by the method described above. Thereafter, the laminate having the resin protective layer 18, the silver reflection layer 16, and the silver corrosion inhibitor 20 is adhered to the support 12 via an easy adhesion layer (primer layer) 28, which is a resin intermediate layer. Film mirrors 26, 30, and 32 as shown in FIG. 6 are obtained.
  • an easy-adhesion layer 28 is provided to improve the adhesion between the support 12 and the silver reflection layer 16.
  • This easy-adhesion layer 28 may be provided as a lower layer of the polymer layer 14 described above to improve the adhesion between the support 12 and the polymer layer 14.
  • the easy-adhesion layer 28 is the same resin as the resin constituting the support 12 or a resin having an affinity for the resin constituting the support 12 from the viewpoint of adhesion to the adjacent support 12. It is preferable that it contains.
  • the resin contained in the easy-adhesion layer 28 may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, isocyanate resin, and the like.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
  • the thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. The combined use of two or more kinds of resins is performed for the purpose of expressing a more excellent effect by compensating for each defect.
  • an easy adhesion layer 28 is provided between the polymer layer 14 and the support 12, the mutual adhesion between the polymer layer 14 and the polymer compound having a polymerizable group contained in the polymer layer 14 described above is performed. It is preferable to contain an active species that generates an active site that can act.
  • Such an easy adhesion layer 28 is preferably, for example, a polymerization initiation layer containing a radical polymerization initiator or a polymerization initiation layer made of a resin having a functional group capable of initiating polymerization.
  • the easy-adhesion layer 28 is made of a layer containing a polymer compound and a radical polymerization initiator, a layer containing a polymerizable compound and a radical polymerization initiator, or a resin having a functional group capable of initiating polymerization.
  • a resin having a functional group capable of initiating polymerization include polyimides having a polymerization initiating site described in paragraphs [0018] to [0078] of JP-A-2005-307140 in the skeleton.
  • a compound having a polymerizable double bond specifically, an acrylate compound or a methacrylate compound may be used in order to promote crosslinking in the layer. It is preferable to use a functional one.
  • a compound having a polymerizable double bond a part of a thermosetting resin or a thermoplastic resin such as an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, etc.
  • a (meth) acrylated resin using acrylic acid or the like may be used.
  • the thickness of the easy-adhesion layer 28 is preferably in the range of 0.1 to 10 ⁇ m, and more preferably in the range of 0.2 to 5 ⁇ m.
  • the silver reflective layer 16 having the silver corrosion inhibitor 20 on the surface of the easy adhesion layer 28 side and the support 12 are brought into close contact with each other via the easy adhesion layer 28, so that the film mirror 32 is formed. can get.
  • a well-known means can be employ
  • the surface coating layer described above may be further formed on the surface of the resin protective layer 18.
  • the surface of the silver reflecting layer 16 and the surface of the silver reflecting layer 16A, and the surface of the resin intermediate layer adjacent to the silver reflecting layer 16 and / or the surface layer are highly concentrated. Therefore, the oxidation of the silver reflection layer 16 is suppressed, and excellent reflection performance and adhesion between the resin intermediate layer and the silver reflection layer 16 are maintained over a long period of time.
  • Example 1 Formation of Plating Undercoat Polymer Layer (Resin Intermediate Layer) A polyethylene terephthalate (PET) film (manufactured by TOYOBO, Cosmo Shine A4300) was prepared as the support 12. -Preparation of coating solution for plating undercoat polymer layer formation- In a mixed solution of acrylic polymer 1 (7 parts by mass), 1-methoxy-2-propanol (74 parts by mass), and water (19 parts by mass) having the following structure, a photopolymerization initiator (Esacure KTO-46, manufactured by Lamberdy) ) (0.35 parts by mass) was added and stirred to prepare a coating solution containing a plating undercoat polymer (acrylic polymer 1).
  • a photopolymerization initiator Esacure KTO-46, manufactured by Lamberdy
  • the obtained coating solution containing the plating undercoat polymer was applied to the surface of the support 12 by a bar coating method so that the film thickness after drying was about 0.55 ⁇ m, dried at 25 ° C. for 10 minutes, and continued. And dried at 80 ° C. for 5 minutes. Thereafter, UV exposure was performed at 1000 mJ / cm 2 at a wavelength of 254 nm using a UV irradiation apparatus (UV lamp: metal halide lamp manufactured by GS Yuasa Co., Ltd.), and a polymer layer 14 was formed on the support 12.
