WO2011077816A1 - フィルムミラー、その製造方法及び太陽熱発電用反射装置 - Google Patents
フィルムミラー、その製造方法及び太陽熱発電用反射装置 Download PDFInfo
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- WO2011077816A1 WO2011077816A1 PCT/JP2010/068320 JP2010068320W WO2011077816A1 WO 2011077816 A1 WO2011077816 A1 WO 2011077816A1 JP 2010068320 W JP2010068320 W JP 2010068320W WO 2011077816 A1 WO2011077816 A1 WO 2011077816A1
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- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- WUBJXWWQGDPUCE-UHFFFAOYSA-N propan-1-olate yttrium(3+) Chemical compound [Y+3].CCC[O-].CCC[O-].CCC[O-] WUBJXWWQGDPUCE-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- TYSXNZUFDKPFED-UHFFFAOYSA-N zinc;propan-1-olate Chemical compound [Zn+2].CCC[O-].CCC[O-] TYSXNZUFDKPFED-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- 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
- F24S23/81—Arrangements for concentrating solar-rays for solar heat collectors with reflectors flexible
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- 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 having excellent light resistance and weather resistance, and having a good regular reflectance with respect to solar heat, a manufacturing method thereof, and a solar power generation reflector using the film mirror.
- a glass mirror Since the reflection device is exposed to ultraviolet rays, heat, wind and rain, sandstorms, etc. due to solar heat, a glass mirror has been conventionally used. Glass mirrors are highly durable against the environment, but they are damaged during transportation and have a large mass, so that the strength of the frame on which the mirrors are installed increases, which increases the construction cost of the plant.
- Patent Document 2 For the purpose of concentrating solar heat, from the viewpoint of obtaining a high reflectance, as disclosed in Patent Document 2, a technique for forming a metal layer with silver having a high reflectance in the visible light region has been proposed.
- silver for the reflective layer it is possible to increase the initial reflectivity, but due to deterioration of the resin due to ultraviolet rays, it is possible to sufficiently suppress the decrease in reflectivity when used for a long time. It was difficult.
- Patent Document 3 proposes a technique of providing a layer containing a benzotriazole ultraviolet absorber on the surface layer of a film mirror.
- Patent Document 3 by adding a crosslinkable monomer having a vinyl group to the surface layer, the compatibility between the benzotriazole-based UV absorber and the resin in the surface layer is improved, and the amount of the UV absorber added is increased.
- ultraviolet absorbers contained in large quantities are aged. The problem of peeling due to lower adhesion between layers and the deformation of the silver reflective layer and the reduction of regular reflectance as a film mirror became apparent.
- This invention is made
- a film mirror that is light and flexible, can be manufactured in a large area and mass-produced with low manufacturing cost, has excellent light resistance and weather resistance, and has good regular reflectance to solar heat,
- An object of the present invention is to provide a manufacturing method and a solar power generation reflecting device using the film mirror.
- a film mirror having a resin base material, a silver reflective layer provided on the resin base material, and a layer containing an ultraviolet absorber provided on the light incident side of the resin base material and the silver reflective layer. And at least one of the ultraviolet absorbers satisfies the following formula 1.
- Formula 1 Aa ⁇ 1.2 ⁇ Ab
- Aa Absorbance of an absorption maximum peak at 260 to 320 nm (0 when no absorption peak exists at 260 to 320 nm)
- Ab Absorbance of absorption maximum peak at 321 to 400 nm (0 when no absorption peak exists at 321 to 400 nm) 2.
- the gas barrier layer having a water vapor transmission rate at 40 ° C. and 90% RH of 1 g / m 2 ⁇ day / ⁇ m or less on the light incident side of the resin base material and the silver reflective layer is 1 to 3. 4.
- the film mirror according to any one of 3 above.
- the resin base material is a layer having polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and is provided on a side farther from the light incident side than the silver reflecting layer.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- the present invention it is possible to efficiently shield the wavelength that is transmitted through the silver reflection layer, and the regular reflectance is reduced when the layer provided on the side far from the light incident side of the silver reflection layer is deteriorated by ultraviolet rays. Can be suppressed.
- a film mirror that has excellent light resistance and weather resistance and can be mass-produced and has good specular reflectance with respect to solar heat, a manufacturing method thereof, and a solar power generation reflector using the film mirror. I was able to.
- the present inventor has a high reflectance at the start of use due to the high reflectance of the silver reflective layer when a film mirror having a silver reflective layer is used as a reflective device for solar power generation. Although it can be obtained, it has become clear that the problem of a decrease in regular reflectance occurs when exposed to strong sunlight for a long time.
- the silver reflective layer was considered to be one of the factors, unlike the reflective layer made of aluminum or the like, having a property of transmitting ultraviolet light of 320 nm or less.
- the ultraviolet light transmitted through the silver reflecting layer passes through the layer below the silver reflecting layer (the side far from the light incident side), is reflected by the metal support, and then enters the lower layer of the silver reflecting layer again. Become. Therefore, the lower layer of the silver reflecting layer is deteriorated by ultraviolet light, or the silver reflecting layer is deteriorated by being excited between the silver reflecting layer and the lower layer, and the regular reflectance of the silver reflecting layer is lowered. I found it.
- an ultraviolet absorber as in Reference 3.
- a normal ultraviolet absorber is required to have a characteristic of absorbing the entire ultraviolet region of 400 nm or less, an ultraviolet absorber having an average large absorption with respect to light in the entire ultraviolet region is used.
- an ultraviolet absorber having a high ultraviolet absorption function in the entire ultraviolet region is practically difficult to manufacture, and the ultraviolet absorber described in Reference 3 also exhibits a sufficient absorption function for ultraviolet rays having a wavelength of 320 nm or less. Therefore, when it is used in an environment where it is directly exposed to sunlight for a long period of time, the decrease in regular reflectance could not be suppressed. Therefore, the present inventor has caused the above-described decrease in regular reflectance caused by deterioration of a resin layer such as a resin base material or an adhesive layer provided as an adjacent layer far from the light incident side of the silver reflection layer. Focused on that.
- unnecessary ultraviolet rays can be obtained by using an ultraviolet absorber that has a large ultraviolet absorption effect for light in the ultraviolet region of 320 nm or less that transmits through the silver reflection layer and that has a small absorption effect for light in the region of 321 to 400 nm.
- an ultraviolet absorber that has a large ultraviolet absorption effect for light in the ultraviolet region of 320 nm or less that transmits through the silver reflection layer and that has a small absorption effect for light in the region of 321 to 400 nm.
- the film mirror of the present invention includes a resin base material, a silver reflective layer provided on the resin base material, and a layer containing an ultraviolet absorber provided on the light incident side of the resin base material and the silver reflective layer.
- the film mirror is characterized in that at least one of the ultraviolet absorbers satisfies the above formula (1). It is also a preferable aspect to provide a special functional layer such as a gas barrier layer or a scratch prevention layer.
- UV absorber used in the film mirror of the present invention is characterized in that at least one of them satisfies the following formula 1.
- Formula 1 Aa ⁇ 1.2 ⁇ Ab Aa: Absorbance of an absorption maximum peak at 260 to 320 nm (0 when no absorption peak exists at 260 to 320 nm)
- Ba Absorbance of an absorption maximum peak at 321 to 400 nm (0 when no absorption peak exists at 321 to 400 nm)
- the absorption maximum peak and absorbance at 260 to 400 nm can be measured with a spectrophotometer.
