WO2013141304A1 - Miroir à film, et dispositif de réflexion pour la génération d'énergie solaire - Google Patents

Miroir à film, et dispositif de réflexion pour la génération d'énergie solaire Download PDF

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Publication number
WO2013141304A1
WO2013141304A1 PCT/JP2013/058094 JP2013058094W WO2013141304A1 WO 2013141304 A1 WO2013141304 A1 WO 2013141304A1 JP 2013058094 W JP2013058094 W JP 2013058094W WO 2013141304 A1 WO2013141304 A1 WO 2013141304A1
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Prior art keywords
film
resin
layer
group
film mirror
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PCT/JP2013/058094
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English (en)
Japanese (ja)
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鈴木　利継
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コニカミノルタ株式会社
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Publication of WO2013141304A1 publication Critical patent/WO2013141304A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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 solar power generation reflector using the film mirror.
  • a method for solving the problem of low energy density of solar energy in the above problem in utilizing solar energy by collecting solar energy with a huge reflecting device has been proposed.
  • solar thermal power generation has been proposed in which power generated by collecting sunlight with a reflection device is used as a medium. Since this reflecting device is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, and the like, a glass mirror has been conventionally used.
  • glass mirrors are highly durable against the environment, but they may be damaged during transportation, and the weight of the glass mirrors is so large that it is necessary to reinforce the mounting base for the mirrors. There was a problem that the construction cost of the plant was high.
  • the film mirror as a mirror for solar power generation that is lightweight and highly flexible, and has low production costs and transportation costs.
  • the film mirror suppresses corrosion of the metal constituting the reflection layer by laminating a corrosion prevention layer made of resin on the reflection layer provided on the film base.
  • durability is improved by suppressing deterioration by laminating a resin layer containing a UV absorber on the upper layer and suppressing damage by providing a hard coat layer or the like on the outermost surface.
  • solar power mirrors are installed in an outdoor environment, high-pressure water discharge and brushing are regularly performed for the purpose of suppressing a decrease in reflectance caused by dust and the like adhering to the mirror surface. Yes.
  • patent document 1 The technique of patent document 1 is mentioned regarding the already reported film mirror for solar power generation.
  • an acrylic layer containing a UV absorber is provided on the outermost layer of the film, and a decrease in reflectance due to discoloration of the resin layer due to UV exposure is suppressed.
  • the PET layer and the adhesive layer are sandwiched between the reflective layer and the acrylic layer, and when the cleaning by brushing is performed after outdoor exposure for more than half a year, the reflective layer and the PET layer are separated. There was a problem that peeling occurred and the reflectance was greatly reduced.
  • the corrosion resistance cannot be maintained by simply including a material capable of enhancing the adhesion with the reflective layer in the corrosion prevention layer.
  • the main object of the present invention is to provide a film mirror that has high adhesion between the reflective layer and the corrosion prevention layer and can suppress the corrosion of the reflective layer, and a solar power generation reflector using the film mirror. .
  • a film mirror provided with a reflective layer on a film substrate, A corrosion prevention layer laminated adjacent to the light reflecting side of the reflective layer;
  • the corrosion prevention layer is formed by including a silicone-modified resin and a silane coupling agent, and further contains a compound having a thiol group in the molecule.
  • the invention according to claim 2 is the film mirror according to claim 1,
  • the compound has two or more thiol groups in the molecule.
  • the invention according to claim 3 is the film mirror according to claim 1 or 2
  • the silicone-modified resin is an acrylic silicone resin.
  • the invention according to claim 4 is the film mirror according to any one of claims 1 to 3,
  • the compound is characterized by being trimethylolpropane tristhiopropionate.
  • the invention according to claim 5 is the film mirror according to any one of claims 1 to 3,
  • the compound is characterized in that it is pentaerythritol tetrakisthiopropionate.
  • the invention according to claim 6 is the film mirror according to any one of claims 1 to 5, A layer mainly composed of a resin is provided by coating on the corrosion prevention layer.
  • Claim 7 is a solar power generation reflective apparatus, Comprising: A film mirror according to any one of claims 1 to 6 is formed by being attached to a supporting substrate.
  • the present invention it is possible to provide a film mirror that has high adhesion between the reflective layer and the corrosion prevention layer and that can suppress the corrosion of the reflective layer, and a solar power generation reflector using the film mirror.
  • the compound having a thiol group in the molecule is represented by the following general formula (3).
