WO2014109354A1 - Miroir en film et réflecteur pour la conversion thermodynamique solaire - Google Patents

Miroir en film et réflecteur pour la conversion thermodynamique solaire Download PDF

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Publication number
WO2014109354A1
WO2014109354A1 PCT/JP2014/050217 JP2014050217W WO2014109354A1 WO 2014109354 A1 WO2014109354 A1 WO 2014109354A1 JP 2014050217 W JP2014050217 W JP 2014050217W WO 2014109354 A1 WO2014109354 A1 WO 2014109354A1
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layer
acrylic
film
resin
weight
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PCT/JP2014/050217
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English (en)
Japanese (ja)
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丈範 熊谷
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コニカミノルタ株式会社
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Priority to JP2014556432A priority Critical patent/JPWO2014109354A1/ja
Publication of WO2014109354A1 publication Critical patent/WO2014109354A1/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
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
    • G02B5/0858—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal the reflecting layers comprising a single metallic layer with one or more dielectric layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S2023/86—Arrangements for concentrating solar-rays for solar heat collectors with reflectors in the form of reflective 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.
  • Patent Document 1 Japanese Patent Publication No. 2009-520174 (corresponding to PCT / US2006 / 062046)
  • Non-Patent Document 1 (“2008 Solar Annual”). Review Meeting "Susannah Clear Bob Messenger 3M Energy Markets)
  • Patent Document 1 Japanese Patent Publication No. 2009-520174 (corresponding to PCT / US2006 / 062046)
  • Patent Document 1 discloses a silver mirror structure in which an acrylic film is bonded to a silver layer with a polymer film via an adhesive layer. Yes.
  • Non-Patent Document 1 (“2008 Solar Annual Review Meeting”, Susannah Clear Bob Messenger 3M Energy Markets) discloses a film mirror for solar power generation in which a silver layer is directly formed on the back surface of an acrylic film. These film mirrors are advantageous in that they can be reduced in weight, have flexibility, can be manufactured at low cost, and can be manufactured in large areas and in large quantities.
  • an acrylic film is usually formed by using a melt-extruded acrylic resin that is melted by heat. Therefore, due to process restrictions, there is a problem with the smoothness of the surface that causes minute irregularities on the surface. Is left. In particular, when it is used as a film mirror, the light is condensed very far away, so that there is a problem that the light collecting performance is adversely affected even if minute irregularities exist on the surface.
  • Non-Patent Document 1 (“2008 Solar Annual Review Meeting” Susannah Clear Bob Messenger 3M Energy Markets)
  • only the acrylic film is used as the base material.
  • a film mirror having excellent smoothness has been developed by forming an acrylic layer by applying an acrylic resin dissolved in a solvent when a film mirror is manufactured.
  • the following problems occurred: When an acrylic resin solution dissolved in a solvent was applied, the solvent or the additive in the acrylic resin solution dissolved in the solvent was transferred to the silver layer.
  • an object of the present invention is to provide a film mirror and a solar power generation reflecting device having high reflectivity, which have excellent smoothness and durability.
  • the acrylic layer has a thickness of 20 to 100 ⁇ m, and the amount of the solvent remaining in the acrylic layer is 0.1% by weight or less based on the total weight of the acrylic layer, Film mirror.
  • FIG. 1 is a schematic side view showing a layer configuration of a film mirror according to Examples 1 to 10 of the present invention.
  • FIG. FIG. 5 is a schematic side view showing a layer configuration of a film mirror according to Comparative Examples 1 to 4.
  • 10 is a schematic side view showing a layer configuration of a film mirror according to Comparative Example 5.
  • FIG. It is a schematic side view which shows the layer structure of the film mirror by the comparative example 6. It is a schematic side view which shows the layer structure of the film mirror by Example 11 and 12 of this invention.
  • a film mirror including a silver reflective layer and an acrylic layer containing an acrylic resin formed by a coating method on a light incident side of the silver reflective layer on a resin film-like support. Is done. At this time, the thickness of the acrylic layer is 20 to 100 ⁇ m, and the amount of the solvent remaining in the acrylic layer is 0.1% by weight or less with respect to the total weight of the acrylic layer.
  • the film mirror which has the outstanding smoothness and durability, and has a high reflectance, and the solar power generation reflective apparatus can be provided.
  • the film mirror of the present invention is excellent in durability because a silver reflective layer is formed on a resin film-like support (for example, a PET substrate). Moreover, since the acrylic layer is formed on the light incident side of the silver reflection layer by the coating method, a film mirror having good smoothness on the surface can be realized.
  • the amount of the solvent remaining in the acrylic layer is 0.1% by weight or less based on the total weight of the acrylic layer, various disadvantageous problems caused by the residual solvent can be solved, and durability It is possible to realize a film mirror that is superior to the above. That is, by suppressing the amount of the solvent used when forming the acrylic layer below a certain amount, it is possible to prevent the solvent used or components such as additives dissolved in the solvent from entering the silver reflective layer. Can prevent discoloration or coloring of silver. In addition, the occurrence of cracks and cracks in the film mirror due to insufficient drying of the acrylic layer is suppressed, and the generation of gaps in the acrylic layer due to volatilization of the residual solvent is also suppressed.
  • the film mirror of the present invention has at least a resin film-like support 1, a silver reflecting layer 3, and an acrylic layer 5.
  • the acrylic layer 5 includes an acrylic resin, and if the acrylic film 5 is provided on the light incident side with respect to the resin film-like support 1 and the silver reflective layer 3, the stacking order of the resin film-like support 1 and the silver reflective layer 3. Is not particularly limited, and may be laminated with, for example, the acrylic layer 5, the silver reflecting layer 3, and the resin film-like support 1 in order from the light incident side, and the acrylic layer 5 and the resin film-like support 1 in this order from the light incident side. , And a silver reflective layer 3.
  • the silver reflection layer 3, and the acrylic layer 5 other layers may be provided on an arbitrary interlayer or an outer surface of the layer. That is, other layers may be interposed between the acrylic layer 5, the silver reflective layer 3, and the resin film-like support 1, and the respective layers may be adjacent to each other, or on the acrylic layer 5 or on the resin
  • the surface of the film-like support opposite to the acrylic layer may have another layer, for example, the hard coat layer 6 may be provided on the acrylic layer 5, and the resin film-like support.
  • An adhesive layer (not shown), a release layer (not shown), or the like may be provided on the surface opposite to the acrylic layer.
  • the hard coat layer 6, the acrylic layer 5, the resin coat layer 4, the silver reflective layer 3, the anchor layer 2, and the resin film-like support 1 are sequentially laminated from the light incident side.
  • An adhesive layer (not shown) can be provided between any of the above layers. Note that each of the layers may be provided as a single layer, may be provided as a plurality of layers, or other layers may be provided adjacent to each other.
  • the thickness of the film mirror is not particularly limited and is preferably 20 to 600 ⁇ m, more preferably 80 to 300 ⁇ m, still more preferably 80 to 200 ⁇ m, and most preferably 80 to 170 ⁇ m.
  • the thickness of the film mirror 20 ⁇ m or more it is preferable from the viewpoint that it is easy to obtain a good reflectance without bending the mirror when bonded to a base material that supports the film mirror.
  • the film mirror of the present invention is very lightweight and flexible from the constituent materials described later and the thickness range of 20 to 600 ⁇ m, and can be manufactured in a large area and mass-produced at a low manufacturing cost.
  • the thickness of each layer (also referred to as “film thickness”) is obtained as follows. That is, when the thickness of the layer is 1 ⁇ m or more, it is obtained by measuring using a micrometer (manufactured by Mitutoyo Corporation). Further, when the thickness of the layer is less than 1 ⁇ m, it is obtained by measuring using an optical interference type film thickness meter (ST2000 DLXn manufactured by X-MAC). Moreover, the thickness of each layer points out a dry film thickness unless there is special description.
  • the surface roughness Ra is used as a measure of the smoothness of the film mirror.
  • the surface roughness Ra of the film mirror of the present invention is not particularly limited, and when the film mirror is produced using a roll-to-roll method capable of continuously forming a film mirror, the surface roughness such as blocking may be caused. From the viewpoint of preventing sticking, it is preferably 3 nm or more, and from the viewpoint of suppressing sunlight scattering, it is preferably 50 nm or less.
  • the surface roughness Ra can be measured by a three-dimensional measuring device NH-3SP (manufactured by Mitaka Kogyo Co., Ltd.). The measurement conditions are a measurement range of 2 mm and a measurement pitch of 2 ⁇ m.
  • the objective lens is 100 ⁇ and the cutoff value is 0.250 mm.
  • the film mirror of the present invention is preferably manufactured by a roll-to-roll method from the viewpoint of manufacturing cost.
  • the acrylic layer according to the present invention has a function of preventing deterioration or discoloration of the layer provided in the lower layer (that is, the lower layer of the acrylic layer viewed from the light incident side) or film peeling.