- the embodiment of the present invention it is possible to effectively absorb the ultraviolet light transmitted through the silver reflecting layer, and therefore, it is not necessary to increase the amount of addition excessively.
- deterioration of the constituent layers over time due to deterioration of the ultraviolet absorber itself due to ultraviolet rays and the accompanying decrease in regular reflectance can be suppressed.
- the ultraviolet absorber satisfying the above-described formula 1 of the present invention is contained in any one layer provided on the light incident side of the resin base material and the silver reflective layer.
- an ultraviolet absorber having a triazine, benzophenone or cyanoacrylate skeleton is preferable. Specific examples thereof include UVINUL3000, UVINUL3008, UVINUL3030, UVINUL3035, UVINUL3039, UVINUL3040, UVINUL3088, TINUVIN400, TINUVIN1577 manufactured by Ciba Japan, and LA51 manufactured by ADEKA. is not.
- the amount of the ultraviolet absorber that satisfies the above-mentioned formula 1 of the present invention is preferably 3 to 14% by mass, and more preferably 3 to 10% by mass. When it exceeds 14% by mass, the bleed-out over time may affect the silver reflective layer and adhesion, and the coating solution stability in the process may also deteriorate. When it is less than 0.1% by mass, the weather resistance improvement effect is small.
- UV absorbers In the present invention, the following ultraviolet absorbers can also be used in combination.
- UV absorbers used in combination include benzophenone, benzotriazole, phenyl salicylate, and triazine.
- benzophenone ultraviolet absorber examples include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetra And hydroxy-benzophenone.
- benzotriazole ultraviolet absorber examples include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.
- phenyl salicylate ultraviolet absorber examples include phenylsalicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
- hindered amine ultraviolet absorber examples include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
- triazine ultraviolet absorbers examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxy
- ultraviolet absorbers examples include compounds having the function of converting the energy held by ultraviolet rays into vibrational energy within the molecule and releasing the vibrational energy as thermal energy. Furthermore, those that exhibit an effect when used in combination with an antioxidant, a colorant, or the like, or a light stabilizer that acts as a light energy conversion agent, called a quencher, can be used in combination.
- the binder for the layer containing the ultraviolet absorber may be a resin layer or a layer made of an inorganic substance, but is preferably a resin layer from the viewpoint of production.
- a resin layer a conventionally known thermoplastic resin or curable resin can be used.
- a polyester resin, an acrylate resin, a melamine resin, an epoxy resin, a polyamide resin, a vinyl chloride resin, a vinyl chloride vinyl acetate copolymer resin, etc. can be used alone or a mixed resin thereof. From the viewpoint, a mixed resin of a polyester resin and a melamine resin is preferable.
- the resin constituting the layer containing the ultraviolet absorber is preferably one having a high resistance to ultraviolet rays, and among them, an acrylate resin is preferably used.
- an acrylate resin is used, an ultraviolet absorber having a cyanoacrylate skeleton and satisfying the above formula 1 is particularly preferably used as the ultraviolet absorber from the viewpoint of compatibility.
- resin base material As the resin base material (support) according to the present invention, various conventionally known resin films can be used.
- a polyester film, a cellulose ester film, a polymethyl methacrylate film, and a polyacryl film are preferable, and polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is particularly preferable.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- These films may be films produced by melt casting film formation or films produced by solution casting film formation.
- the thickness of the resin base material is an appropriate thickness depending on the type and purpose of the resin. For example, it is generally in the range of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
- the film mirror according to the present invention may have an adhesive layer.
- the adhesive layer may be used to increase the adhesiveness between the silver reflective layer and the resin base material (resin film) or may increase the adhesiveness between other constituent layers, but is made of a resin. Is preferred.
- the adjacent layer far from the light incident side of the silver reflective layer is an adhesive layer, it can be considered that the regular reflectance decreases due to the deterioration of the adhesive layer. Reduction of regular reflectance can be suppressed.
- the adhesive layer is used as an adjacent layer of the silver reflective layer, the adhesiveness between the resin base material (resin film) and the silver reflective layer is also in close contact with the heat when the silver reflective layer is formed by a vacuum deposition method or the like. It is preferable to have heat resistance that can be withstood, and smoothness to bring out the high reflection performance inherent to the silver reflective layer.
- the resin used as the binder for the adhesive layer is not particularly limited as long as it satisfies the above conditions for adhesion, heat resistance, and smoothness.
- Polyester resin, acrylate resin, melamine resin, epoxy resin Resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, etc. can be used alone or a mixed resin thereof. From the viewpoint of weather resistance, a polyester resin and a melamine resin mixed resin are preferable. It is more preferable to use a thermosetting resin mixed with a curing agent such as isocyanate.
- polyester resins polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.
- the thickness of the adhesive layer is preferably from 0.01 to 3 ⁇ m, more preferably from 0.1 to 1 ⁇ m, from the viewpoints of adhesion, smoothness, reflectance of the reflecting material, and the like.
- a method for forming the adhesive layer conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
- Silver reflection layer As a method for forming the silver reflective layer according to the present invention, either a wet method or a dry method can be used.
- the wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction.
- the dry method is a general term for a vacuum film-forming method.
- a resistance heating vacuum deposition method an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, 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, as a film mirror manufacturing method for manufacturing the film mirror of the present invention, a manufacturing method in which a silver reflective layer is formed by silver vapor deposition is preferable.
- the thickness of the silver reflective layer is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectivity and the like.
- the silver reflection layer may be on the light incident side or on the opposite side with respect to the resin base material (support), but since the support is a resin, the resin is deteriorated by light rays. For the purpose of preventing, it is preferable to be positioned on the light incident side.
- a silver adjacent layer may be provided adjacent to the upper part (light incident side) of the silver reflective layer.
- the adjacent layer on the light incident side contains a corrosion inhibitor to prevent silver corrosion deterioration and prevent damage to the silver reflective layer. And it is preferable that it contributes to the adhesive force improvement with the barrier layer formed in the outer side of a silver adjacent layer, and a damage prevention layer.
- the resin used as the binder for the silver adjacent layer may be a polyester resin, an acrylic resin, a melamine resin, an epoxy resin or a mixture of these resins, and an acrylic resin is preferred from the viewpoint of weather resistance. Furthermore, it is more preferable to use a thermosetting resin mixed with a curing agent such as isocyanate.
- isocyanate various conventionally used isocyanates such as TDI (tolylene diisocyanate), XDI (xylene diisocyanate), MDI (methylene diisocyanate), and HMDI (hexamethylene diisocyanate) can be used. From the viewpoint of properties, XDI, MDI, and HMDI isocyanates are preferably used.
- the thickness of the silver adjacent layer is preferably from 0.01 to 3 ⁇ m, more preferably from 0.1 to 1 ⁇ m, from the viewpoints of adhesion, weather resistance and the like.
- a method for forming the silver adjacent layer conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
- the film mirror of the present invention preferably has a layer containing a corrosion inhibitor for the silver reflective layer adjacent to the silver reflective layer.
- a corrosion inhibitor refers to a phenomenon in which metal (silver) is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it (see JIS Z0103-2004).
- the adhesive layer contains an antioxidant and the upper adjacent layer contains a corrosion inhibitor having an adsorptive group for silver.
- the optimum amount of the corrosion inhibitor varies depending on the compound to be used, but generally it is preferably in the range of 0.1 to 1.0 / m 2 .