  • R 61 and R 62 represents a hydrogen atom or a substituent, either one of R 61 and R 62 represents a hydrogen atom. However, R 61 and R 62 do not both represent a hydrogen atom. In the general formula (3), specific examples of the substituent represented by R 61 and R 62 will be described later.
  • the number of thiol groups in the molecule is preferably 2 or more, and more preferably 3 or more.
  • the inventors include a compound having a thiol group in the molecule as described above in the corrosion prevention layer, so that the thiol group is bonded to the metal on the surface of the reflective layer adjacent to the corrosion prevention layer, and is high. It is assumed that adhesion can be improved while maintaining corrosion resistance.
  • the film mirrors 10 a and 10 b for solar thermal power generation include at least a reflective layer 5 as a constituent layer and a reflective layer 5 on a first resin base 3 as a film base.
  • the anticorrosion layer 6 laminated adjacent to the light reflection side of the light-emitting layer and the hard coat layer 9 laminated on the outermost surface of the light reflection side are provided.
  • the corrosion prevention layer 6 is formed including at least a silicone-modified resin and a silane coupling agent, and further contains a compound having a thiol group in the molecule.
  • the hard coat layer 9 contains a UV absorber.
  • an anchor layer 4 may be provided between the first resin base material 3 and the reflective layer 5 (see FIGS. 1 and 2).
  • An adhesive layer 7 and a second resin substrate 8 may be provided between the coat layers 9 (see FIG. 1).
  • First resin substrate As the first resin substrate 3 used in the film mirror according to the present invention, various conventionally known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films.
  • cellulose ester film polyester film, poly
  • the first resin substrate 3 may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.
  • the thickness of the first resin substrate 3 is preferably set to an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 10 to 300 ⁇ m. The thickness is preferably 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
  • Anchor layer 4 formed in the film mirror according to the present invention is made of a resin, and the first resin substrate 3 and the reflective layer 5 are brought into close contact with each other. Therefore, the anchor layer 4 has an adhesion property that the first resin substrate 3 and the reflective layer 5 are in close contact, heat resistance that can withstand heat when the reflective layer 5 is formed by a vacuum deposition method, and the reflective layer 5 Smoothness is required to bring out the inherent high reflection performance.
  • the resin used for the anchor layer 4 is not particularly limited as long as it satisfies the above conditions of adhesiveness, heat resistance, and smoothness.
  • Polyester resin acrylic resin, melamine resin, epoxy resin, polyamide resin Resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, and the like, and mixed resins thereof can be used.
  • a mixed resin of a polyester resin and a melamine resin is preferable from the viewpoint of weather resistance, and more preferably a thermosetting resin in which a curing agent such as isocyanate is mixed.
  • the thickness of the anchor layer 4 is preferably 0.01 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m.
  • the thickness of the anchor layer 4 When the thickness of the anchor layer 4 is in the above range, the adhesion is good and the effect of forming the anchor layer 4 is great, and the unevenness on the surface of the first resin substrate 3 can be covered, and the smoothness is smooth. As a result, the reflectance of the reflective layer 5 becomes high. In addition, even if the thickness of the anchor layer 4 is thicker than 3 ⁇ m, improvement in adhesion cannot be expected, and smoothness may deteriorate due to occurrence of coating unevenness. As a method for forming the anchor layer 4, a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method, or the like can be applied.
  • the reflective layer 5 formed on the film mirror according to the present invention is a layer made of metal or the like having a function of reflecting sunlight.
  • the surface reflectance of the reflective layer 5 is preferably 80% or more, more preferably 90% or more.
  • the reflective layer 5 is preferably formed of a material containing any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt, and Au. Among them, it is preferable that Al or Ag is a main component from the viewpoint of reflectance and corrosion resistance, and two or more such metal thin films may be formed.
  • a silver reflecting layer mainly containing silver is particularly preferable.
  • a layer made of a metal oxide such as SiO 2 or TiO 2 may be provided on the reflective layer 5 to further improve the reflectance.
  • a method for forming the reflective layer 5 for example, a silver reflective layer
  • a wet method or a dry method can be used as a method for forming the reflective layer 5 (for example, a silver reflective layer) in the present invention.
  • the wet method is a general term for a plating method or a metal complex solution coating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction and silver layer formation by firing of silver complex ink.
  • the dry method is a general term for a vacuum film forming method, and specifically includes a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, and a sputtering method.