  • it can function as a layer that protects the silver reflective layer from external factors such as water, chlorine, or sulfur in the air.
  • the resin film-like support provided in the lower layer can function as a layer for protecting from UV rays.
  • the thickness of the acrylic layer according to the present invention is 10 to 100 ⁇ m, preferably 20 to 100 ⁇ m, more preferably 20 to 80 ⁇ m, and further preferably 40 to 80 ⁇ m.
  • the thickness of the acrylic layer is less than 20 ⁇ m, the moisture permeability becomes high, and the amount of the ultraviolet absorber contained is limited, so that a sufficient ultraviolet absorption effect cannot be obtained, and durability of 10 years or more is achieved. There is a problem that it cannot be obtained.
  • the thickness of the acrylic layer exceeds 100 ⁇ m, the absorption of the acrylic layer with respect to sunlight increases, resulting in a decrease in light reflectivity, resulting in a decrease in light collecting and heat collecting performance. There is a problem that the flexibility of the layer itself or the layer itself cannot be sufficiently maintained.
  • the surface roughness Ra of the acrylic layer according to the present invention is preferably 1 to 50 nm, more preferably 1 to 10 nm, from the viewpoint of regular reflectance.
  • the acrylic layer according to the present invention mainly contains an acrylic resin as a base resin and can contain additives such as an ultraviolet absorber and an antioxidant.
  • UV absorber The ultraviolet absorber contained in the acrylic layer according to the present invention will be described in detail below.
  • the purpose of adding the ultraviolet absorber is to give the acrylic layer a function of absorbing and blocking ultraviolet rays.
  • an ultraviolet absorber As an organic type, a benzophenone type, a benzotriazole type, a salicylic acid phenyl type, a triazine type, a hindered amine type, a benzoate type, etc. are mentioned, and inorganic types include titanium oxide, zinc oxide, Examples include cerium oxide and iron oxide.
  • a high molecular weight ultraviolet absorber having a weight average molecular weight of 1000 or more. The weight average molecular weight is preferably 1000 or more and 3000 or less.
  • specific examples of the ultraviolet absorber those disclosed in paragraphs “0038” to “0042” of JP2012-232538A are appropriately selected.
  • benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers are preferably used, and triazine ultraviolet absorbers are more preferably used.
  • a resin having an ultraviolet absorbing group or a monomer constituting the resin can be used as the ultraviolet absorber.
  • the ultraviolet absorbing resin examples include a copolymer of methyl methacrylate and a benzophenone ultraviolet absorber (BASF Japan, UVA635L), and a copolymer of methyl methacrylate and a benzotriazole ultraviolet absorber (Shin Nakamura).
  • the ultraviolet absorber a compound having a function of converting the energy held by ultraviolet light into vibration energy in the molecule and releasing the vibration energy as heat energy or the like can be used. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers acting as a light energy conversion agent, called quenchers, can be used in combination.
  • quenchers light stabilizers acting as a light energy conversion agent
  • the ultraviolet absorber disclosed above may be used alone or in combination of two or more thereof as necessary. Further, if necessary, an ultraviolet absorber other than the ultraviolet absorber, for example, a salicylic acid derivative, a substituted acrylonitrile, a nickel complex, or the like can be contained.
  • the ultraviolet absorber when an acrylic layer containing an acrylic resin contains an ultraviolet absorber, the ultraviolet absorption capability of the formed acrylic layer can be sufficiently exerted, and the yellowing of the resin used in the film mirror can be prolonged. Can be suppressed. Further, from the viewpoint of considering the elongation and toughness of the acrylic resin and the bleed-out of the ultraviolet absorber, the ultraviolet absorber is 0.1 to 20 wt% with respect to 100 wt% of the total amount of the acrylic resin contained in the acrylic layer. Is preferably blended at 1 to 10% by weight, more preferably 2 to 8% by weight.
  • content of the ultraviolet absorber with respect to 100 weight% of the total amount of an acrylic resin prepares the raw material which comprises the said acrylic resin, ie, an ultraviolet curable acrylic resin liquid, or a thermosetting acrylic resin liquid. Therefore, it is equal to the blending amount of the UV absorber with respect to the total amount of raw material monomers.
  • the inclusion of the benzotriazole ultraviolet absorber is preferably in the range of 30:70 to 70:30, more preferably in the range of 40:60 to 60:40, and 50:50 A close ratio is particularly preferred.
  • antioxidant in the present invention, an antioxidant may be contained in the acrylic layer in order to prevent deterioration of the acrylic layer. Examples of preferred antioxidants are listed below.
  • an organic antioxidant such as a hindered amine antioxidant, a hindered phenol antioxidant, and a phosphoric acid antioxidant.
  • an organic antioxidant for example, those disclosed in paragraphs “0048” to “0052” of JP2012-232538A are appropriately selected.
  • antioxidants disclosed above may be used alone or in combination of two or more.
  • the total amount of the acrylic resin is 100% by weight.
  • the blending amount of the antioxidant is preferably 0.1% by weight or more, more preferably 1% by weight or more.
  • the upper limit of the blending amount of the oxygen inhibitor is not particularly limited, but is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 6% by weight or less. It is particularly preferable that the amount is not more than wt%.
  • the antioxidant is preferably blended at 0.1 to 20% by weight, more preferably 1 to 10% by weight, and more preferably 1 to 6% by weight based on 100% by weight of the total amount of the acrylic resin. More preferably, it is blended in an amount of 1% by weight, particularly preferably 1-5% by weight.
  • the content of the antioxidant with respect to 100% by weight of the total amount of the acrylic resin is prepared as a raw material constituting the acrylic resin, that is, an ultraviolet curable acrylic resin liquid or a thermosetting acrylic resin liquid. Therefore, the amount of the antioxidant is equal to the total amount of the raw material monomers.
  • the acrylic layer can contain an antioxidant and a UV absorber in combination.
  • the ratio of the antioxidant content to the ultraviolet absorber content is preferably in the range of 1: 1 to 1:20, preferably in the range of 1: 2 to 1:10. More preferably, it is 1: 3 to 1: 6.
  • the acrylic layer according to the present invention may have other additives in addition to the ultraviolet absorber and the antioxidant to such an extent that bleeding out does not occur.
  • additives include leveling agents, fillers such as talc, rust preventives, fluorescent whitening agents, surfactant-based, lithium-based, or organic boron-based antistatic agents, pigments, dyes, thickeners.
  • leveling agents such as talc, rust preventives, fluorescent whitening agents, surfactant-based, lithium-based, or organic boron-based antistatic agents, pigments, dyes, thickeners.
  • Additives common in the paint field such as inorganic fine particles such as colloidal silica and alumina sol, and polymethyl methacrylate acrylic fine particles.
  • the acrylic layer according to the present invention is a first step of preparing an acrylic resin liquid, and the acrylic resin liquid is applied to the upper surface of the light incident side of the resin film-like support on which a silver reflective layer is formed, It can form by the 2nd process of drying and forming a coating film, and the 3rd process of hardening
  • a step (1-a) of preparing an ultraviolet curable acrylic resin solution or a step (1-b) of preparing a thermosetting acrylic resin solution One of these.
  • the ultraviolet curable acrylic resin liquid or thermosetting acrylic resin liquid according to the present invention is prepared at 25 ° C., preferably in the viscosity range of 10 to 2000 poise, more preferably in the viscosity range of 100 to 1000 poise. It is prepared with. In the present invention, the viscosity is measured with a BII viscometer (Toki Sangyo Co., Ltd.).
  • the ultraviolet curable acrylic resin liquid includes an ultraviolet polymerization initiator, and an acrylic vinyl monomer that can undergo a polymerization / curing reaction due to ultraviolet irradiation or an acrylic vinyl monomer has a predetermined polymerization degree.
  • it means a mixed resin liquid containing an ultraviolet curable partial polymer that has been partially polymerized in advance.
  • the thermosetting acrylic resin liquid contains a pyrolytic polymerization initiator, and an acrylic vinyl monomer that can undergo a polymerization / curing reaction when heated, or the acrylic vinyl monomer has a predetermined polymerization degree. It means a mixed resin liquid containing a thermosetting partial polymer that has been partially polymerized in advance.
  • the weight average molecular weight of the partially polymerized ultraviolet curable partial polymer or thermosetting partial polymer is usually 50,000 to 1,500,000, preferably 100,000 to 1,200,000. In the present invention, the weight average molecular weight is measured by GPC.
  • step (1-a) for preparing the ultraviolet curable acrylic resin liquid and the step (1-b) for preparing the thermosetting acrylic resin liquid will be described.
  • the ultraviolet curable acrylic resin liquid may be prepared by blending an ultraviolet polymerization initiator with an ultraviolet curable acrylic vinyl monomer.