- a corrosion inhibitor and an antioxidant having an adsorptive group for silver are preferably used.
- Corrosion inhibitor having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole It is desirable to select from a compound having a ring, a copper chelate compound, a thiourea, a compound having a mercapto group, at least one kind of naphthalene, or a mixture thereof.
- amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, O-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2N- Dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysoidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium
- Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, 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 a mixture 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-ethyl
- 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
- naphthalene-based compounds examples include thionalide.
- An antioxidant can also be used as a corrosion inhibitor for the silver reflective layer used in the film mirror of the present invention.
- the antioxidant it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, and a phosphite-based antioxidant.
- phenolic antioxidants examples include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t- Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl- ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propi , Triethylene glycol bis [3- (3-
- thiol-based antioxidant examples include distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thiopropionate), and the like.
- phosphite antioxidant examples include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol.
- Diphosphite bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-diphosphonite 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like.
- the above antioxidant and the following light stabilizer can be used in combination.
- hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl- 8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-Tetrame Lupiperidine, tetrakis (2,2,2,
- nickel-based UV stabilizers include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, etc. can also be used.
- a hindered amine light stabilizer containing only a tertiary amine is preferable.
- bis (1,2,2,6,6-pentamethyl-4-piperidyl) is preferable.
- a condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.
- the film mirror of the present invention preferably has a gas barrier layer on the light incident side of the resin base material and the silver reflective layer.
- the gas barrier layer according to the present invention is intended to prevent deterioration of the humidity, particularly deterioration of the resin base material and various functional elements protected by the resin base material due to high humidity. As long as the above characteristics are maintained, various types of gas barrier layers can be provided. In the present invention, it is preferable to provide a gas barrier layer above the silver adjacent layer.
- the water vapor permeability at 40 ° C. and 90% RH is 1 g / m 2 ⁇ day / ⁇ m or less, preferably 10 ⁇ 1 g / m 2 ⁇ day / ⁇ m or less, more preferably 10 ⁇ . It is preferable to adjust the moisture barrier property of the gas barrier layer so that it becomes 2 g / m 2 ⁇ day / ⁇ m or less. Also.
- the oxygen permeability is preferably 0.6 ml / m 2 / day / atm or less under the conditions of 23 ° C. and 90% RH.
- the gas barrier layer according to the present invention is not particularly limited in its formation method, but after applying the ceramic precursor of the inorganic oxide film, the inorganic oxide film is formed by heating and / or ultraviolet irradiation of the coating film.
- the method is preferably used.
- the gas barrier layer according to the present invention can be formed by applying a general heating method after applying a ceramic precursor that forms an inorganic oxide film by heating, but is preferably formed by local heating.
- the ceramic precursor is preferably a sol-like organometallic compound or polysilazane.
- the organometallic compound according to the present invention includes silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), and indium. It is preferable to contain at least one element of (In), tin (Sn), lanthanum (La), yttrium (Y), and niobium (Nb).
- the organometallic compound is at least one element of silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), zinc (Zn), and barium (Ba). It is preferable to contain. Furthermore, it is preferable to contain at least one element of silicon (Si), aluminum (Al), and lithium (Li).
- the organometallic compound is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include metal alkoxides.
- the metal alkoxide is represented by the following general formula (I).
- M represents a metal having an oxidation number n.
- R 1 and R 2 each independently represents an alkyl group.
- m represents an integer of 0 to (n ⁇ 1).
- R 1 and R 2 may be the same or different.
- R 1 and R 2 are preferably alkyl groups having 4 or less carbon atoms, for example, a methyl group CH 3 (hereinafter represented by Me), an ethyl group C 2 H 5 (hereinafter represented by Et), a propyl group.
- C 3 H 7 (hereinafter represented by Pr), isopropyl group i-C 3 H 7 (hereinafter represented by i-Pr), butyl group C 4 H 9 (hereinafter represented by Bu), isobutyl group i- A lower alkyl group such as C 4 H 9 (hereinafter referred to as i-Bu) is more preferred.
- Examples of the metal alkoxide represented by the general formula (I) include lithium ethoxide LiOEt, niobium ethoxide Nb (OEt) 5 , magnesium isopropoxide Mg (OPr-i) 2 , aluminum isopropoxide Al (OPr -I) 3 , zinc propoxide Zn (OPr) 2 , tetraethoxysilane Si (OEt) 4 , titanium isopropoxide Ti (OPr-i) 4 , barium ethoxide Ba (OEt) 2 , barium isopropoxide Ba ( OPr-i) 2 , triethoxyborane B (OEt) 3 , zirconium propoxide Zn (OPr) 4 , lanthanum propoxide La (OPr) 3 , yttrium propoxide Y (OPr) 3 , lead isopropoxide Pb (OPr- i) 2 etc. are mentioned suitably. All of these metal alkoxide
- the inorganic oxide according to the present invention is formed by local heating from a sol using the organometallic compound as a raw material. Therefore, silicon (Si), aluminum (Al), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), indium (In) contained in the organometallic compound, It is an oxide of an element such as tin (Sn) or niobium (Nb).
- silicon oxide aluminum oxide, zirconium oxide and the like. Of these, silicon oxide is preferable.
- a method for forming an inorganic oxide from an organometallic compound it is preferable to use a so-called sol-gel method and a method of applying polysilazane.
- the “sol-gel method” is to obtain a hydroxide sol by hydrolyzing an organometallic compound, etc., dehydrate it into a gel, and further heat-treat the gel. It refers to a method for preparing a metal oxide glass having a certain shape (film, particle, fiber, etc.).
- a multi-component metal oxide glass can be obtained by a method of mixing a plurality of different sol solutions, a method of adding other metal ions, or the like.
- an inorganic oxide by a sol-gel method having the following steps.
- the organometallic compound in a reaction solution containing at least water and an organic solvent, is hydrolyzed and dehydrated and condensed while adjusting the pH to 4.5 to 5.0 using a halogen ion as a catalyst in the presence of boron ion.
- Generation of fine pores due to high-temperature heat treatment is produced by a sol-gel method having a step of obtaining a reaction product by heating and vitrifying the reaction product at a temperature of 200 ° C. or less. And is particularly preferable from the viewpoint that no deterioration of the film occurs.
- the organometallic compound used as a raw material is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include the metal alkoxides. .
- the organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction.
- the solvent for dilution is not particularly limited as long as it can dissolve the organometallic compound and can be uniformly mixed with water.
- Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof.
- a mixed solvent of butanol, cellosolve, and butyl cellosolve or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.
- the metal when the metal is Ca, Mg, Al or the like, it reacts with water in the reaction solution to form a hydroxide, or when carbonate ion CO 3 2- is present, a carbonate is formed. Therefore, it is preferable to add an alcohol solution of triethanolamine as a masking agent to the reaction solution.
- the concentration of the organometallic compound when mixed and dissolved in a solvent is preferably 70% by mass or less, and more preferably diluted to a range of 5 to 70% by mass.
- the reaction solution used in the sol-gel method contains at least water and an organic solvent.
- the organic solvent is not particularly limited as long as it can form a uniform solution with water, acid, and alkali, and usually the same aliphatic lower alcohols used for diluting the organometallic compound are preferably used.
- the aliphatic lower alcohols propanol, isopropanol, butanol, and isobutanol having a larger number of carbon atoms are preferable to methanol and ethanol. This is because the growth of the metal oxide glass film to be generated is stable.