  • Etc. a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. That is, in the film mirror manufacturing method of the present invention, it is preferable to form the reflective layer 5 by silver vapor deposition.
  • the thickness of the reflective layer 5 is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectance and the like.
  • Corrosion prevention layer The corrosion prevention layer 6 formed on the film mirror according to the present invention is provided adjacent to the reflection layer 5 to prevent corrosion of the material of the reflection layer 5 (for example, silver). It is.
  • corrosion refers to a phenomenon in which an environmental substance surrounding the metal material (silver) causes the metal material to be chemically or electrochemically eroded or deteriorated in material quality (JIS Z0103-2004). reference).
  • the corrosion prevention layer 6 in the film mirror of the present invention is formed by including a silicone-modified resin, a silane coupling agent, and a compound having a thiol group in the molecule as a corrosion inhibitor.
  • the compound having a thiol group in the molecule is preferably a compound containing a plurality (two or more) of thiol groups.
  • the corrosion prevention layer 6 can maintain high adhesion with the reflective layer 5 even when installed for a long time in an outdoor environment.
  • the silicone-modified resin is a resin having a siloxane bond part (—Si—O—) n at the main chain, side chain, or terminal part of the resin skeleton.
  • n is an integer of 1 or more.
  • the silicone-modified resin used in the present invention may be, for example, a resin having a polysiloxane structure bonded to a resin serving as a main skeleton in a graft form, or a resin obtained by bonding a silane coupling agent to a resin serving as a main skeleton. May be.
  • Sites other than siloxane bonds in silicone-modified resins include, for example, cellulose esters, polyesters, polycarbonates, polyarylates, polysulfones (including polyether sulfones), polyethylene terephthalates, polyethylene naphthalates and other polyesters, cellulose diacetates, cellulose triacetates, and celluloses.
  • those having an acrylic resin skeleton and an alkyd resin skeleton are preferable, and an acrylic silicone resin having an acrylic resin skeleton is more preferable. More preferably, an acrylic resin skeleton having an amino group is used.
  • silicone-modified resins having a polysiloxane structure bonded in a graft form in the resin skeleton include Beckolite M-6665-60 (manufactured by Dainippon Ink and Chemicals), Beckolite M-6650-60 (Dainippon Ink).
  • Baysilone Resin UD-460M (Bayern), KP-541 (Shin-Etsu Silicone), KP-543 (Shin-Etsu Silicone), KP-545 (Shin-Etsu Silicone), KP-549 (Manufactured by Shin-Etsu Silicone), KP-550 (manufactured by Shin-Etsu Silicone), Metatron (manufactured by Daiho Chemical Co., Ltd.) and the like.
  • acrylic resin having an amino group in the skeleton examples include PTC-05 (manufactured by Fujikura Kasei), PTC-0505 (manufactured by Fujikura Kasei), PTC-05-B2 (manufactured by Fujikura Kasei), PTC.
  • silane coupling agent examples include 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- Glycidoxyethoxytrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- Butylidene) propylamine, N-phenyl-3-amin
  • the compound having a thiol group in the molecule is represented by the following general formula (3).
  • R 61 and R 62 represent a hydrogen atom or a substituent, and one of R 61 and R 62 represents a hydrogen atom. However, R 61 and R 62 do not both represent a hydrogen atom.
  • substituent represented by R 61 and R 62 include a halogen atom (eg, fluorine atom, chlorine atom), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trimethyl group).
  • 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.
  • cyano group acylamino group (eg acetylamino group, Propionylamino group, etc.), alkylthio group (eg methylthio group, ethyl) Thio group, butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamin
  • the number of thiol groups in the molecule is preferably 2 or more, and more preferably 3 or more.
  • the compound having a thiol group in the molecule is preferably a compound having no aromatic ring or unsaturated bond in the molecule, whereby the light resistance of the corrosion prevention layer can be further improved.
  • the compound having a thiol group in the molecule include, for example, mercaptoacetic acid, thiophenol, 1,2-ethanedithiol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto-1 , 2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, thionalide, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, butanediol bisthioglycolate, trimethylolpropane Tristhiopropionate, triethylene glycol dimercaptan, dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3 , 3-thiodipropionate, pentaerythritol tetra
  • trimethylolpropane tristhiopropionate and pentaerythritol tetrakisthiopropionate from the viewpoint of improving layer adhesion and corrosion resistance.
  • numerator is marketed with the brand name of BDTG, TMTG, PETG, TMTP, and PETP from Sakai Chemical Co., Ltd., for example.