  • it may be prepared by blending an ultraviolet polymerization initiator into a mixture of a partially polymerized product obtained by polymerization and an unreacted acrylic vinyl monomer.
  • the precursor acrylic vinyl monomer also referred to as a raw material monomer
  • a wide range of radical polymerizable acrylic vinyl monomers can be used up to the monomer.
  • the acrylic layer according to the present invention has a thickness of 20 to 100 ⁇ m, if the degree of crosslinking of the acrylic layer is too high, the flexibility of the film itself is lost, and the monofunctional group monomer and / or Alternatively, a form in which a bifunctional monomer is partially polymerized as a raw material monomer is preferable.
  • radical polymerizable acrylic vinyl monomer examples include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl ( (Meth) acrylate, uncanyl (meth) acrylate, dodecanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, 2-hydroxyethyl ( (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) arylate, (meth) acrylic acid amide, dimethylamide methacrylate, dimethylamide acrylate, stearyl (meth) acrylate, behenyl
  • radical polymerizable acrylic vinyl monomers may be used alone or in combination.
  • other monomers such as vinyl acetate, styrene, vinylbenzene, ethylene, crotonic acid, vinyl propionate, ⁇ -methylstyrene, dicyclopentene and coumarone may be used in combination. .
  • a polymerization initiator can be appropriately selected depending on the type of the monomer.
  • a photopolymerization initiator disclosed by polymerization by light such as ultraviolet rays or visible light, or a thermal decomposition type polymerization initiator is used.
  • photopolymerization initiators 2,2-diethoxycetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, methoxycetophenone, 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Geigy Corp.) , Trade name: Icure 651), ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone (Ciba Geigy Corp., trade name: Darocur 1173), 2-hydroxy-2-cyclohexylacetophenone (BASF, trade name: Irgacure) 184), or acetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-montforinopropan-1-one (manufactured by Ciba Geigy KK, trade name: Irgacure 907), benzoin, benzoin Methyl ether, benzoin ethyl
  • thermal decomposition type polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile (manufactured by Wako Pure Chemical Industries, Ltd., product) Name: V-70), 2,2′-azobiscyclohexylnitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-40), Azo initiators such as 2-phenylazo-4-methoxy-2,4-dimethylvalerotolyl, dimethyl-2,2′-azobisisobutyrate, or 2,2′-azobis (2-methylbutyronitrile); Or benzoyl peroxide, 2,4-di-chlorobenzoyl peroxide, 1-butyl-oxy-2-ethylhexanoate, 1-butylperoxy-3,5,5-trimethylhexanoate, Prop
  • a photopolymerization initiator is preferably used, and an ultraviolet polymerization initiator is more preferably used from the viewpoint of increasing productivity. Moreover, it is preferable to perform it in the atmosphere of nitrogen gas, when superposing
  • a lamp having an illuminance of 100 to 1500 mW / cm 2 the ultraviolet irradiation was intermittently performed in the range of 100 to 1500 mJ / cm 2 , and the ultraviolet irradiation was repeated until the following preferable viscosity range was reached.
  • the acrylic resin remaining in the obtained ultraviolet curable acrylic resin liquid is used.
  • the amount of the vinyl monomer is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, and more preferably 2 to 10% by weight based on the total weight of the ultraviolet curable acrylic resin liquid. It is particularly preferred.
  • the acrylic resin liquid according to the present invention within the preferable viscosity range, it can be carried out by appropriately selecting the amount of the polymerization initiator or reaction conditions.
  • the amount of the polymerization initiator used here is preferably 0.001 to 6% by weight, and more preferably 0.003 to 4% by weight, based on 100% by weight of the total amount of raw material monomers.
  • An ultraviolet polymerization initiator is blended into the mixed solution of the obtained ultraviolet curable partial polymer and unreacted acrylic vinyl monomer to prepare an ultraviolet curable acrylic resin liquid according to step (1-a). Can do.
  • the blending amount of the ultraviolet polymerization initiator is preferably 1 to 10% by weight and more preferably 2 to 4% by weight with respect to 100% by weight of the total amount of raw material monomers.
  • the ultraviolet polymerization initiator is used when producing
  • the thermosetting acrylic resin liquid may be prepared by blending a thermosetting polymerization initiator with a thermosetting acrylic vinyl monomer.
  • a thermally decomposable polymerization initiator is added to a thermosetting partial polymer obtained by partial polymerization in advance and an unreacted acrylic vinyl monomer that is a precursor of the partial polymer. It may be prepared by blending.
  • the amount of the acrylic vinyl monomer remaining in the obtained thermosetting acrylic resin liquid is preferably 2 to 20% by weight of the total weight of the thermosetting acrylic resin liquid. It is more preferably 2 to 15% by weight, and particularly preferably 2 to 10% by weight.
  • the acrylic vinyl monomer used as a precursor thereof and a preferred embodiment are not particularly limited, and in the above step (1-a). Used from the disclosed acrylic vinyl monomers and preferred embodiments thereof.
  • the polymerization initiator and preferred embodiments are used in the same manner as the polymerization initiator disclosed in the above step (1-a) and preferred embodiments thereof, from the viewpoint of polymerization efficiency and productivity. Therefore, it is more preferable to perform partial polymerization using a thermal decomposition polymerization initiator.
  • a system resin solution can be prepared.
  • step (1-b) it is preferable to blend two types of thermal decomposition polymerization initiators having different 10-hour half-lives. More specifically, a low temperature pyrolysis polymerization initiator having a 10-hour half-life in the range of 25 to 55 ° C. and a high-temperature pyrolysis polymerization having a 10-hour half-life in the range of more than 55 ° C. and 90 ° C. or less. It is preferable to use in combination with an initiator.
  • low temperature pyrolysis polymerization initiator examples include 2,2′-azobis-2,4-dimethylvaleronitrile (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-70), isobutyl peroxide, ( ⁇ , ⁇ '-bis-neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylisopropyloxycarbonate, 1,1,3,3 -Tetramethylbutyl peroxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydi-carbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2-ethoxyethyl-peroxydi-carbonate, Di (2-ethylethylperoxy) dicarbonate, t-hexylperoxyn
  • 1,1′-azobis (cyclohexane-1-carbonitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-40), 3, 5, 5 Trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-di -Methyl-2,5-di (2-ethylhexylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1- Butyl peroxy-2-oxy-2-ethylhexanoate, m-toluyl, benzoy
  • the low temperature thermal decomposition type polymerization initiator and the high temperature thermal decomposition type polymerization initiator are usually in a weight ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, more preferably. It is blended at a ratio of 1: 1.
  • the polymerization reaction in the heat polymerization step (step (3-b) in the third step described later) and the aging polymerization are performed. Both polymerization reactions proceed smoothly.
  • the blending amount of the low-temperature pyrolysis polymerization initiator is usually 0.05 to 5% by weight, preferably 0.1 to 100% by weight of the total amount of raw material monomers. ⁇ 2% by weight, more preferably 0.5-2% by weight.
  • the blending amount of the high-temperature thermal decomposition type polymerization initiator is usually from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight, more preferably from 0.5 to 2% by weight.
  • step (1-b) if necessary, other components such as a crosslinking agent, a molecular weight modifier, a filler, particles, and a tackifying resin may be blended to prepare a thermally decomposable acrylic resin liquid. it can.
  • Examples of the other crosslinking agent include divinylbenzene, diethyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexaneol di (meth) acrylate, bisphenol A dioxydiethyl glycol di Reaction with a radical polymerizable polyfunctional monomer such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, or pentaerythritol tri (meth) acrylate, or a functional group contained in the thermally decomposable acrylic resin liquid A compound having a property can be used.
  • cross-linking agents examples include isocyanate adducts such as epoxy compounds, isocyanate compounds, isocyanurates of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate HX), or organometallic compounds. .
  • the blending amount when blending the crosslinking agent is usually 0.05 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 1 to 1% by weight based on 100% by weight of the total amount of raw material monomers. 5% by weight.
  • Examples of the other component molecular weight modifier include mercaptan compounds, thioglycol, carbon tetrachloride, ⁇ -methylstyrene dimer, and the like.
  • the blending amount when blending the molecular weight modifier is usually 0.01 to 2% by weight, preferably 0.05 to 1% by weight, based on 100% by weight of the total amount of raw material monomers.
  • Examples of the filler as the other component include particles having an average particle diameter of 10 to 100 ⁇ m such as polyethylene particles (PE particles), silica particles, alumina particles, cerium oxide particles, and zirconia oxide particles.
  • the blending amount when blending the filler is usually 1 to 60% by weight, preferably 5 to 40% by weight, based on 100% by weight of the total amount of raw material monomers.
  • Examples of the other component particles include silica, alumina, titanium oxide, silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, and zinc sulfate.