- the water ratio is preferably in the range of 0.2 to 50 mol / L as the concentration of water.
- an organometallic compound is hydrolyzed in the reaction solution in the presence of boron ions using a halogen ion as a catalyst.
- Preferred examples of the compound that gives the boron ion B 3+ include trialkoxyborane B (OR) 3 . Among these, triethoxyborane B (OEt) 3 is more preferable.
- the B 3+ ion concentration in the reaction solution is preferably in the range of 1.0 to 10.0 mol / L.
- halogen ion a fluorine ion and / or a chlorine ion are mentioned suitably. That is, fluorine ions alone, chlorine ions alone or a mixture thereof may be used.
- the compound to be used is not particularly limited as long as it generates fluorine ions and / or chlorine ions in the reaction solution.
- a fluorine ion source ammonium hydrogen fluoride NH 4 HF ⁇ HF, sodium fluoride NaF or the like is preferable.
- Preferred examples of the chlorine ion source include ammonium chloride NH 4 Cl.
- the concentration of the halogen ions in the reaction solution varies depending on the film thickness of an inorganic composition having an inorganic matrix to be produced and other conditions, but generally the reaction solution containing a catalyst. Is preferably in the range of 0.001 to 2 mol / kg, particularly 0.002 to 0.3 mol / kg. If the halogen ion concentration is lower than 0.001 mol / kg, hydrolysis of the organometallic compound does not proceed sufficiently, and film formation becomes difficult. Moreover, since the produced
- boron used during the reaction, if to be contained as a B 2 O 3 component in the design the composition of the resulting inorganic matrix, by leaving product was added calculated amount of organic boron compound in accordance with the content of
- boron can be removed by evaporation as boron methyl ester by heating after film formation in the presence of methanol as a solvent or by immersion in methanol.
- a main agent solution in which a predetermined amount of the organometallic compound is usually mixed and dissolved in a mixed solvent containing a predetermined amount of water and an organic solvent,
- the pH of the reaction solution is adjusted to a desired value with acid or alkali.
- the reaction product is obtained by aging for several hours.
- a predetermined amount of the boron compound is mixed and dissolved in advance in the main agent solution or reaction solution. Further, when alkoxyborane is used, it is advantageous to dissolve it in the main agent solution together with other organometallic compounds.
- the pH of the reaction solution is selected depending on the purpose, and for the purpose of forming a film (film) made of an inorganic composition having an inorganic matrix (metal oxide glass), for example, the pH is adjusted using an acid such as hydrochloric acid. It is preferable to ripen the mixture by adjusting it to the range of 4.5 to 5. In this case, for example, it is convenient to use a mixture of methyl red and bromocresol green as an indicator.
- the main component solution having the same concentration of the same component and the reaction solution including B 3+ and halogen ions
- the reaction product can also be produced simply and continuously.
- the concentration of the reaction solution is in the range of ⁇ 50% by mass
- the concentration of water (including acid or alkali) is in the range of ⁇ 30% by mass
- the concentration of halogen ions is in the range of ⁇ 30% by mass. Can be changed.
- reaction product reaction solution after aging
- reaction solution after aging reaction solution after aging
- the temperature is raised gradually while paying particular attention to a temperature range of 50 to 70 ° C., followed by a preliminary drying (solvent volatilization) step and further raising the temperature.
- This drying is important for forming a non-porous film in the case of film formation.
- the temperature for heating and drying after the preliminary drying step is preferably 70 to 150 ° C, more preferably 80 to 130 ° C.
- the gas barrier layer according to the present invention contains an inorganic oxide formed by local heating of a coating film after applying a ceramic precursor that forms an inorganic oxide film by heating.
- the resin substrate is coated with a solution containing a catalyst in the polysilazane represented by the following general formula (II) and an organic solvent as necessary, and the solvent is added to the ceramic precursor. Evaporate and remove, thereby leaving a polysilazane layer having a layer thickness of 0.05-3.0 ⁇ m on the resin substrate, and oxygen, active oxygen, in some cases, and nitrogen in an atmosphere containing water vapor It is preferable to employ a method of forming a glass-like transparent film on the resin substrate by locally heating the polysilazane layer in the presence.
- R 1 , R 2 , and R 3 are the same or different and independently of each other, hydrogen, or an optionally substituted alkyl group, aryl group, vinyl group, or (trialkoxysilyl)
- An alkyl group preferably consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl)
- n is an integer
- n is defined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
- catalysts preferably basic catalysts, in particular N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine or N-heterocyclic compounds are used.
- the catalyst concentration is usually in the range of 0.1 to 10 mol%, preferably 0.5 to 7 mol%, based on polysilazane.
- a solution containing perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is used.
- the coating according to the present invention comprises at least one polysilazane of the following general formula (III):
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, optionally substituted alkyl group, aryl group, vinyl group or ( Represents a trialkoxysilyl) alkyl group, wherein n and p are integers, and n is defined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
- R 1 , R 3 and R 6 represent hydrogen and R 2 , R 4 and R 5 represent methyl, R 1 , R 3 and R 6 represent hydrogen and R 2 , A compound in which R 4 represents methyl and R 5 represents vinyl, R 1 , R 3 , R 4 and R 6 represent hydrogen and R 2 and R 5 represent methyl.
- a solution containing at least one polysilazane represented by the following general formula (IV) is also preferable.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently of one another hydrogen or optionally substituted alkyl.
- R 1 , R 3 and R 6 represent hydrogen and R 2 , R 4 , R 5 and R 8 represent methyl, R 9 represents (triethoxysilyl) propyl and R 7 Is a compound in which represents alkyl or hydrogen.
- the proportion of polysilazane in the solvent is generally 1 to 80% by mass, preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass.
- an organic system that does not contain water and a reactive group (for example, a hydroxyl group or an amine group) and is inert to polysilazane, preferably an aprotic solvent, is particularly suitable.
- a reactive group for example, a hydroxyl group or an amine group
- an aprotic solvent is particularly suitable.
- An additional component of the polysilazane solution can be a further binder such as those conventionally used in the manufacture of paints.
- cellulose ethers and cellulose esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose acetobutyrate, natural resins such as rubber or rosin resins, or synthetic resins such as polymerized resins or condensed resins such as aminoplasts, in particular Urea resins and melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, or polysiloxanes.
- Still other components of the polysilazane formulation include, for example, additives that affect the formulation viscosity, substrate wetting, film formability, lubrication or exhaust properties, or inorganic nanoparticles such as SiO 2 , TiO 2 , It can be ZnO, ZrO 2 or Al 2 O 3 .
- the thickness of the coating film to be formed is preferably in the range of 100 nm to 2 ⁇ m.
- scratch prevention layer In the present invention, it is preferable to provide a scratch preventing layer as the outermost layer of the film mirror.
- the scratch prevention layer is provided for preventing scratches.
- the scratch prevention layer can be composed of acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicone resin, and the like.
- silicone resins and acrylic resins are preferable in terms of hardness and durability. Further, in terms of curability, flexibility, and productivity, those made of an active energy ray-curable acrylic resin or a thermosetting acrylic resin are preferable.
- the active energy ray-curable acrylic resin or thermosetting acrylic resin is a composition containing a polyfunctional acrylate, an acrylic oligomer, or a reactive diluent as a polymerization curing component.