  • the concentration of the compound having a thiol group in the molecule contained in the corrosion prevention layer 6 is preferably 0.01 to 5 wt%, more preferably 0.1 to 3 wt%.
  • a corrosion-preventing layer containing a silicone-modified resin effectively prevents chemical intrusion and has high corrosion resistance, but has low adhesion to the metal surface of the reflective layer and may gradually peel off.
  • the thiol group is bonded to the metal on the surface of the reflective layer, while maintaining high corrosion resistance. Adhesion can be improved.
  • the corrosion prevention layer 6 further contains a corrosion inhibitor such as a benztriazole compound, an imidazole compound, a tetrazaindene compound, or a thiadiazole compound. Also good.
  • a corrosion inhibitor such as a benztriazole compound, an imidazole compound, a tetrazaindene compound, or a thiadiazole compound. Also good.
  • the hard coat layer 9 formed on the film mirror according to the present invention is provided as the outermost surface layer of the film mirror.
  • the hard coat layer 9 is laminated on the second resin substrate 8 and provided on the outermost surface.
  • the film mirror 10b shown in FIG. Is laminated on the corrosion prevention layer 6 and provided on the outermost surface.
  • the hard coat layer 9 is provided to prevent the surface of the film mirror from being scratched or soiled, and to carry the UV absorber so as to function efficiently and for a long time.
  • the hard coat layer 9 can be formed by UV curing or thermosetting using, for example, an acrylic resin, a urethane resin, a melamine resin, an epoxy resin, an organic silicate compound, a silicone resin, or the like as a binder.
  • the hard coat layer 9 may contain a UV absorber made of an organic material or an inorganic material. Moreover, you may make it contain a photosensitizer, a photoinitiator, a thermal-polymerization initiator, a modifier, etc. as needed.
  • silica fine particles In order to obtain a hard coat layer 9 having a sufficiently high hardness and capable of sufficiently suppressing curling due to cure shrinkage, a curable resin composition used for forming the hard coat layer 9 is used. It is preferable to add silica fine particles.
  • the silica fine particles include powdery silica and colloidal silica, and those having an average particle diameter in the range of 0.01 to 20 ⁇ m are preferably used.
  • the silica fine particles are preferably those that do not affect the light transmittance of the hard coat film, and for that purpose, the primary particle diameter is preferably in the range of 10 to 350 nm, and in the range of 10 to 50 nm. More preferably, it is within.
  • the average particle size of the silica fine particles described above can be measured, for example, by observation with a transmission electron microscope.
  • the primary particle size of the silica fine particles is, for example, dispersed in a solvent such as isopropyl alcohol.
  • the dispersion can be measured by a Coulter particle size distribution measurement method, a laser diffraction scattering method, a dynamic light scattering method, or the like. Among these, the Coulter particle size distribution measurement method is common.
  • the shape of the silica fine particles may be spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, but in order to disperse the particles appropriately without agglomerating in the curable resin. , Preferably spherical.
  • the specific surface area of the silica fine particles is preferably in the range of 0.1 to 3000 m 2 / g, more preferably 1 m 2 / g or more, especially 10 m. More preferably, it is 2 / g or more and 1500 m 2 / g or less.
  • Such silica fine particles are also commercially available. Examples of commercially available silica fine particles include methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.), IPA-ST (manufactured by Nissan Chemical Industries, Ltd.), and MEK-ST (manufactured by Nissan Chemical Industries, Ltd.).
  • NBA-ST manufactured by Nissan Chemical Industries, Ltd.
  • XBA-ST manufactured by Nissan Chemical Industries, Ltd.
  • DMAC-ST manufactured by Nissan Chemical Industries, Ltd.
  • ST-UP manufactured by Nissan Chemical Industries, Ltd.
  • ST-OUP manufactured by Nissan Chemical Industries, Ltd.
  • ST-20 manufactured by Nissan Chemical Industries, Ltd.
  • ST-40 manufactured by Nissan Chemical Industries, Ltd.
  • ST-C Nonsan Chemical Industries, Ltd.
  • ST-N Nonsan Chemical Industry Co., Ltd.
  • ST-O Nissan Chemical Industry Co., Ltd.
  • ST-50 Nissan Chemical Industry Co., Ltd.
  • ST-OL Nissan) Chemical Industry Co., Ltd.