  • the support 12 on which the polymer layer 14 was formed was immersed in a 1% by mass aqueous sodium hydrogen carbonate solution for 5 minutes, and then washed by pouring with pure water for 1 minute to remove unreacted polymer.
  • the support 12 provided with silver ions on the polymer layer 14 was immersed in the prepared reducing solution at 25 ° C. for 10 minutes, and then washed by pouring with pure water for 1 minute to reduce silver ions.
  • the amount of silver contained in the polymer layer 14 was measured by elemental analysis using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer) (ICP-1000IV, manufactured by Shimadzu Corporation) by the method described above.
  • Silver Corrosion Inhibitor 3-mercapto-1,2,4-triazole was used as silver corrosion inhibitor 20, and a 0.3 mass% aqueous solution of this 3-mercapto-1,2,4-triazole (silver corrosion inhibitor) Solution) was prepared.
  • the “support 12 with the polymer layer 14 provided with reduced silver” obtained in the above step was immersed in the prepared silver corrosion inhibitor solution at 25 ° C. for 3 minutes and then immersed in pure water for 1 minute.
  • the silver corrosion inhibitor 20 was applied to the polymer layer 14 by washing with a sink.
  • the adhesion amount of the silver corrosion inhibitor 20 on the polymer layer 14 after washing was calculated by a method using 25% HCl.
  • the support 12 with the polymer layer 14 provided with the silver corrosion inhibitor 20 is immersed in 25% HCl to elute the silver corrosion inhibitor 20, and UV-3100 (trade name: Shimadzu Corporation)
  • the adhesion amount of the silver corrosion inhibitor 20 was calculated by measuring the UV absorption spectrum using
  • a silver reflective layer 16 was formed on the polymer layer 14. After the silver reflective layer 16 is formed, the total amount of silver contained in the silver reflective layer 16 and the polymer layer 14 is determined using an ICP-AES (inductively coupled plasma emission spectrometer) (ICP-1000IV, manufactured by Shimadzu Corporation). Measured by elemental analysis. The amount of silver contained in the silver reflecting layer 16 was calculated by subtracting the amount of silver in the polymer layer 14 from the total amount of silver measured. Table 1 below shows the values calculated from the measured adhesion amount of the silver corrosion inhibitor 20 to the content ratio (parts by mass) of the silver corrosion inhibitor 20 with respect to 100 parts by mass of silver contained in the silver reflection layer 16.
  • ICP-AES inductively coupled plasma emission spectrometer
  • Resin Protective Layer As a resin protective layer forming coating solution for forming the resin protective layer 18, acrylic resin (Dianar BR-102, manufactured by Mitsubishi Rayon Co., Ltd.) (21 parts by mass), benzotriazole ultraviolet absorption Agent (Sumisorb 250, manufactured by Sumitomo Chemical Co., Ltd.) (4 parts by mass), cyclohexanone (5 parts by mass), methyl ethyl ketone (70 parts by mass), fluorosurfactant (Megafac F-780F, solid content: 30% by mass, A mixed solution of DIC Corporation (0.04 parts by mass) was prepared.
  • the obtained coating liquid for forming a protective resin layer was applied on the silver reflective layer 16 by a bar coating method so that the film thickness after drying was 10 ⁇ m, and dried at 130 ° C. for 1 minute. Thereby, the resin protective layer 18 was formed on the silver reflective layer 16.
  • a fluorine-based UV curable resin (Defenser FH-700, solid content: 91% by mass, manufactured by DIC Corporation) (22 parts by mass)
  • Cyclohexanone (5 parts by mass), methyl ethyl ketone (72 parts by mass)
  • fluorosurfactant (Megafac F-780F, solid content: 30% by mass, manufactured by DIC Corporation) (0.04 parts by mass)
  • a solution was prepared.
  • the obtained coating solution for forming a surface coating layer was applied on the resin protective layer 18 by a bar coating method so as to have a dry film thickness of 15 ⁇ m, and dried at 130 ° C. for 1 minute.