  • inorganic particles such as aluminum hydroxide, aluminum oxide, glass mica, barium sulfate, alumina white, zeolite, polymethyl (meth) acrylate, polystyrene, benzoguanamine resin, melamine resin, phenol resin, silicone resin, urea resin, polyethylene resin
  • resin particles produced from resins such as polyolefin resin, nylon resin, urethane resin, fluororesin, polyimide resin, and epoxy resin, and polyethylene wax. These can be used alone or in combination.
  • thermosetting acrylic resin liquid can be prepared by mixing a crosslinking agent, filler, etc., stirring and partially polymerizing in a temperature range of 25 to 35 ° C., and preferably adding a defoaming treatment.
  • a commercially available acrylic resin liquid can be used in place of the above-described acrylic vinyl monomer and the corresponding polymerization initiator.
  • examples of such commercially available acrylic resin liquids include Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M -5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR -77, BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101 BR-102, BR-105, BR-106, BR-107, BR-108, BR
  • the acrylic layer contains an ultraviolet absorber or an antioxidant
  • it can be blended when preparing the acrylic resin liquid, and becomes a raw material before synthesizing the partial polymer.
  • the ultraviolet absorber or antioxidant may be added when mixing the acrylic vinyl monomer, or after synthesizing the partial polymer, that is, after the acrylic resin liquid can be prepared, An antioxidant may be added. More preferably, after the partial polymer is synthesized, an ultraviolet absorber or an antioxidant is added.
  • Solvents used here include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, formic acid Esters such as ethyl, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate, 1-octa , 2-octanone, 1-nonanone, 2-n
  • a highly hydrophobic solvent such as an ester solvent, a ketone solvent, an alkyl ketone solvent, or a hydrocarbon solvent is preferably used.
  • the amount of the solvent remaining in the formed acrylic layer is preferably 0.1% by weight or less with respect to the total weight of the acrylic layer.
  • the residual solvent here (also referred to as residual solvent) means that the solvent positively added as described above remains in the acrylic layer through the reaction in the third step described later, The corresponding solvent has no polymerizability.
  • a monomer component such as methyl methacrylate is liquid at room temperature, and other components that form the resin liquid may be dissolved or dispersed. However, since such a monomer component has polymerizability, In the invention, these components are not treated as solvents.
  • the drying temperature and / or the adjustment of the drying temperature and the solvent content are used This can be achieved by reducing the amount of the raw material to be formed, or adjusting the thickness of the formed acrylic layer.
  • the solvent is preferably blended at 20 wt% or less with respect to 100 wt% of the total solid content of the acrylic resin used. It is more preferable that the amount is not more than wt%, and it is particularly preferable that the solvent is not substantially mixed.
  • the fact that the solvent here is not substantially blended means that the solvent is not actively blended.
  • the solvent used in the production of the monomer remains in the monomer or the like and is contained in the composition. It does not exclude even a solvent that is contained when preparing an acrylic resin liquid, such as a solvent to be used.
  • the second step for forming the acrylic layer according to the present invention includes the ultraviolet curable acrylic resin solution prepared in the step (1-a) and the thermosetting acrylic resin prepared in the step (1-b).
  • a liquid or a commercially available acrylic resin liquid is applied to the upper surface on the light incident side of the resin film-like support on which a silver reflective layer or the like is formed, and dried to form a coating film.
  • thermosetting acrylic resin liquid for the ultraviolet curable acrylic resin liquid, thermosetting acrylic resin liquid, or commercially available acrylic resin liquid, before being applied, from the viewpoint of suppressing the possibility of poor appearance due to foam generation at the time of application, It is preferable to perform a defoaming process.
  • the defoaming treatment is usually performed by holding any of the acrylic resin liquids in a reduced pressure state at room temperature. By performing the defoaming treatment, bubbles are not contained in the resulting acrylic layer, and an acrylic layer with high surface smoothness and high density can be formed.
  • the acrylic resin liquid of any one of the above for example, by using a coating device such as an applicator, gravure coater, doctor blade, comma coater, die coater, reverse coater, roll coater, etc. It can apply
  • a coating device such as an applicator, gravure coater, doctor blade, comma coater, die coater, reverse coater, roll coater, etc. It can apply
  • the ultraviolet curable acrylic resin liquid prepared in the step (1-a), the thermosetting acrylic resin liquid prepared in the step (1-b), and a commercially available acrylic resin liquid are used.
  • the coating thickness at the time of coating is not particularly limited as long as the thickness of the cured acrylic layer is in the range of 20 to 100 ⁇ m.
  • Any one of the acrylic resin liquids is applied and dried to form a coating film.
  • the acrylic layer formed by the coating method has a higher surface smoothness than the acrylic layer formed by the bonding method or the like, and a film mirror with higher reflectance can be obtained.
  • the acrylic resin liquid used here can increase the solid content concentration and can be applied even with a small amount of solvent, the penetration of the solvent or the raw material dissolved by the solvent into the silver reflective layer is suppressed. It is possible to suppress coloring of silver and the like.
  • the adhesion between the formed acrylic layer and the adjacent layer is improved compared to the acrylic layer formed by dissolving the acrylic resin solution with a solvent without applying the curing process. be able to.
  • the third step for forming the acrylic layer according to the present invention is a step of curing the coating film formed in the second step, and more specifically, UV curing when using the UV curable coating film.
  • Step (3-a) or a thermosetting step (3-b) in the case of using the thermosetting coating film is included.
  • the said ultraviolet curable coating film or a thermosetting coating film hardens
  • the third step can be omitted depending on the type of commercially available acrylic resin liquid used.
  • each of the step (3-a) and the step (3-b) will be described.
  • Step (3-a) Step (3-a) according to the present invention is a step of forming an acrylic layer by reacting the ultraviolet curable acrylic resin liquid. That is, the ultraviolet curable coating film obtained in the second step is intermittently irradiated with a lamp having an illuminance of 100 to 1000 mW / cm 2 and an ultraviolet irradiation amount of 100 to 1000 mJ / cm 2 . This is a step of repeating the ultraviolet irradiation until the raw material monomer does not remain.
  • the ultraviolet irradiation lamp may be a known one, and for example, a light hammer (manufactured by FUSION JAPAN) is used.
  • Step (3-b) is a step of forming an acrylic layer by reacting the thermosetting acrylic resin liquid. That is, it is a step of curing the thermosetting coating film through two stages of heat polymerization and aging polymerization of the thermosetting coating film obtained in the second step.
  • thermosetting coating is polymerized by self-heating, preferably self-heating by adiabatic polymerization (heating polymerization stage).
  • the adiabatic polymerization mentioned here means that the polymerization is started without bringing the coating film that has started polymerization into contact with a medium having a large heat transfer coefficient equal to or lower than the polymerization start temperature, and is usually carried out in air.
  • the support having the thermosetting coating film formed as described above is heated to a temperature of 60 ° C. or higher, preferably 65 ° C. or higher, particularly preferably 70 to 120 ° C. by air heating.
  • the heating is performed at a temperature of 60 to 200 ° C. under the condition that the support having the thermosetting coating film does not undergo deformation such as heat shrinkage. Start by.
  • the coating thickness of the thermosetting acrylic resin liquid prepared in the step (1-b) is thick, the support having the thermosetting coating film when the polymerization reaction is started by heating in the initial stage. Since the amount of heat generated is greater than the amount of heat released from the surface, when the reaction is started by heating a support having a thermosetting coating film in the initial stage, the reaction is accelerated by self-heating, and the applied thermosetting acrylic is applied.
  • the temperature of the coating film of the system resin liquid becomes higher than the heating temperature, and instantaneously becomes 20 to 70 ° C. higher than the heating temperature.
  • the reaction at this time is initiated mainly by a low-temperature pyrolytic polymerization initiator having a 10-hour half-life in the range of 25 to 55 ° C.
  • the reaction time in the heat polymerization stage may be very short, and in the case of air heating, several tens of seconds to 20 minutes, preferably 0.5 to The time is 10 minutes.
  • the time is 0.1 second to 20 minutes, preferably 0.5 second to 1 minute.
  • the heating in the heat polymerization step is usually at least until the low temperature pyrolysis polymerization initiator starts to function by heating, preferably until the low temperature pyrolysis polymerization initiator is consumed. It is heated for 2 to 10 minutes, preferably 0.5 to 5 minutes.
  • the raw material monomer components remaining in the thermosetting coating film are polymerized to 2 to 20% by weight of the total weight of the coating film. It is preferably 2 to 15% by weight, more preferably 2 to 10% by weight.
  • the amount of the raw material monomer component is measured by gas chromatography.
  • the aging polymerization stage according to the present invention is a stage in which the support having the thermosetting coating film that has undergone the heating polymerization stage is maintained at a temperature lower than the heating temperature of the heating polymerization stage of 60 ° C. or higher.
  • the aging polymerization step is preferably performed at a temperature of 35 to 75 ° C.