  • powdered silica examples include Aerosil 130 (Nippon Aerosil Co., Ltd.), Aerosil 300 (Nippon Aerosil Co., Ltd.), Aerosil 380 (Nippon Aerosil Co., Ltd.), Aerosil TT600 (Nippon Aerosil Co., Ltd.).
  • Aerosil OX50 produced by Nippon Aerosil Co., Ltd.
  • Sildex H31 produced by Asahi Glass Co., Ltd.
  • Sildex H32 produced by Asahi Glass Co., Ltd.
  • Sildex H51 produced by Asahi Glass Co., Ltd.
  • Sildex H52 Asahi Glass Co., Ltd.
  • Sildex H121 Asahi Glass Co., Ltd.
  • Sildex H122 Asahi Glass Co., Ltd.
  • E220A Nippon Silica Industry Co., Ltd.
  • E220 Nippon Silica Industry Co., Ltd.
  • Silysia 470 manufactured by Fuji Silysia Co., Ltd.
  • SG flake manufactured by Nippon Sheet Glass Co., Ltd.
  • a leveling agent is preferably added to the curable resin composition used for forming the hard coat layer 9 in order to ensure the surface smoothness of the resulting hard coat layer 9.
  • a leveling agent is an agent having an effect of adding to a paint to reduce the surface tension of the paint and improving the surface smoothness of the paint film.
  • Substances generally used as leveling agents include, for example, polyacrylate polymers such as polyalkyl acrylate, polyvinyl ether polymers such as polyalkyl vinyl ether, dimethyl polysiloxane, methylphenyl polysiloxane, and polyethers and polyesters. Examples thereof include silicone polymers such as organically modified polysiloxane introduced with aralkyl and the like.
  • a leveling agent having a fluorine atom can be obtained, for example, by copolymerizing a monomer having a fluorine-containing group.
  • Specific examples of commercially available products include Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, “SC-104” (any Manufactured by Asahi Glass Co., Ltd.), FLORARD “FC-430”, “FC-431”, “FC-173” (all manufactured by Fluorochemicals-Sumitomo 3M), F-top “EF352”, “EF301”, “EF303” ( All are made by Shin-Akita Kasei Co., Ltd.), Schwegofuller “8035”, “8036” (both made by Schwegman), “BM1000”, “BM1100” (both made by BM Himmy), MegaFuck “F” -171 ",” F-470 ",” RS-75 ",”
  • the UV absorber contained in the hard coat layer 9 may be a UV absorber made of an organic compound (organic UV absorber) or a UV absorber made of an inorganic compound (inorganic UV absorber). It may be good, and both may be contained.
  • a conventionally well-known UV absorber can be used as an organic UV absorber and an inorganic UV absorber. Examples of organic UV absorbers include triazine UV absorbers, benzophenone UV absorbers, and benztriazole UV absorbers, and it is particularly preferable to use triazine UV absorbers.
  • antioxidant it is preferable to add an antioxidant to the curable resin composition used for forming the hard coat layer 9.
  • an antioxidant it can select from the antioxidant group of a hindered phenol type compound, a hindered amine type compound, and a phosphorus compound, for example.
  • Specific examples of hindered phenol compounds include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t-butyl.
  • phenol compound of the above type is commercially available from Ciba Japan Co., Ltd. under the trade names “IRGANOX1076” and “IRGANOX1010”.
  • Specific examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like.
  • it may be a polymer type compound, and in particular, polycondensation of dibutylamine with 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine.
  • ADK STAB LA-52 Specific examples of the phosphorus compound include triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite.
  • Phosphorus compounds of the above type are, for example, from Sumitomo Chemical Co., Ltd. “Sumilizer GP”, from ADEKA Co., Ltd. “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, Ciba Japan Co., Ltd. It is commercially available under the trade name “IRGAFOS P-EPQ” from the company and “GSY-P101” from Sakai Chemical Industry Co., Ltd.
  • the coating liquid used for forming the hard coat layer 9 is solid content of ionizing radiation curable resin using at least one of ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone as a solvent. Can be obtained by diluting to a concentration of 30 to 70% by mass.
  • the solvent concentration is too high when the coating solution is applied onto the substrate, and the coating solution has a thickness of 10 to 30 ⁇ m.
  • Adhesive layer 7 formed on the film mirror (10a) according to the present invention is particularly limited as long as it has a function of improving the adhesion between the corrosion prevention layer 6 and the second resin substrate 8. There is no. Therefore, the adhesive layer 7 needs to have adhesion and smoothness for closely contacting the corrosion prevention layer 6 and the second resin base material 8.