- Acrylic oligomers include polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, etc., including those in which a reactive acrylic group is bonded to an acrylic resin skeleton, and rigid materials such as melamine and isocyanuric acid. A structure in which an acrylic group is bonded to a simple skeleton can also be used.
- the reactive diluent has a function of a solvent in the coating process as a medium of the coating agent, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a copolymerization component.
- polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam (registered trademark)” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol (registered trademark)” series, etc. ), Shin-Nakamura Co., Ltd.
- various additives can be further blended in the scratch-preventing layer as required, as long as the effects of the present invention are not impaired.
- stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, surfactants, leveling agents, antistatic agents, and the like can be used.
- ⁇ Leveling agents are effective in reducing surface irregularities, especially when functional layers are applied.
- a dimethylpolysiloxane-polyoxyalkylene copolymer for example, SH190 manufactured by Toray Dow Corning Co., Ltd.
- SH190 manufactured by Toray Dow Corning Co., Ltd. is suitable as the silicone leveling agent.
- the total thickness of the film mirror according to the present invention is preferably 75 to 250 ⁇ m, more preferably 90 to 230 ⁇ m, and still more preferably 100 to 220 ⁇ m, from the viewpoints of prevention of deflection of the mirror, regular reflectance, handling properties, and the like.
- the film mirror of the present invention can be preferably used for the purpose of collecting solar heat. Although it can also be used as a solar heat collector mirror with a single film mirror, more preferably, through an adhesive layer coated on the resin substrate surface opposite to the side having the silver reflective layer across the resin substrate, The film mirror is affixed on another base material, particularly on a metal base material, and used as a reflection device for solar thermal power generation.
- the reflector When used as a reflector for solar power generation, the reflector is shaped like a bowl (semi-cylindrical), and a cylindrical member having fluid inside is provided in the center of the semicircle, and the solar heat is condensed on the cylindrical member.
- the form which heats an internal fluid and converts the heat energy and generates electric power is mentioned as one form.
- heat is obtained by installing flat reflectors at multiple locations, concentrating the solar heat reflected by each reflector on a single reflector (central reflector), and reflecting it by the reflector.
- a form in which power is generated by converting energy in the power generation unit is also an example.
- the film mirror of the present invention is particularly preferably used because a high regular reflectance is required for the reflection device used.
- the adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.
- polyester resin urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber or the like is used.
- the laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity.
- the thickness of the pressure-sensitive adhesive layer 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.
- the other substrate to be bonded to the film mirror of the present invention may be any substrate that can impart the protective property of the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, Polyarylate film or sheet, polyethylene naphthalate film or sheet, polyethylene terephthalate film or sheet, plastic film or sheet such as fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc.
- a resin film or sheet coated with a resin kneaded with a resin or surface-treated such as metal deposition is used.
- the thickness of the laminated film or sheet is not particularly limited, but is usually preferably in the range of 12 to 250 ⁇ m.
- these other base materials may be bonded after providing a concave portion or a convex portion before being bonded to the film mirror of the present invention, or may be formed to have a concave portion or a convex portion after being bonded.
- the bonding and the molding so as to have a concave portion or a convex portion may be performed at the same time.
- Metal substrate of the solar heat collecting mirror As the metal substrate of the solar heat collecting mirror according to the present invention, the steel sheet, copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin plated steel plate, chrome plated steel plate, stainless steel plate, etc. High metal material can be used.
- a plated steel plate In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate or the like having good corrosion resistance.
- a UV-absorbing agent (Comparative Compound 1, TINUVIN 928, manufactured by Ciba Japan Co., Ltd.) was contained in the acrylic film at the time of film formation of the acrylic film to prepare a resin base film having a thickness of 100 ⁇ m.
- polyester resin Polyethylene SP-181, manufactured by Nippon Synthetic Chemical Co., Ltd.
- melamine resin Super Becamine J-820, manufactured by Dainippon Ink & Chemicals, Inc.
- TDI isocyanate (2,4-tolylene) Isocyanate
- HDMI-based isocyanate (1,6-hexamethylene diisocyanate) in a resin solid content ratio of 20: 1: 1: 2, and a resin mixed in toluene so that the solid content concentration is 10% by mass.
- Coating was performed by a method to form a silver adjacent layer having a thickness of 0.1 ⁇ m, and a silver reflective layer having a thickness of 80 nm was formed as a silver reflective layer on the silver adjacent layer by a vacuum deposition method.
- Gravure coating a resin in which polyester resin and TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 on the silver reflection layer as an adjacent layer far from the light incident side of the silver reflection layer Coating was performed by a method to form a layer having a thickness of 0.1 ⁇ m, and a film mirror 1 of a comparative example was produced.
- TDI tolylene diisocyanate
- a film mirror 2 of a comparative example was produced in the same manner except that an ultraviolet absorber (Comparative Compound 1, TINUVIN 928, manufactured by Ciba Japan Co., Ltd.) was contained in 17% by mass in the acrylic film.
- an ultraviolet absorber Comparative Compound 1, TINUVIN 928, manufactured by Ciba Japan Co., Ltd.
- the film mirror 5 of the present invention was produced in the same manner except that the ultraviolet absorber (present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.) was contained in an acrylic film in an amount of 9% by mass.
- the ultraviolet absorber present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.
- the film mirror 8 of the present invention was produced in the same manner except that the ultraviolet absorber (present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.) was contained in an acrylic film in an amount of 14% by mass.
- the ultraviolet absorber present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.
- the film mirror 9 of the present invention was produced in the same manner except that the ultraviolet absorber (the present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.) was contained in 17% by mass in the acrylic film.
- the ultraviolet absorber the present compound 1, TINUVIN400, manufactured by Ciba Japan Co., Ltd.
- the film mirrors 1 to 13 prepared above are pasted on a stainless steel (SUS304) plate with a thickness of 0.1 mm and a length of 4 cm and a width of 5 cm, with an acrylic film surface as the top and an adhesive layer with a thickness of 3 ⁇ m. Reflector devices 1 to 13 for solar thermal power generation were produced.
- SUS304 stainless steel
- the rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Regular reflectance reduction rate is 20% or more (Test B Moisture and Heat Resistance Test) After standing for 10 days under conditions of 85 ° C. and 85% RH, ultraviolet irradiation was performed for 5 days in an environment of 60 ° C. using an I-Super UV tester manufactured by Iwasaki Electric. After these tests were repeated three times, the regular reflectance was measured by the same method as the light reflectance measurement.
- the reduction rate of the regular reflectance of the film mirror before and after the forced deterioration test was calculated and evaluated according to the following criteria. 5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Regular reflectance reduction rate is 20% or more (Test C heat resistance / light resistance test) After leaving it to stand at 85 ° C. for 1000 hours, it was irradiated with ultraviolet rays for 5 days in an environment of 65 ° C. using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and evaluated in the same manner as the above light resistance test.
- the various characteristics of the solar power generation reflecting device of the present invention are superior to the various characteristics of the solar power generation reflecting device of the comparative example. That is, by the above means of the present invention, it is possible to prevent a decrease in the regular reflectance of the silver reflecting layer due to the deterioration of the constituent layers, and to be lightweight and flexible, to suppress the manufacturing cost, and to increase the area and mass production. It can be seen that a solar power generation reflecting device using a film mirror having excellent light resistance, heat and moisture resistance, heat resistance and light resistance, and having good regular reflectance with respect to solar heat can be obtained.