  • the high temperature thermal decomposition type polymerization initiator remaining after the heating polymerization stage gradually acts to polymerize the remaining raw material monomer over a long period of time, and the amount of the remaining raw material monomer is applied.
  • the support subjected to the heating polymerization step is at the temperature, It is preferable to hold for 1 hour to 10 days.
  • the support that has undergone the heat polymerization step is wound, and the wound product is preferably held in an aging polymerization apparatus heated to 35 to 75 ° C.
  • the high-temperature decomposable polymerization initiator is gradually decomposed, and the polymerization of the remaining raw material monomers proceeds under mild conditions to form an acrylic layer.
  • the coating film can be cured by the ultraviolet curing reaction in the step (3-a) or the thermal curing reaction in the step (3-b). From the viewpoint of productivity, it is more preferable to perform an ultraviolet curing reaction.
  • the acrylic layer according to the present invention can be obtained by reacting the ultraviolet curable acrylic resin liquid through the steps (1-a), 2 and (3-a), Alternatively, the thermosetting resin liquid can be reacted through step (1-b), step 2, and step (3-b). From the viewpoint of productivity, it is more preferable to react an ultraviolet curable acrylic resin liquid.
  • the silver reflective layer which concerns on this invention is a layer which has as a main component the silver which has the function to reflect the sunlight of a resin film-like support body, Preferably it is a layer which consists of silver.
  • the silver reflective layer which concerns on this invention consists of aluminum, chromium, nickel, titanium, magnesium, rhodium, platinum, palladium, tin, gallium, indium, bismuth, and gold other than silver from a viewpoint of improving durability.
  • a silver alloy comprising one or more other metals from the group may be included as a main component.
  • the silver atom is 90 to 99.8 atomic% in the total of silver and other metals (100 atomic%) in the silver reflective layer. It is preferable that the other metal atom is 0.2 to 10 atom% from the viewpoint of durability.
  • gold is more preferable as the other metal from the viewpoint of high temperature humidity resistance and reflectance.
  • the surface reflectance of the silver reflective layer according to the present invention is preferably 80% or more, more preferably 90% or more.
  • the surface reflectance can be measured using a commercially available spectrophotometer, such as U-4100 (manufactured by JASCO Corporation).
  • the thickness of the silver reflective layer according to the present invention is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectivity and the like.
  • a thickness of 10 nm or more is preferable because it does not transmit light and can sufficiently ensure the reflectance in the visible light region of the film mirror.
  • the reflectance in the visible light region of the film mirror increases in proportion to the thickness of the silver reflection layer up to a thickness of about 200 nm, but tends to become independent when the thickness exceeds 200 nm.
  • the surface roughness Ra of the silver reflecting layer according to the present invention is preferably 0.01 to 0.1 ⁇ m, and more preferably 0.02 to 0.07 ⁇ m.
  • the film mirror may have two or more silver reflective layers.
  • the reflectance from the infrared region to the visible light region of the film mirror can be increased, and the dependency of the reflectance on the incident angle can be reduced.
  • the infrared region to visible light region means a wavelength region of 400 to 2500 nm.
  • the incident angle means an angle with respect to a line (normal line) perpendicular to the film surface of the film mirror.
  • the silver reflection layer may be provided on the surface side from the resin film-like support on the sunlight incident side, and on the opposite side (on the back side from the resin film-like support on the sunlight incidence side). It may be provided. It is preferable that the resin film-like support is provided on the surface side from the resin incident support on the sunlight incident side or the like from the viewpoint that the resin is not easily deteriorated by the ultraviolet rays of sunlight.
  • the silver reflective layer according to the present invention and the acrylic layer according to the present invention may be adjacent to each other or may be interposed with other layers, but the ultraviolet absorber or ultraviolet absorptivity contained in the acrylic layer.
  • the resin has another layer.
  • the other layers mentioned here may exist as a single layer, or may exist as a plurality of layers, but the total thickness thereof, that is, the silver reflective layer and the book according to the present invention.
  • the distance from the acrylic layer according to the invention is preferably 1 ⁇ m or more, and from the viewpoint of contributing to thinning of the entire film mirror of the present invention, it is preferably 30 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the distance of a silver reflection layer and an acrylic layer here means the distance between each surface which the silver reflection layer and an acrylic layer approach most.
  • 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 methods.
  • 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, a sputtering method, and the like. is there.
  • a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used. That is, in the film mirror manufacturing method of the present invention, the silver reflective layer is preferably formed by vapor deposition.
  • the silver reflective layer according to the present invention may be formed by heating and baking a coating film containing a silver complex compound from which a ligand can be vaporized / desorbed.
  • a silver complex compound having a ligand that can be vaporized and desorbed has a ligand for stably dissolving silver in a solution, but it is coordinated by removing the solvent and heating and baking.
  • This is a silver complex compound in which the child is thermally decomposed to become CO 2 or a low molecular weight amine compound, vaporized and eliminated, and only metallic silver can remain.
  • a silver complex compound and a method for producing the same for example, a silver complex compound and a method for producing the same described in paragraphs “0064” to “0089” of JP-A-2012-137579, which are publicly known, can be used as appropriate. .
  • the silver reflective layer according to the present invention is formed by heating and baking a coating film containing a silver complex compound from which the ligand can be vaporized and desorbed, a nitrogen-containing cyclic layer is formed in the adjacent layer of the silver reflective layer. It is preferable to contain a compound.
  • a corrosion inhibitor and an antioxidant having an adsorptive group for silver are preferably used.
  • Examples of the corrosion inhibitor having an adsorptive group for silver which is the nitrogen-containing cyclic compound include a compound having a pyrrole ring, a compound having a triazole ring, a compound having a pyrazole ring, a compound having an imidazole ring, and an indazole ring. It is preferably selected from at least one kind of compound or a mixture thereof.
  • the term “corrosion” refers to a phenomenon in which silver is chemically or electrochemically eroded or deteriorated by the environmental material that takes it in (see JIS Z0103-2004). ).
  • the corrosion inhibitor as a compound having a pyrrole ring, a compound having a triazole ring, a compound having a pyrazole ring, a compound having an imidazole ring, and a compound having an indazole ring is disclosed in the [resin coat layer] column described later.
  • nitrogen cyclic compounds corresponding to each of the above may be used.
  • the antioxidant having an adsorptive group for silver which is the nitrogen-containing cyclic compound among the antioxidants disclosed in the [Acrylic layer] column, a phenol-based antioxidant having a nitrogen ring, a thiol-based oxidation Inhibitors and phosphite antioxidants are preferably used. Furthermore, the antioxidant and the light stabilizer can be used in combination. As the light stabilizer, known ones are appropriately selected, and for example, those disclosed in paragraphs “0049” to “0053” of JP2012-232538A are used.
  • resin film-like support As the resin film-like support 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, polyester film such as polyethylene terephthalate, polyethylene naphthalate, 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 , Polymethylpentene Irumu, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and the like acrylic film.
  • polyester film such as polyethylene
  • polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable.
  • a polyester film such as polyethylene terephthalate or an acrylic film, and it may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.
  • the resin film support according to the present invention is preferably at a position farther from the sunlight incident side than the silver reflection layer from the viewpoint that ultraviolet rays hardly reach the resin film support.
  • the presence of an acrylic layer on the sunlight incident side of the resin film-like support, an acrylic layer with an ultraviolet absorber added, and a hard coat layer to be described later are arranged on the sunlight incidence side of the resin film-like support.
  • ultraviolet rays are less likely to reach the resin film support. Therefore, the resin film-like support according to the present invention can be used even if it is a resin that easily deteriorates with respect to ultraviolet rays. From such a viewpoint, it is possible to use a polyester film such as polyethylene terephthalate as the resin film-like support.
  • the thickness of the resin film-like support according to the present invention is preferably an appropriate thickness depending on the type and purpose of the resin. For example, it is generally 10 to 250 ⁇ m, preferably 20 to 200 ⁇ m.
  • the film mirror of the present invention does not have a problem such as being easily broken unlike a conventional glass support, and further has flexibility.
  • a hard coat layer may be provided on the light incident side of the acrylic layer.
  • the hard coat layer according to the present invention is provided for the purpose of preventing the film mirror surface from being damaged or contaminated.
  • the transparent hard coat layer is preferably the outermost layer, the second layer, or the third layer from the light incident side, and the film mirror surface is also damaged by washing away dirt adhering to the film mirror with a brush or the like. From the viewpoint of reducing the reflection efficiency and, as a result, preventing a decrease in reflection efficiency, it is more preferable to provide the outermost layer as a position.
  • a thinner layer (preferably having a thickness of 1 ⁇ m or less) may be provided on the hard coat layer.