  • the thickness of the adhesive layer 7 is preferably 0.01 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m, from the viewpoints of adhesion, smoothness, the reflectance of the reflective layer 5 and the like.
  • the adhesive layer 7 is a resin
  • polyester resin acrylic resin, melamine resin, epoxy resin, polyamide resin, Single or mixed resins such as vinyl chloride resins and vinyl chloride vinyl acetate copolymer resins
  • a mixed resin of a polyester resin and a melamine resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is mixed is more preferable.
  • a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method or the like can be used.
  • the adhesive layer 7 is a metal oxide
  • silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like formed by various vacuum film forming methods can be used.
  • a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, or a sputtering method can be used as a method for forming the adhesive layer 7 (film formation method).
  • the second resin base material 8 is a layer that mainly exists on the reflective surface side and suppresses protection from ultraviolet rays and entry of foreign substances from the external environment.
  • the second resin substrate 8 may be provided on an adjacent layer by being bonded via an adhesive, or may be provided directly by application or the like.
  • As the second resin substrate 8 used in the film mirror (10a) according to the present invention various conventionally known resin films can be used.
  • the second resin substrate 8 may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.
  • the thickness of the second resin substrate 8 is preferably set to an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 10 to 300 ⁇ m. The thickness is preferably 20 to 200 ⁇ m, more preferably 50 to 150 ⁇ m.
  • Reflector for solar power generation 20a, 20b is composed of at least film mirrors 10a, 10b and a metal substrate 1 as a support substrate, as shown in FIGS. Yes. In other words, the adhesive layers 2 of the film mirrors 10a and 10b are adhered to the metal substrate 1, so that the solar power generation reflecting devices 20a and 20b are formed.
  • the metal substrate 1 of the solar power generation reflectors 20a and 20b according to the present invention includes, for example, a steel plate, a copper plate, an aluminum plate, an aluminum plated steel plate, an aluminum alloy plated steel plate, a copper plated steel plate.
  • Metal materials such as a tin-plated steel plate, a chrome-plated steel plate, and a stainless steel plate can be used.
  • the thickness of the metal substrate 1 is preferably about 0.05 mm to 3 mm from the viewpoints of handleability, thermal conductivity, heat capacity, and the like.
  • the adhesive layer 2 for adhering the film mirrors 10a, 10b to the metal substrate 1 is not particularly limited.
  • a dry laminating agent, a wet laminating agent, an adhesive, a heat sealant, hot A melt agent or the like can be used.
  • a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like may be used.
  • the laminating method in particular which provides the adhesion layer 2 in the back surface of the 1st resin base material 3 is not restrict
  • the thickness of the pressure-sensitive adhesive layer 2 is usually preferably in the range of about 1 to 50 ⁇ m from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.
  • Specific materials used for the adhesive layer 2 include, for example, “SK Dyne Series” manufactured by Soken Chemical Co., Ltd., Oribain BPW Series, BPS Series manufactured by Toyo Ink Co., Ltd., “Arcon”, “Superester”, “High Pale” manufactured by Arakawa Chemical Co., Ltd.
  • the pressure-sensitive adhesive can be suitably used.
  • Example 1 A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 ⁇ m) was used as the first resin substrate 3. On one side of the polyethylene terephthalate film, a resin in which polyester resin, melamine resin, TDI isocyanate, and HMDI isocyanate are mixed at a resin solid content ratio of 20: 1: 1: 2 is coated by a gravure coating method. An anchor layer 4 having a thickness of 0.1 ⁇ m was formed. Next, a silver reflective layer having a thickness of 80 nm was formed as the reflective layer 5 on the anchor layer 4 by vacuum deposition.
  • an Origin resin # 100 clear which is an acrylic resin (silicone-modified resin) having an amino group in the side chain, a polyhard G21 as a curing agent containing a silane coupling agent having an epoxy group, and an origin thinner as a solvent.
  • the corrosion prevention layer 6 was formed by laminating a film made of an acrylic silicone resin having a thickness of 1 ⁇ m by drying at 150 ° C. for 5 minutes.
  • an acrylic resin adhesive (manufactured by Showa Polymer Co., Ltd.) is applied and coated to a thickness of 10 ⁇ m on the corrosion prevention layer 6 to form an adhesive layer 7 composed mainly of a resin. 7 was laminated as a second resin base material 8 with a thickness of 100 ⁇ m Technoloy S001 (manufactured by Sumitomo Chemical Co., Ltd.).