  • UV exposure was performed at 500 mJ / cm 2 at a wavelength of 254 nm using a UV irradiation apparatus (GS Yuasa Co., Ltd., UV lamp: metal halide lamp). Thereby, a surface coating layer was formed on the resin protective layer 18. Thus, the film mirror 10 was formed.
  • Adhesiveness evaluation was performed using the support body 12 (state which remove
  • Light resistance evaluation was performed using the support body 12 (state which remove
  • the obtained film mirror 10 was placed in a xenon lamp light resistance tester (manufactured by ATLAS, Ci5000, power: 180 W, Black Panel Temperature: 83 ° C.) and left standing for 500 hours.
  • the decrease in reflectance (reflectance before standing (%)-reflectance after standing (%) was evaluated.
  • the reflectance was measured using an ultraviolet-visible near-infrared spectrophotometer UV-3100 (manufactured by Shimadzu Corporation).
  • Light resistance was evaluated according to the following criteria. Practically, it is preferably A to C. “A”: Less than 3% of reflectance decrease “B”: Less than 3% to less than 5% “C”: Less than 5% to less than 10% “D”: Lower reflectance 10% or more
  • Example 2> As the silver corrosion inhibitor solution used for applying the silver corrosion inhibitor 20, a solution in which the concentration of 3-mercapto-1,2,4-triazole was changed from 0.3% by mass to 0.1% by mass was used. Except for the above, a film mirror of Example 2 was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
  • Example 3> A film mirror of Example 3 was prepared and carried out in the same manner as in Example 1 except that benzotriazole was used instead of 3-mercapto-1,2,4-triazole as the silver corrosion inhibitor 20. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 below.
  • Example 4> Formation of Silver Reflective Layer by Vapor Deposition
  • a UV absorber-containing PMMA film manufactured by Sumitomo Chemical Co., Ltd., S001G is used as the resin protective layer 18, and this is used as a vapor deposition substrate to form a vacuum vapor deposition method (vacuum degree 5 ⁇ 10 ⁇ 2 Pa, film formation
  • the silver reflective layer 16 having a thickness of 100 nm was formed on the resin protective layer 18 at a speed of 40 m / min. 2.
  • Silver Corrosion Inhibitor 3-mercapto-1,2,4-triazole was used as silver corrosion inhibitor 20, and a 0.3 mass% aqueous solution of this 3-mercapto-1,2,4-triazole (silver corrosion inhibitor) Solution) was prepared.
  • the PMMA film (resin protective layer 18) formed with the silver reflective layer 16 obtained in the above step is immersed in the prepared silver corrosion inhibitor solution at 25 ° C. for 3 minutes, and then poured in pure water for 1 minute. Washed with Thereby, the silver corrosion inhibitor 20 was provided to the surface of the silver reflective layer 16 on the side where the support 12 is formed. 3.
  • the obtained adhesive solution was applied to a polyethylene terephthalate (PET) film (manufactured by TOYOBO, Cosmo Shine A4300) as the support 12 by a bar coating method so that the film thickness after drying was about 10 ⁇ m. For 2 minutes, followed by drying at 80 ° C. for 10 minutes. As a result, an easy adhesion layer (resin intermediate layer) 28 containing an adhesive was formed on the support 12.
  • the easy-adhesion layer 28 side of the support 12 and the silver reflection layer 16 provided with the silver corrosion inhibitor 20 on the surface were superposed and bonded together by a laminator.
  • the laminating speed was 0.1 m / min, and the laminating pressure was 0.5 MPa.
  • the easy-adhesion layer 28 is cured by heating at 60 ° C. for 12 hours, and the support 12, the easy-adhesion layer 28, the silver corrosion inhibitor 20, the silver reflection layer 16, and the resin protective layer 18 are provided in this order.
  • the film mirror 32 of Example 4 was obtained.
  • the film mirror 32 of Example 4 is configured as shown in FIG.
  • the obtained film mirror 32 was evaluated in the same manner as in Example 1. The results are shown in Table 1 below. * In Table 1 below, “parts by mass” of the adhesion amount of the silver corrosion inhibitor represents the content ratio of the silver corrosion inhibitor 20 to 100 parts by mass of silver contained in the silver reflection layer 16.