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Abstract
Description
Aa:260~320nmの吸収極大ピークの吸光度(260~320nmに吸収ピークが存在しない場合は0とする。)
Ab:321~400nmの吸収極大ピークの吸光度(321~400nmに吸収ピークが存在しない場合は0とする。)
2.前記紫外線吸収剤を含む層が、前記式1を満足する紫外線吸収剤を3~14質量%含有することを特徴とする前記1に記載のフィルムミラー。
本発明のフィルムミラーは、樹脂基材と、該樹脂基材上に設けられた銀反射層と、該樹脂基材及び銀反射層よりも光入射側に設けられた紫外線吸収剤を含む層とを有するフィルムミラーであって、前記紫外線吸収剤の少なくとも1種が上記式1を満足することを特徴とするフィルムミラーである。ガスバリア層、傷防止層等の特別な機能層を設けることも好ましい態様である。
本発明のフィルムミラーに用いられる紫外線吸収剤は、その少なくとも1種が下記式1を満足することを特徴とする。
Aa:260~320nmの吸収極大ピークの吸光度(260~320nmに吸収ピークが存在しない場合は0とする。)
Ba:321~400nmの吸収極大ピークの吸光度(321~400nmに吸収ピークが存在しない場合は0とする。)
260~400nmの吸収極大ピークと吸光度は、分光光度計により測定できる。
本発明においては、さらに下記の紫外線吸収剤を併用して使うこともできる。
本発明に係る樹脂基材(支持体)としては、従来公知の種々の樹脂フィルムを用いることができる。例えば、セルロースエステル系フィルム、ポリエステル系フィルム、ポリカーボネート系フィルム、ポリアリレート系フィルム、ポリスルホン(ポリエーテルスルホンを含む)系フィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、セルロースジアセテートフィルム、セルローストリアセテートフィルム、セルロースアセテートプロピオネートフィルム、セルロースアセテートブチレートフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、シンジオタクティックポリスチレン系フィルム、ポリカーボネートフィルム、ノルボルネンフィルム、ポリメチルペンテンフィルム、ポリエーテルケトンフィルム、ポリエーテルケトンイミドフィルム、ポリアミドフィルム、フッ素樹脂フィルム、ナイロンフィルム、ポリメチルメタクリレートフィルム、ポリアクリルフィルム等を挙げることができる。ポリカーボネートフィルム、ポリエステルフィルム、ノルボルネンフィルム、及びセルロースエステルフィルム、ポリメチルメタクリレートフィルム、ポリアクリルフィルムがより好ましい。
本発明に係るフィルムミラーは、接着層を有していてもよい。接着層は、銀反射層と樹脂基材(樹脂フィルム)との接着性を高めるために用いられるものや、他の構成層同士の接着性を高めるものであってもよいが、樹脂からなることが好ましい。銀反射層の光入射側から遠い側の隣接層が接着層となる場合は、接着層が劣化することで正反射率が低下することが考えられるが、本発明の構成であれば、そのような正反射率の低下を抑制できる。当該接着層が銀反射層の隣接層として用いられる場合は、樹脂基材(樹脂フィルム)と銀反射層とを密着する密着性、銀反射層を真空蒸着法等で形成する時の熱にも耐え得る耐熱性、及び銀反射層が本来有する高い反射性能を引き出すための平滑性があることが好ましい。
本発明に係る銀反射層の形成法としては、湿式法及び乾式法のどちらも使用することができる。
本発明のフィルムミラーには、銀反射層の上部(光入射側)に隣接して銀隣接層を設けてもよい。銀反射層が樹脂基材に対して、光入射側から遠い側に設けられる場合、光入射側の隣接層は、腐食防止剤を含み、銀の腐食劣化を防ぐとともに、銀反射層の傷防止及び、銀隣接層の外側に形成されるバリア層や傷防止層との接着力向上に寄与するものであることが好ましい。
本発明のフィルムミラーには、銀反射層に隣接して銀反射層の腐食防止剤を含有する層を有することが好ましい。ここで、「腐食」とは、金属(銀)がそれを取り囲む環境物質によって、化学的または電気化学的に浸食されるかもしくは材質的に劣化する現象をいう(JIS Z0103-2004参照)。
銀に対する吸着性基を有する腐食防止剤としては、アミン類及びその誘導体、ピロール環を有する化合物、トリアゾール環を有する化合物、ピラゾール環を有する化合物、チアゾール環を有する化合物、イミダゾール環を有する化合物、インダゾール環を有する化合物、銅キレート化合物類、チオ尿素類、メルカプト基を有する化合物、ナフタレン系の少なくとも一種またはこれらの混合物から選ばれることが望ましい。
本発明のフィルムミラーに用いられる銀反射層の腐食防止剤としては、酸化防止剤を用いることもできる。
本発明のフィルムミラーは、樹脂基材及び銀反射層よりも光入射側に、ガスバリア層を有することが好ましい。
本発明に係るガスバリア層は、加熱により無機酸化物膜を形成するセラミック前駆体を塗布した後に、一般的な加熱方法が適用して形成することができるが、局所的加熱により形成することが好ましい。セラミック前駆体は、ゾル状の有機金属化合物またはポリシラザンが好ましい。
本発明に係る有機金属化合物は、ケイ素(Si)、アルミニウム(Al)、リチウム(Li)、ジルコニウム(Zr)、チタン(Ti)、タンタル(Ta)、亜鉛(Zn)、バリウム(Ba)、インジウム(In)、スズ(Sn)、ランタン(La)、イットリウム(Y)、及びニオブ(Nb)のうちの少なくとも一つの元素を含有することが好ましい。特に、当該有機金属化合物が、ケイ素(Si)、アルミニウム(Al)、リチウム(Li)、ジルコニウム(Zr)、チタン(Ti)、亜鉛(Zn)、及びバリウム(Ba)のうちの少なくとも一つの元素を含有することが好ましい。さらに、ケイ素(Si)、アルミニウム(Al)、及びリチウム(Li)のうちの少なくとも一つの元素を含有することが好ましい。
一般式(I)において、Mは、酸化数nの金属を表す。R1及びR2は、各々独立に、アルキル基を表す。mは、0~(n-1)の整数を表す。R1及びR2は、同一でもよく、異なっていてもよい。R1及びR2としては、炭素原子4個以下のアルキル基が好ましく、例えば、メチル基CH3(以下、Meで表す。)、エチル基C2H5(以下、Etで表す)、プロピル基C3H7(以下、Prで表す。)、イソプロピル基i-C3H7(以下、i-Prで表す。)、ブチル基C4H9(以下、Buで表す)、イソブチル基i-C4H9(以下、i-Buで表す)等の低級アルキル基がより好ましい。
本発明に係る無機酸化物は、上記有機金属化合物を原料とするゾルから局所的加熱により形成されたものである。従って、有機金属化合物に含有されているケイ素(Si)、アルミニウム(Al)、ジルコニウム(Zr)、チタン(Ti)、タンタル(Ta)、亜鉛(Zn)、バリウム(Ba)、インジウム(In)、スズ(Sn)、ニオブ(Nb)等の元素の酸化物であることを特徴とする。
ここで、「ゾル-ゲル法」とは、有機金属化合物を加水分解すること等により、水酸化物のゾルを得て、脱水処理してゲルとし、さらにこのゲルを加熱処理することで、ある一定の形状(フィルム状、粒子状、繊維状等)の金属酸化物ガラスを調製する方法をいう。異なる複数のゾル溶液を混合する方法、他の金属イオンを添加する方法等により、多成分系の金属酸化物ガラスを得ることも可能である。
本発明に係るガスバリア層は、加熱により無機酸化物膜を形成するセラミック前駆体を塗布した後に、塗布膜の局所的加熱により形成された無機酸化物を含有することも好ましい。
一般式(II)において、R1、R2、及びR3は、同一または異なり、互いに独立して、水素、あるいは場合によっては置換されたアルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基、好ましくは水素、メチル、エチル、プロピル、iso-プロピル、ブチル、iso-ブチル、tert-ブチル、フェニル、ビニルまたは3-(トリエトキシシリル)プロピル、3-(トリメトキシシリルプロピル)からなる群から選択される基を表し、nは整数であり、そしてnは当該ポリシラザンが150~150,000g/モルの数平均分子量を有するように定められる。