  • ZX-049 (Fuji Kasei Kogyo Co., Ltd.) as a fluorine-based leveling agent is added to the resin solid content on the second resin substrate 8 as a fluorine-based leveling agent.
  • Example 1 1% by weight, Tinuvin 477 (manufactured by Ciba Japan Co., Ltd.) as a triazine-based UV absorber added in an amount of 1.0% by weight based on the resin solid content is applied with a gravure coat to a wet film thickness of 40 ⁇ m, 80 A hard coat layer 9 was provided by heat treatment at 2 ° C. for 2 hours. In this way, a film mirror for solar power generation of Example 1 was prepared, which was provided with the corrosion prevention layer 6 containing “ORIJITZUKU # 100 clear” as a silicone-modified resin and “TMTP” as a compound having a thiol group.
  • corrosion prevention layer 6 containing “ORIJITZUKU # 100 clear” as a silicone-modified resin and “TMTP” as a compound having a thiol group.
  • Example 2 In the production of the film mirror for solar power generation in Example 1, as the coating solution for forming the corrosion-preventing layer 6, "Origigaku # 100 clear, polyhard G21 of curing agent containing a silane coupling agent having an epoxy group, origin thinner of solvent instead of using a solution of # 111NO2 at a mass ratio of 40:10:20, a solution of Beckolite M-6665-60 (Dainippon Ink Chemical Co., Ltd.), which is a silicone alkyd resin (silicone-modified resin), and epoxy
  • the corrosion prevention layer 6 was formed using a solution in which 2-glycidoxyethyltriethoxysilane (manufactured by Shin-Etsu Silicone), which is a silane coupling agent having a group, was used at a mass ratio of 40: 1. In this way, the film mirror for solar power generation of Example 2 is prepared, which includes the corrosion prevention layer 6 including “Beckolite M-6665-60” as the silicone-modified resin and “TM
  • Example 3 In preparation of the film mirror for solar power generation of Example 1, what added 5 mass% of pentaerythritol tetrakisthiopropionate (PETP) with respect to the solution instead of trimethylolpropane tristhiopropionate (TMTP) The corrosion prevention layer 6 was formed using it. Thus, a film mirror for solar power generation of Example 3 was prepared, which was provided with the corrosion prevention layer 6 containing “ORIJITZUKU # 100 clear” as the silicone-modified resin and “PETP” as the compound having a thiol group.
  • PETP pentaerythritol tetrakisthiopropionate
  • TMTP trimethylolpropane tristhiopropionate
  • Example 4 In the production of the film mirror for solar power generation in Example 1, the corrosion prevention layer 6 was formed by using Origitsuku # 200 clear (manufactured by Origin Electric Co., Ltd.) instead of Origitsuku # 100 clear. In this way, a film mirror for solar power generation of Example 4 was prepared, which was provided with a corrosion prevention layer 6 containing “Origid Tug # 200 Clear” as a silicone-modified resin and “TMTP” as a compound having a thiol group.
  • Example 5 In the production of the film mirror for solar power generation in Example 1, thionalide (2-mercapto-N- (2-naphthyl) acetamide, N--) was used instead of Origitsuk # 100 clear and trimethylolpropane tristhiopropionate (TMTP).
  • TMTP trimethylolpropane tristhiopropionate
  • the corrosion prevention layer 6 was formed using (2-naphthalenyl) -2-mercaptoacetamide).
  • a film mirror for solar power generation of Example 5 having a corrosion prevention layer 6 containing thionalide was produced.
  • Example 1 In the production of the film mirror for solar power generation of Example 2, the corrosion prevention layer was formed using a solution in which a curing agent (polyhard G21) containing a silane coupling agent was not added to the solution for forming the corrosion prevention layer.
  • a curing agent polyhard G21
  • TMTP silane coupling agent
  • Comparative Example 3 In the production of the film mirror for solar power generation of Comparative Example 2, 0.5% by mass of trimethylolpropane tristhiopropionate (TMTP) was contained in the corrosion prevention layer. Thus, the solar thermal power generation of Comparative Example 3 including “PMMA” as a silicone-modified resin and “TMTP” as a compound having a thiol group, and including a corrosion prevention layer not including a silane coupling agent (curing agent). A film mirror was prepared.
  • TMTP trimethylolpropane tristhiopropionate
  • the average value of regular reflectance is 87% or more.