  • the thickness of the hard coat layer according to the present invention is preferably 0.05 to 10 ⁇ m, more preferably 1 to 4 ⁇ m, and even more preferably 1.5 to 3 ⁇ m. If the thickness of the hard coat layer is 0.05 ⁇ m or more, sufficient scratch resistance can be obtained. In addition, if the thickness of the hard coat layer is 10 ⁇ m or less, it is possible to prevent the hard coat layer from cracking due to excessive stress, and from the viewpoint of preventing electrostatic adhesion of dirt such as dust. Is preferably 10 ⁇ m or less.
  • the scratch resistance of the hard coat layer according to the present invention is preferably 30 or less in a steel wool test with a pencil hardness of H or more and less than 6H and a load of 500 g / cm 2 .
  • the pencil hardness is evaluated based on the pencil hardness test JIS-K5400.
  • the pencil hardness of each sample at 45 ° inclination and 1 kg load is evaluated.
  • the electric resistance value of the outermost surface of the film mirror is 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 12 ⁇ ⁇ ⁇ . More preferably, it is 3.0 ⁇ 10 9 to 2.0 ⁇ 10 11 ⁇ ⁇ ⁇ .
  • the surface electrical resistance value is measured according to the standard of JIS K 7194 using Hiresta manufactured by Mitsubishi Chemical Corporation. However, after leaving the sample in an environment with a humidity of 50% and a temperature of 50 ° C. for 2 hours or more, placing the sample on a conductive metal plate, applying a voltage of 500 V, and measuring the surface electricity of the sample 30 seconds after the start of measurement. The resistance value is measured using a probe.
  • the falling angle of the hard coat layer is larger than 0 ° and not larger than 30 ° because water droplets adhering to the surface of the film mirror easily fall off due to rain or condensation.
  • the falling angle refers to a value obtained by dropping a water drop on a horizontal mirror and then gradually increasing the tilt angle of the mirror to measure the minimum angle at which a predetermined weight of water drop falls. Say. It can be said that the smaller the tumbling angle, the easier the water droplets to roll off the surface, and the surface to which the water droplets hardly adhere.
  • steel wool # 0000
  • steel wool # 0000
  • HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.
  • This test evaluates the number of scratches by reciprocating the surface of the article 10 times at a speed of 10 mm / sec.
  • the sliding angle was measured by attaching a sliding method kit DM-SA01 to a contact angle meter DM501 (Kyowa Interface Chemistry), dropping 50 ⁇ l of water, tilting the support from a horizontal state at a speed of 0.5 ° / second, The angle at which the rolls down is measured as the fall angle. A smaller rolling angle is preferable because water droplets can be easily dropped and have excellent antifouling properties.
  • the hard coat layer according to the present invention can be composed of an acrylic resin, a urethane resin, a melamine resin, an epoxy resin, an organic silicate compound, a silicone resin, or the like.
  • a silicone resin or an acrylic resin is preferable from the viewpoint of scratch resistance.
  • 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 oligomer examples include polyester acrylate, urethane acrylate, epoxy acrylate, polyether acrylate, and the like in which a reactive acrylic group is bonded to an acrylic resin skeleton, and also melamine, isocyanuric acid, and the like.
  • a material in which an acrylic group is bonded to a rigid skeleton may also be used.
  • the oligomer has a molecular weight that is somewhat large, for example, a weight average molecular weight of 1000 or more and less than 10,000.
  • the reactive diluent serves as a solvent for the coating process as a coating agent medium, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a copolymerization component of the film.
  • polyfunctional acrylic cured paints such as “Diabeam (registered trademark)” series (Mitsubishi Rayon Co., Ltd.), and “Denacol” (registered trademark) series (Nagase Sangyo Co., Ltd.) ), Product name “NK Ester” series (made by Shin-Nakamura Co., Ltd.), product name “UNIDIC (registered trademark)” series (made by Dainippon Ink & Chemicals, Inc.), product name “Aronix (registered trademark)” series (Made by Toagosei Co., Ltd.), brand name “Blemmer (registered trademark)” series (made by NOF Corporation), brand name “KAYARAD (registered trademark)” series (made by Nippon Kayaku Co., Ltd.), brand name, etc. Examples include the “light ester” series or “light acrylate” series (manufactured by Kyoeisha Chemical Co., Ltd.).
  • thermosetting polysiloxane resin such as a trade name Perma-New (registered trademark) 6000 (manufactured by California Hardcoating Co., Ltd.), a hard coating that is cured by irradiation with electron beams or ultraviolet rays.
  • Coating liquids especially thermosetting silicone hard coat liquids composed of partially hydrolyzed oligomers of alkoxysilane compounds, ultraviolet curable acrylic hard coat liquids composed of acrylic compounds having unsaturated groups, and thermosetting inorganic materials. It is preferable.
  • an aqueous colloidal silica-containing acrylic resin Japanese Patent Laid-Open No. 2005-66824
  • a polyurethane-based resin composition Japanese Patent Laid-Open No. 2005-110918
  • an aqueous silicone compound as a binder.
  • Resin film used Japanese Patent Laid-Open No. 2004-142161
  • photocatalytic oxide-containing silica film such as titanium oxide or alumina
  • photocatalytic film such as titanium oxide or niobium oxide having a high aspect ratio
  • photocatalyst examples thereof include a fluorine-containing resin coating (Pierex Technologies), an organic / inorganic polysilazane film, and a film using a hydrophilization accelerator (AZ Electronics) in organic / inorganic polysilazane.
  • thermosetting silicone hard coat layer a partially hydrolyzed oligomer of an alkoxysilane compound synthesized by a known method can be used.
  • An example of the synthesis method is as follows. First, tetramethoxysilane or tetraethoxysilane is used as an alkoxysilane compound, and a predetermined amount of water is added to the alkoxysilane compound in the presence of an acid catalyst such as hydrochloric acid or nitric acid to remove by-produced alcohol from room temperature to 80 ° C. React with.
  • an acid catalyst such as hydrochloric acid or nitric acid
  • the alkoxysilane is hydrolyzed, and further, a partially hydrolyzed oligomer of the alkoxysilane compound having an average polymerization degree of 4 to 8 having two or more silanol groups or alkoxy groups in one molecule is obtained by the condensation reaction.
  • a curing catalyst such as acetic acid or maleic acid is added to this and dissolved in an alcohol or glycol ether organic solvent to obtain a thermosetting silicone hard coat liquid. And this is apply
  • an acrylic compound having an unsaturated group such as pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra
  • a polyfunctional (meth) acrylate mixture such as (meth) acrylate can be used, and a photopolymerization initiator such as benzoin, benzoin methyl ether, or benzophenone is blended and used.
  • a hard-coat layer is formed by apply
  • the hard coat layer is preferably composed of a resin having a high degree of polymerization in order to achieve both the thinness of the hard coat layer and the scratch resistance.
  • the hard coat layer may contain various additives such as an ultraviolet absorber and an antioxidant. Various additives will be described in detail below.
  • the hard coat layer according to the present invention may contain an additive such as an ultraviolet absorber or an antioxidant, and the ultraviolet absorber or antioxidant disclosed in the [Acrylic layer] column is preferably used.
  • the content of the ultraviolet absorber in the hard coat layer is 0.1 to 20 with respect to 100% by weight of the total composition of the hard coat layer in order to improve the durability while maintaining good adhesion. % By weight is preferable, 0.25 to 15% by weight is more preferable, and 0.5 to 10% by weight is particularly preferable.
  • the content of the antioxidant in the hard coat layer is 0.01 to 3% by weight with respect to 100% by weight of the total composition of the hard coat layer in consideration of the balance between the function of the antioxidant and the bleed out. It is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight.
  • known light stabilizers, surfactants, leveling agents, antistatic agents, and the like can be blended in the hard coat layer according to the present invention as necessary.
  • the hard coat layer according to the present invention may be subjected to a surface treatment.
  • a surface treatment for example, corona treatment (JP-A-11-172028), plasma surface treatment, ultraviolet / ozone treatment, surface projection formation (JP-A-2009-226613), surface micromachining treatment, and the like can be mentioned.
  • Formation of hard coat layer As a method for forming the hard coat layer according to the present invention, conventionally known coating methods such as a wire bar coating method, a gravure coating method, a reverse coating method, and a die coating method can be used.
  • the hard coat layer according to the present invention uses the hard coat liquid, for example, when the hard coat liquid to be used is a thermosetting type, the hard coat liquid is coated on a support having an acrylic layer with a wire bar. After drying, the film can be formed by performing heat treatment at 30 to 130 ° C. for 0.5 to 168 hours.
  • the hard coat layer according to the present invention can be formed of an inorganic material such as polysilazane, silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, or lanthanum nitride.
  • it can be formed by forming a film by a vacuum film forming method.
  • the vacuum film forming method include 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.
  • a resin coat layer is preferably provided adjacent to the silver reflective layer.
  • a resin coating layer is further provided below the silver reflection layer between the acrylic layer and the silver reflection layer, or when the silver reflection layer is located below the resin film-like support as viewed from the light incident side. Can be done.