一般式(III)において、R1、R2、R3、R4、R5及びR6は、互いに独立して、水素、あるいは場合によっては置換されたアルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基を表し、この際、n及びpは整数であり、そしてnは、当該ポリシラザンが150~150,000g/モルの数平均分子量を有するように定められる。
一般式(IV)において、R1、R2、R3、R4、R5、R6、R7、R8及びR9は、互いに独立して、水素、あるいは場合によっては置換されたアルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基を表し、この際、n、p及びqは整数であり、そしてnは、当該ポリシラザンが150~150,000g/モルの数平均分子量を有するように定められる。
本発明においては、フィルムミラーの最外層として傷防止層を設けることが好ましい。傷防止層は、傷防止のために設けられる。
本発明に係るフィルムミラー全体の厚さは、ミラーがたわみ防止、正反射率、取り扱い性等の観点から、75~250μmが好ましく、さらに好ましくは90~230μm、さらに好ましくは100~220μmである。
本発明のフィルムミラーは、太陽熱を集光する目的に好ましく使用できる。フィルムミラー単体で太陽熱集光ミラーとして用いることもできるが、より好ましくは、樹脂基材を挟んで銀反射層を有する側と反対側の樹脂基材面に塗設された粘着層を介して、他基材上に、特に金属基材上に、当該フィルムミラーを貼り付けて太陽熱発電用反射装置として用いることである。
粘着層としては、特に制限されず、例えばドライラミネート剤、ウエットラミネート剤、粘着剤、ヒートシール剤、ホットメルト剤等のいずれもが用いられる。
本発明に係る太陽熱集光ミラーの金属基材としては、鋼板、銅板、アルミニウム板、アルミニウムめっき鋼板、アルミニウム系合金めっき鋼板、銅めっき鋼板、錫めっき鋼板、クロムめっき鋼板、ステンレス鋼板等熱伝導率の高い金属材料を用いることができる。
(フィルムミラー1の作製)
アクリルフィルム製膜時に紫外線吸収剤(比較化合物1、TINUVIN928、チバ・ジャパン社製)をアクリルフィルムに9質量%含有させて、100μmの厚さの樹脂基材フィルムを作製した。このフィルム上に、ポリエステル樹脂(ポリエスター SP-181、日本合成化学社製)、メラミン樹脂(スーパーベッカミンJ-820、大日本インキ化学工業社製)、TDI系イソシアネート(2,4-トリレンジイソシアネート)、HDMI系イソシアネート(1,6-ヘキサメチレンジイソシアネート)を樹脂固形分比率で20:1:1:2に、固形分濃度10質量%となるようにトルエン中に混合した樹脂を、グラビアコート法によりコーティングして、厚さ0.1μmの銀隣接層を形成し、銀隣接層上に銀反射層として、真空蒸着法により厚さ80nmの銀反射層を形成した。銀反射層上に、銀反射層の光入射側から遠い側の隣接層として、ポリエステル系樹脂とTDI(トリレンジイソシアネート)系イソシアネートを樹脂固形分比率で10:2に混合した樹脂を、グラビアコート法によりコーティングして、厚さ0.1μmの層を形成し、比較例のフィルムミラー1を作製した。
フィルムミラー1の作製において、紫外線吸収剤(比較化合物1、TINUVIN928、チバ・ジャパン社製)をアクリルフィルムに17質量%含有させた以外は同様にして、比較例のフィルムミラー2を作製した。
フィルムミラー1の作製において、紫外線吸収剤(比較化合物1、TINUVIN928、チバ・ジャパン社製)を紫外線吸収剤(比較化合物2、UVINUL3049、BASF社製)に代えた以外は同様にして、比較例のフィルムミラー3を作製した。
フィルムミラー1の作製において、紫外線吸収剤(比較化合物1、TINUVIN928、チバ・ジャパン社製)を紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)に代えて、アクリルフィルムに4質量%含有させた以外は同様にして、本発明のフィルムミラー4を作製した。
フィルムミラー4の作製において、紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)をアクリルフィルムに9質量%含有させた以外は同様にして、本発明のフィルムミラー5を作製した。
フィルムミラー5の作製において、紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)を紫外線吸収剤(本発明化合物2、LA-51、ADEKA社製)に代えた以外は同様にして、本発明のフィルムミラー6を作製した。
フィルムミラー5の作製において、紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)を紫外線吸収剤(本発明化合物3、UVINUL3035、BASF社製)に代えた以外は同様にして、本発明のフィルムミラー7を作製した。
フィルムミラー5の作製において、紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)をアクリルフィルムに14質量%含有させた以外は同様にして、本発明のフィルムミラー8を作製した。
フィルムミラー5の作製において、紫外線吸収剤(本発明化合物1、TINUVIN400、チバ・ジャパン社製)をアクリルフィルムに17質量%含有させた以外は同様にして、本発明のフィルムミラー9を作製した。
フィルムミラー5の作製において、ポリエステル樹脂とメラミン樹脂とTDI系イソシアネートとHDMI系イソシアネート樹脂混合層に、酸化防止剤(1、2,2′-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト)を層内樹脂に対し0.3質量%加えた以外は同様にして、本発明のフィルムミラー10を作製した。
フィルムミラー10の作製において、ポリエステル樹脂とメラミン樹脂とTDI系イソシアネートとHDMI系イソシアネート樹脂混合層と、銀反射層の間に、パーヒドロポリシラザン液(NL120、3質量%ジブチルエーテル溶液、クラリアント社製)を用いて、乾燥後の膜厚が100nmとなるようにバーコーティングし、3分間自然乾燥した後、90℃のオーブンで30分間アニールし、0.5g/d/24hの湿度ガスバリア層を設けた以外は同様にして、本発明のフィルムミラー11を作製した。
前記フィルムミラー1の銀反射層の光入射側から最も遠い側の隣接層(樹脂層)にアクリレート系樹脂を接着層として、0.5μmの膜厚になるようグラビアコート法で塗布し、ポリエチレンテレフタレート(PET)を接着して、比較例のフィルムミラー12を作製した。
前記フィルムミラー5の銀反射層の光入射側から最も遠い側の隣接層(樹脂層)にアクリレート系樹脂を接着層として、0.5μmの膜厚になるようグラビアコート法で塗布し、ポリエチレンテレフタレート(PET)を接着して、本発明のフィルムミラー13を作製した。
厚さ0.1mmで、縦4cm×横5cmのステンレス(SUS304)板上に、上記作製したフィルムミラー1~13を、アクリルフィルム面を上面にして、厚さ3μmの粘着層を介して貼り付け、それぞれ太陽熱熱発電用反射装置1~13を作製した。
上記で得られた太陽熱発電用反射装置について、下記の方法により正反射率、耐光性、耐湿熱性、耐熱・耐光性の評価を行った。
島津製作所社製の分光光度計「UV265」に、積分球反射付属装置を取り付けたものを改造し、反射面の法線に対して、入射光の入射角を5°となるように調整し、反射角5°の正反射率を測定した。評価は、350~700nmの平均反射率として測定した。
岩崎電気製アイスーパーUVテスターを用いて、65℃の環境下で10日間紫外線照射を行った後、上記方法により正反射率を測定し、紫外線照射前後における正反射率の低下率を算出し、下記基準で評価した。
5:正反射率の低下率が5%未満
4:正反射率の低下率が5%以上10%未満