  • ⁇ The average value of regular reflectance is 82% or more and less than 87%.
  • ⁇ The average value of regular reflectance is 77% or more, 82%.
  • X The average value of regular reflectance is less than 77%
  • Table 1 shows the results of the evaluation of the film adhesion and the corrosion resistance.
  • the corrosion prevention layer 6 containing a silicone-modified resin and a silane coupling agent and further containing a compound having a thiol group in the molecule is provided on the light reflection side of the reflection layer 5.
  • the film mirrors for solar power generation of Examples 1 to 5 provided adjacent to each other maintain the film adhesion between the reflective layer 5 and the corrosion prevention layer 6 even after the UV deterioration treatment, and the reflective layer 5 is also altered. It has not occurred, and it can be seen that the weather resistance is excellent.
  • the film mirrors for solar power generation in Comparative Examples 1 to 3 in which any of the silicone-modified resin, the silane coupling agent, and the compound having a thiol group in the molecule is deficient are reduced in film adhesion after UV deterioration treatment. It can be seen that both or any of the alterations of the reflective layer 5 occur and cannot be used outdoors for a long time.
  • the film mirrors 10a and 10b of the present invention are excellent in adhesion at the interface between the reflective layer 5 and the corrosion prevention layer 6, and are based on the corrosion prevention layer 6.
  • the reflective layer 5 is also excellent in corrosion resistance.
  • the film mirrors 10a and 10b according to the present invention have excellent weather resistance, and peeling occurs at the interface between the reflective layer 5 and the corrosion prevention layer 6 even if the film mirrors 10a and 10b are cleaned after being installed outdoors for a long period of time. And good regular reflectance with respect to sunlight can be maintained.
  • the solar power generation reflecting devices 20a and 20b formed by attaching such film mirrors 10a and 10b to the metal substrate 1 through the adhesive layer 2 also maintain good regular reflectance with respect to sunlight. It can be said that it is possible.
  • the present invention provides a film mirror that has high adhesion between the reflective layer and the corrosion prevention layer and can suppress the corrosion of the reflective layer, and a solar power generation reflector using the film mirror. Is suitable.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
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  • Optical Elements Other Than Lenses (AREA)

Abstract

Dans un miroir à film (10a) ayant une couche réfléchissante (5) prévue sur un premier substrat de résine (3), une couche de prévention de la corrosion (6) amenée à être adjacente au côté réflexion de la lumière de la couche réfléchissante (5) contient une résine modifiée de silicium et un agent de couplage silane, et est également configurée pour contenir un composé ayant un groupe thiol dans chaque molécule.
PCT/JP2013/058094 2012-03-22 2013-03-21 Miroir à film, et dispositif de réflexion pour la génération d'énergie solaire WO2013141304A1 (fr)

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WO2017002814A1 (fr) * 2015-06-30 2017-01-05 コニカミノルタ株式会社 Film réflecteur de lumière, procédé de fabrication de film réflecteur de lumière et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
WO2017047649A1 (fr) * 2015-09-15 2017-03-23 コニカミノルタ株式会社 Film de réflexion de lumière, et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
WO2017164226A1 (fr) * 2016-03-25 2017-09-28 コニカミノルタ株式会社 Film réfléchissant la lumière et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
WO2023190477A1 (fr) * 2022-03-30 2023-10-05 日東電工株式会社 Structure multicouche

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JP2000106017A (ja) * 1998-09-29 2000-04-11 Koito Mfg Co Ltd 車両用灯具
WO2011158665A1 (fr) * 2010-06-18 2011-12-22 コニカミノルタオプト株式会社 Film miroir et dispositif réfléchissant pour la production d'énergie thermique solaire
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WO2017002814A1 (fr) * 2015-06-30 2017-01-05 コニカミノルタ株式会社 Film réflecteur de lumière, procédé de fabrication de film réflecteur de lumière et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
WO2017047649A1 (fr) * 2015-09-15 2017-03-23 コニカミノルタ株式会社 Film de réflexion de lumière, et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
WO2017164226A1 (fr) * 2016-03-25 2017-09-28 コニカミノルタ株式会社 Film réfléchissant la lumière et unité de rétroéclairage pour dispositif d'affichage à cristaux liquides
CN108885285A (zh) * 2016-03-25 2018-11-23 柯尼卡美能达株式会社 光反射膜及液晶显示装置用背光单元
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