  • the resin coating layer according to the present invention prevents moisture or chemicals in the air from entering the silver reflecting layer and corroding the silver reflecting layer, and further mechanical pressure such as impact and scratching from the outside. Therefore, it has a function of protecting the silver reflection layer.
  • the resin coat layer according to the present invention may have an ultraviolet absorbing function.
  • the resin coat layer according to the present invention may consist of only one layer or a plurality of layers.
  • the thickness of the resin coat layer is preferably 0.01 to 10 ⁇ m, and more preferably 0.05 to 8 ⁇ m.
  • the resin coat layer according to the present invention is preferably mainly composed of a binder resin in order to maintain high adhesion with a silver reflective layer or the like even when installed over a long period of time in an outdoor environment.
  • the binder resin include cellulose ester resins, polyester resins, isocyanate resins, polycarbonate resins, polyarylate resins, polysulfone (including polyethersulfone) resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate.
  • Polyethylene resin Polypropylene resin, cellophane resin, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinylidene chloride resin, polyvinyl alcohol resin, Ethylene vinyl alcohol resin, syndiotactic polystyrene resin, polycarbonate resin, norbornene resin, polymethylpentene resin
  • Polyether ketone resin, polyether ketone imide resin polyamide resin, fluorine resin, nylon resin, polymethyl methacrylate-based resins, acrylic resin or the like resin.
  • polyester resins, isocyanate resins, and acrylic resins are more preferable.
  • the corrosion inhibitor is added.
  • it may be provided apart from (without adjoining) the silver reflective layer. In such a case, it is preferable to include a silver corrosion inhibitor.
  • an adsorptive group for silver or a silver alloy which is a main constituent material of the silver reflecting layer it is preferable to have.
  • the corrosion inhibitor examples include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, and indazole rings. It is desirable that the compound is selected from at least one of a compound having a compound, a copper chelate compound, a thiourea, a compound having a mercapto group, and a naphthalene compound, or a mixture thereof. Of these, corrosion inhibitors containing nitrogen cyclic compounds are more preferred.
  • the compound such as benzotriazole is an ultraviolet absorber and sometimes serves as a corrosion inhibitor.
  • silicone-modified resin It is also possible to use a silicone-modified resin. It does not specifically limit as a silicone modified resin.
  • the corrosion inhibitor for example, those disclosed in paragraphs “0061” to “0073” of JP2012-232538A are appropriately selected.
  • a conventionally known coating method such as a gravure coating method, a reverse coating method, or a die coating method can be used.
  • anchor layer In the film mirror of the present invention, it is preferable to provide an anchor layer in order to bring the resin film-like support and the silver reflective layer into close contact. Therefore, the anchor layer has an adhesive property that allows the resin film-like support and the silver reflective layer to be in close contact, heat resistance that can withstand heat when the silver reflective layer is formed by a vacuum deposition method, and the silver reflective layer that is inherently high. Smoothness is required to bring out the reflection performance.
  • the resin used for the anchor layer according to the present invention is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness, and polyester resin, acrylic resin, melamine resin, epoxy Resins, polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, etc., or a mixture of these resins can be used.
  • polyester resins and melamine resins are mixed resins or polyester resins.
  • a mixed resin of a resin and an acrylic resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable.
  • the thickness of the anchor layer according to the present invention is preferably 0.01 to 3 ⁇ m, and more preferably 0.05 to 2 ⁇ m. By satisfying the thickness range of 0.01 to 3 ⁇ m, it is possible to cover the unevenness on the surface of the resin film-like support while maintaining the adhesiveness, improve the smoothness, and sufficiently cure the anchor layer. As a result, the reflectance of the film mirror can be increased.
  • the anchor layer according to the present invention contains the corrosion inhibitor disclosed in the [resin coat layer] column.
  • a method for forming the anchor layer according to the present invention conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
  • the fill mirror of the present invention can further have an antistatic layer.
  • the antistatic layer according to the present invention has a function of preventing the outermost layer on the sunlight incident side of the film mirror from being charged.
  • Film mirrors have a resin film-like support compared to glass mirrors and the surface is often made of resin, so they are easily charged and easily attract dirt such as sand and dust. . Therefore, sand, dust, etc. adhere and it is mentioned as a problem that reflection efficiency falls.
  • the presence of an antistatic layer in the layer closest to the outermost layer of the film mirror can suppress the charging of the surface of the film mirror, can suppress the adhesion of dirt such as sand and dust, This is preferable because high reflection efficiency can be maintained.
  • the antistatic layer according to the present invention is preferably present through a very thin layer between the layer adjacent to the outermost layer of the film mirror or the outermost layer. Further, any other layer such as an acrylic layer may also serve as the antistatic layer.
  • the thickness of the antistatic layer according to the present invention is preferably 100 nm to 1 ⁇ m. If the thickness of the antistatic layer is 1 ⁇ m or less, good light transmittance can be obtained.
  • a technique for imparting antistatic ability to the antistatic layer there is a technique of reducing the electric resistance value of the antistatic layer by imparting conductivity to the antistatic layer.
  • an antistatic technique a method in which a conductive filler which is a conductive substance is dispersed and contained in an antistatic layer, a method using a conductive polymer, a method in which a metal compound is dispersed or coated on a surface, an organic sulfonic acid And an internal addition method using an anionic compound such as organic phosphoric acid, a method using a surface active type low molecular weight antistatic agent such as polyoxyethylene alkylamine, polyoxyethylene alkenylamine, and glycerin fatty acid ester, carbon There is a method of dispersing conductive fine particles such as black.
  • conductive fillers which are conductive substances
  • conductive filler contained in the antistatic layer there are conductive inorganic fine particles, among which metal fine particles, conductive inorganic oxide fine particles and the like can be used.
  • conductive inorganic oxide fine particles can be preferably used.
  • the electrical resistance value of the antistatic layer if the coating film resistance is largely divided in the first place, it can be divided into particle internal resistance and contact resistance.
  • the internal resistance of the particles is affected by the amount of doping / oxygen defects of different metals and crystallinity.
  • the contact resistance is affected by the particle diameter and shape, the dispersibility of the fine particles in the paint, and the conductivity of the binder resin. Since a film having a relatively high conductivity is considered to have a larger influence of contact resistance than internal resistance of the particle, it is important to form a conductive path by controlling the particle state.
  • the antistatic layer has an antistatic property by containing a conductive filler.
  • a conductive filler contained in the antistatic layer, there are conductive inorganic fine particles, among which metal fine particles, conductive inorganic oxide fine particles and the like can be used.
  • conductive inorganic oxide fine particles can be preferably used.
  • an organic binder or an inorganic binder can be used as a binder for holding a conductive filler.
  • a resin can be used, and examples thereof include acrylic resins, cycloolefin resins, and polycarbonate resins.
  • a hard coat can be used as a binder, and an ultraviolet curable polyfunctional acrylic resin, urethane acrylate, epoxy acrylate, oxetane resin, polyfunctional oxetane resin, and the like can be used.
  • the inorganic binder examples include inorganic oxide binders (may be inorganic oxide binders using a sol-gel method) and tetrafunctional inorganic binders.
  • Preferable examples of the inorganic oxide binder include silicon dioxide, titanium oxide, aluminum oxide, strontium oxide and the like. Particularly preferred is silicon dioxide.
  • Preferred examples of the tetrafunctional inorganic binder include polysilazane (for example, trade name: Aquamica (manufactured by AZ Electronics Co., Ltd.)), siloxane compounds (for example, Colcoat P (manufactured by Colcoat Co., Ltd.)), alkyl silicates and metal alcoholates.
  • a tetrafunctional inorganic binder a sol-gel solution containing tetraethoxysilane as a main raw material and a catalyst added may be used.
  • materials having both organic and inorganic properties include polyorganosiloxane and polysilazane. These materials can be said to be organic binders and inorganic binders.
  • a mixture of an inorganic binder and an organic binder may be used as the binder for the antistatic layer, but the total amount of the binder is preferably an inorganic binder.
  • the binder is an inorganic binder, it is desirable because it has weather resistance to ultraviolet rays and can maintain high reflectivity over a long period even when used outdoors.
  • the adhesion between the antistatic layer and the hard coat layer is good when the binder of the antistatic layer is an inorganic binder.
  • the binder of the antistatic layer is an inorganic binder.
  • inorganic binders are more susceptible to cracking than organic binders, but by providing a hard coat layer as the upper layer of the antistatic layer, cracking prevention, chipping prevention and chipping scattering prevention effects can be obtained, and inorganic cracking is easy. Since a binder can be used without any problem, the film mirror preferably has two layers, an antistatic layer and a hard coat layer.
  • the antistatic layer according to the present invention preferably contains a conductive filler (conductive inorganic fine particles) at 75% or more from the viewpoint of ensuring conductivity, and a ratio of 95% or less from the viewpoint of light transmission. It is preferable to contain.