3:正反射率の低下率が10%以上15%未満
2:正反射率の低下率が15%以上20%未満
1:正反射率の低下率が20%以上
(試験B 耐湿熱性試験)
85℃、85%RHの条件で10日間放置後、岩崎電気製アイスーパーUVテスターを用いて、60℃の環境下で5日間紫外線照射を行った。これらの試験を3回繰り返した後、上記光線反射率測定と同様の方法により正反射率を測定した。強制劣化試験前後のフィルムミラーの正反射率の低下率を算出し、下記基準で評価した。
5:正反射率の低下率が5%未満
4:正反射率の低下率が5%以上10%未満
3:正反射率の低下率が10%以上15%未満
2:正反射率の低下率が15%以上20%未満
1:正反射率の低下率が20%以上
(試験C 耐熱・耐光性試験)
85℃、1000時間放置した後、岩崎電気製アイスーパーUVテスターを用いて、65℃の環境下で5日間紫外線照射を行い、上記耐光性試験と同様に評価した。
島津製作所社製の分光光度計「UV265」を用い、紫外線吸収剤の吸収極大ピークの吸光度を測定し、吸収極大ピークの吸光度比Aa/Abを算出した。
Claims (11)
- 樹脂基材と、該樹脂基材上に設けられた銀反射層と、該樹脂基材及び前記銀反射層よりも光入射側に設けられた紫外線吸収剤を含む層とを有するフィルムミラーであって、前記紫外線吸収剤の少なくとも1種が下記式1を満足することを特徴とするフィルムミラー。
式1:Aa≧1.2×Ab
Aa:260~320nmの吸収極大ピークの吸光度(260~320nmに吸収ピークが存在しない場合は0とする。)
Ab:321~400nmの吸収極大ピークの吸光度(321~400nmに吸収ピークが存在しない場合は0とする。) - 前記紫外線吸収剤を含む層が、前記式1を満足する紫外線吸収剤を3~14質量%含有することを特徴とする請求項1に記載のフィルムミラー。
- 前記紫外線吸収剤が、トリアジン、ベンゾフェノンまたはシアノアクリレート骨格を有する紫外線吸収剤であることを特徴とする請求項1または2に記載のフィルムミラー。
- 前記樹脂基材及び前記銀反射層よりも光入射側に、40℃、90%RHにおける水蒸気透過度が、1g/m2・day/μm以下のガスバリア層を有することを特徴とする請求項1~3のいずれか1項に記載のフィルムミラー。
- 前記紫外線吸収剤を含む層が、アクリレート系樹脂を含有し、前記式1を満足する紫外線吸収剤がシアノアクリレート骨格を有することを特徴とする請求項1~4のいずれか1項に記載のフィルムミラー。
- 前記樹脂基材がポリエチレンテレフタレート(PET)またはポリエチレンナフタレート(PEN)を有する層であり、前記銀反射層よりも光入射側から遠い側に設けられることを特徴とする請求項1~5のいずれか1項に記載のフィルムミラー。
- 前記銀反射層に隣接して腐食防止剤を含有する層を有することを特徴とする請求項1~6のいずれか1項に記載のフィルムミラー。
- 最外層として、傷防止層を有することを特徴とする請求項1~7のいずれか1項に記載のフィルムミラー。
- 全体の厚さが75~250μmであることを特徴とする請求項1~8のいずれか1項に記載のフィルムミラー。
- 請求項1~9のいずれか1項に記載のフィルムミラーを製造するフィルムミラーの製造方法であって、前記銀反射層を銀蒸着によって形成することを特徴とするフィルムミラーの製造方法。
- 請求項1~9のいずれか1項に記載のフィルムミラー、または請求項10に記載のフィルムミラーの製造方法により得られたフィルムミラーを用いた太陽熱発電用反射装置であって、前記樹脂基材を挟んで前記銀反射層を有する側とその反対側の樹脂基材面に塗設された粘着層を介して、金属基材上に前記フィルムミラーを貼り付けて形成されたことを特徴とする太陽熱発電用反射装置。
Priority Applications (3)
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US13/516,867 US20120257273A1 (en) | 2009-12-21 | 2010-09-19 | Film mirror, and method of manufacturing the same and reflection device for solar heat power generation |
JP2011547374A JP5516603B2 (ja) | 2009-12-21 | 2010-10-19 | フィルムミラー、その製造方法及び太陽熱発電用反射装置 |
EP10839053.5A EP2518535A4 (en) | 2009-12-21 | 2010-10-19 | FILM MIRROR, METHOD FOR THE PRODUCTION THEREOF AND REFLECTION DEVICE FOR SOLAR POWER GENERATION THEREWITH |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011162153A1 (ja) * | 2010-06-23 | 2011-12-29 | コニカミノルタオプト株式会社 | 太陽熱発電用フィルムミラー、その製造方法及び太陽熱発電用反射装置 |
JP2014133403A (ja) * | 2012-02-14 | 2014-07-24 | Fujifilm Corp | ミラーフィルム、その製造方法、及びそれを用いた反射鏡 |
KR101741771B1 (ko) * | 2012-03-27 | 2017-05-30 | 미쓰비시 세이시 가부시키가이샤 | 은도금 도장체 |
Families Citing this family (3)
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JP5424091B2 (ja) * | 2009-03-31 | 2014-02-26 | コニカミノルタ株式会社 | 紫外反射膜を有するフィルムミラー |
CN105403938B (zh) * | 2015-12-25 | 2018-06-19 | 巨洋神州(苏州)数字技术有限公司 | 一种光学消光反射片及背投影系统 |
CN112123684B (zh) * | 2019-06-25 | 2022-04-15 | 江苏想靓眼镜有限公司 | 一种多种变色太阳镜加工工艺 |
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- 2010-10-19 WO PCT/JP2010/068320 patent/WO2011077816A1/ja active Application Filing
- 2010-10-19 JP JP2011547374A patent/JP5516603B2/ja active Active
- 2010-10-19 EP EP10839053.5A patent/EP2518535A4/en not_active Withdrawn
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JP2014133403A (ja) * | 2012-02-14 | 2014-07-24 | Fujifilm Corp | ミラーフィルム、その製造方法、及びそれを用いた反射鏡 |
KR101741771B1 (ko) * | 2012-03-27 | 2017-05-30 | 미쓰비시 세이시 가부시키가이샤 | 은도금 도장체 |
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JPWO2011077816A1 (ja) | 2013-05-02 |
EP2518535A1 (en) | 2012-10-31 |
JP5516603B2 (ja) | 2014-06-11 |
EP2518535A4 (en) | 2013-08-14 |
US20120257273A1 (en) | 2012-10-11 |
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