  • the film mirrors of Examples 1 to 4 have good adhesion between the support 12 and the silver reflective layer 16 and excellent light resistance over a long period of time. Moreover, even when the silver corrosion inhibitor 20 is applied to the surface of the polymer layer 14, which is a resin intermediate layer, or when it is applied to the surface of the silver reflective layer 16, there is a good effect. On the other hand, even if the same silver corrosion inhibitor 20 is used as in Comparative Example 1, when it is used by being dispersed together with a resin in the polymer layer 14, a practically preferable evaluation can be obtained for adhesion and light resistance. There wasn't. This is presumably because the concentration of the silver corrosion inhibitor 20 per unit area is large but the concentration in contact with the silver reflective layer 16 is low.

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Abstract

L'invention concerne: un film miroir qui a une excellent résistance à la lumière et présente une bonne adhésion entre une couche réfléchissante d'argent et un corps de support en résine; et un procédé de fabrication du film miroir. Ce film miroir comprend un corps de support, une couche intermédiaire en résine, une couche réfléchissante contenant de l'argent et une couche de protection en résine, dans cet ordre, et contient un inhibiteur de corrosion de l'argent dans la couche superficielle et la surface côté couche réfléchissante contenant de l'argent de la couche intermédiaire en résine et/ou dans la couche superficielle et la surface coté couche intermédiaire en résine de la couche réfléchissante contenant de l'argent à l'interface entre la couche intermédiaire en résine et la couche réfléchissante contenant de l'argent.
PCT/JP2014/064142 2013-06-24 2014-05-28 Film miroir et procédé de fabrication de film miroir WO2014208255A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017032809A1 (fr) * 2015-08-25 2017-03-02 Alanod Gmbh & Co. Kg Matériau composite réfléchissant avec support en aluminium laqué et avec une couche de réflexion en argent, et procédé de fabrication dudit matériau composite

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6394437B2 (ja) * 2015-02-27 2018-09-26 三菱マテリアル株式会社 スパッタリングターゲット
WO2017033740A1 (fr) * 2015-08-26 2017-03-02 住友金属鉱山株式会社 Substrat conducteur
WO2021100366A1 (fr) * 2019-11-19 2021-05-27 コニカミノルタ株式会社 Dispositif électronique, inhibiteur de sulfuration et produit d'étanchéité

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096320A1 (fr) * 2010-02-05 2011-08-11 コニカミノルタオプト株式会社 Miroir sous forme de film, miroir sous forme de film permettant une production d'énergie solaire thermique et dispositif de réflexion permettant une production d'énergie solaire photovoltaïque
JP2012181301A (ja) * 2011-03-01 2012-09-20 Konica Minolta Advanced Layers Inc フィルムミラーの製造方法、フィルムミラー及び太陽熱発電用反射装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7612937B2 (en) * 2001-02-09 2009-11-03 Alliance For Sustainable Energy, Llc Advanced ultraviolet-resistant silver mirrors for use in solar reflectors
US9316415B2 (en) * 2009-12-21 2016-04-19 Konica Minolta Advanced Layers, Inc. Film mirror, production process of same and reflection device for solar power generation comprising same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096320A1 (fr) * 2010-02-05 2011-08-11 コニカミノルタオプト株式会社 Miroir sous forme de film, miroir sous forme de film permettant une production d'énergie solaire thermique et dispositif de réflexion permettant une production d'énergie solaire photovoltaïque
JP2012181301A (ja) * 2011-03-01 2012-09-20 Konica Minolta Advanced Layers Inc フィルムミラーの製造方法、フィルムミラー及び太陽熱発電用反射装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017032809A1 (fr) * 2015-08-25 2017-03-02 Alanod Gmbh & Co. Kg Matériau composite réfléchissant avec support en aluminium laqué et avec une couche de réflexion en argent, et procédé de fabrication dudit matériau composite
CN107924004A (zh) * 2015-08-25 2018-04-17 阿兰诺德股份有限两合公司 具有涂漆的铝衬底和银反射层的反射性复合材料及其制造方法
US20180239067A1 (en) * 2015-08-25 2018-08-23 Alanod Gmbh & Co. Kg Reflective composite material having a varnished aluminium carrier having a silver reflection layer and method for production thereof
US11822104B2 (en) 2015-08-25 2023-11-21 Alanod Gmbh & Co. Kg Reflective composite material having a varnished aluminum carrier having a silver reflection layer and method for production thereof

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