  • a conductive filler conductive inorganic fine particles
  • the antistatic layer according to the present invention can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, or a die coating method.
  • a gas barrier layer may be provided on the light incident side of the silver reflecting layer. It is preferable to provide a gas barrier layer between the acrylic layer and the silver reflective layer.
  • the gas barrier layer according to the present invention is intended to prevent deterioration of humidity, particularly deterioration of the resin film-like support and each component layer supported by the resin film-like support due to high humidity.
  • -It may have a use, and as long as it has the function of preventing deterioration, a gas barrier layer of various modes can be provided.
  • paragraphs “0044” to “0096” of the publicly known international publication number WO2011 / 096151 A1 can be applied.
  • the adhesion layer in order to join the film mirror of this invention to the base material mentioned later, the adhesion layer can be provided.
  • the film mirror may have the layer by a peeling sheet in the reverse side to the sunlight incident side of an adhesion layer.
  • the adhesive layer according to the present invention 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.
  • a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used.
  • the laminating method for joining the adhesive layer and the substrate is not particularly limited. 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 100 ⁇ m from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.
  • a thickness of 1 ⁇ m or more is preferable because a sufficient adhesive effect can be obtained.
  • the thickness is 100 ⁇ m or less, the pressure-sensitive adhesive layer is not too thick and the drying speed is not slowed, which is efficient.
  • the original adhesive strength can be obtained, and no adverse effects such as residual solvent can occur.
  • the film mirror of the present invention may have a release layer (also referred to as a release sheet) on the side opposite to the sunlight incident side of the adhesive layer.
  • a release layer also referred to as a release sheet
  • the film mirror when shipped, it can be shipped with the release sheet attached to the adhesive layer, and the release sheet can be peeled off to expose the adhesive layer and bonded to the substrate.
  • the release sheet according to the present invention is not particularly limited as long as it can provide the protective property of the silver reflective layer.
  • a plastic such as an acrylic film, a polycarbonate film, a polyarylate film, a polyethylene naphthalate film, a polyethylene terephthalate film, and a fluorine film.
  • the thickness of the release sheet according to the present invention is not particularly limited, but is usually preferably in the range of 12 to 250 ⁇ m.
  • the surface roughness Ra of the release layer is preferably 0.01 to 0.1 ⁇ m. Due to the surface roughness of the release layer, the surface of the solar reflective film mirror or the silver reflective layer also becomes rough, so even when using a roll-to-roll system that continuously forms films in the production stage of film mirrors, blocking, etc. Can be prevented.
  • a method for manufacturing a film mirror is provided.
  • the process is characterized by the step of forming the acrylic layer. That is, the step of forming an acrylic layer includes a step of applying and drying an acrylic resin liquid by a roll-to-roll method, and in particular, applying an acrylic resin liquid by a roll-to-roll method and drying, heat or ultraviolet light. It is characterized in that it includes a step of curing by the method.
  • FIG. 1 an example of a film mirror manufacturing method will be described.
  • the anchor layer 2 can be formed on the upper surface of the resin film-like support 1 on the incident light side by a gravure coating method, and the silver reflection layer 3 can be formed on the upper surface by a vacuum deposition method.
  • the resin coat layer 4 can be formed on the upper surface of the silver reflective layer 3 by a gravure coating method.
  • an acrylic layer 5 containing an acrylic resin is formed on the upper surface of the resin coat layer 4.
  • a first step of preparing an acrylic resin liquid as a raw material of the acrylic resin a second step of applying the acrylic resin liquid to the resin coat layer 4 by a roll-to-roll method, and forming a coating film;
  • the acrylic layer 5 can be formed by the third step of curing the coating film. More specifically, the method for forming the acrylic layer 5 disclosed in the column of [Acrylic layer] is referred to.
  • a hard coat layer 6 can be formed on the upper surface of the acrylic layer 5.
  • the film filler according to one embodiment of the present invention can be manufactured, the present invention is not limited to the above-described layer configuration.
  • a solar reflective mirror is provided.
  • the solar reflective mirror has a film mirror and a self-supporting base material (supporting base material), and the film mirror is bonded to the self-supporting base material (supporting base material) via an adhesive layer. Yes.
  • the film mirror is cut into a predetermined size (for example, a size for attaching to a support base material).
  • the film mirror of the present invention is preferably attached to a self-supporting substrate and used as a solar reflective mirror.
  • self-supporting substrate means supporting the opposite edge portions when cut to a size that can be used as a substrate for a solar reflective mirror. This means that the substrate has rigidity enough to support the substrate.
  • the base material of the solar reflective mirror has a self-supporting property, so that it is easy to handle when installing the solar reflective mirror, and the holding member for holding the solar reflective mirror has a simple configuration. Therefore, it is possible to reduce the weight of the reflection device, and it is possible to suppress power consumption during solar tracking.
  • the base material according to the present invention may be a single layer or a shape in which a plurality of layers are laminated. Moreover, a single structure may be sufficient and it may be divided
  • the shape of the base material according to the present invention preferably has a concave shape or can be a concave shape. Therefore, a base material that is variable from a flat shape to a concave shape may be used, or a base material that is fixed to a concave shape may be used.
  • the base material that can be changed into the concave shape can adjust the curvature of the film mirror that is bonded by adjusting the curvature of the base material. It is preferable because a rate can be obtained.
  • the base material having the concave shape fixed is preferable from the viewpoint of adjustment cost because it is not necessary to adjust the curvature.
  • the base material according to the present invention includes 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, a tin-plated steel plate, a chrome-plated steel plate, a stainless steel plate, and a veneer plate (preferably May be a wooden board such as a waterproof board), a fiber reinforced plastic (FRP) board, a resin board, and the like.
  • a metal plate from the viewpoint of high thermal conductivity. More preferably, it is a plated steel plate, stainless steel plate, aluminum plate or the like having not only high thermal conductivity but also good corrosion resistance. Most preferably, a steel plate combining a resin and a metal plate is used.
  • the base material when most of the base material is made of resin, it is preferable to use a resin material having a hollow structure. This is because when the substrate is made of a resin material that does not have a hollow structure, the thickness required to obtain rigidity sufficient to provide self-supporting properties increases, and as a result, the substrate mass increases. However, when the layer is made of a resin material having a hollow structure, it is possible to reduce the weight while maintaining the self-supporting property. In addition, since a function as a heat insulating material due to the hollow structure also occurs, it is possible to suppress the temperature change of the surface opposite to the light incident side from being transmitted to the film mirror, to prevent condensation and to suppress deterioration due to heat It becomes.
  • a layer having a resin material having a hollow structure it is preferable to provide a resin film having a smooth surface as a surface layer and to use a resin material having a hollow structure as an intermediate layer from the viewpoint of increasing the reflection efficiency of the film mirror. .
  • various conventionally known resin films can be used.
  • polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable.
  • a polyester film such as polyethylene terephthalate or an acrylic film, and it may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.
  • the thickness of the resin film is preferably an appropriate thickness depending on the type and purpose of the resin. For example, it is generally 10 to 250 ⁇ m, preferably 20 to 200 ⁇ m.
  • a cellular structure made of a foamed resin a three-dimensional structure having a wall surface made of a resin material (such as a honeycomb structure), a resin material to which hollow fine particles are added, or the like can be used.
  • the cellular structure of the foamed resin refers to a material in which a gas is finely dispersed in a resin material and formed into a foamed or porous shape, and a known foamed resin material can be used as the material.
  • Polyurethane, polyethylene, polystyrene and the like are preferably used.
  • the honeycomb structure represents a general three-dimensional structure composed of a plurality of small spaces surrounded by side walls.
  • the resin material constituting the wall surface is a homopolymer or copolymer of olefins such as ethylene, propylene, butene, isoprene pentene, and methylpentene.
  • Acrylic derivatives such as polyolefin (for example, polypropylene, high-density polyethylene), polyamide, polystyrene, polyvinyl chloride, polyacrylonitrile, ethylene-ethyl acrylate copolymer, vinyl acetate copolymers such as polycarbonate, ethylene-vinyl acetate copolymer
  • Thermoplastic resins such as ionomers, ABS resins, polyolefin oxides and polyacetals are preferably used. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.
  • thermoplastic resins olefin-based resins or resins mainly composed of olefin-based resins
  • polypropylene-based resins or resins based mainly on polypropylene-based resins are preferable because of excellent balance between mechanical strength and moldability.
  • the resin material may contain an additive.
  • the additive include silica, mica, talc, calcium carbonate, glass fiber, carbon fiber, and other inorganic fillers, plasticizers, stabilizers, colorants, charging agents.
  • An inhibitor, a flame retardant, a foaming agent, etc. are mentioned.
  • a solar power generation reflector is provided.
  • the solar power generation reflecting device of the present invention has a solar reflective mirror and a holding member for holding the solar reflective mirror.
  • a cylindrical member having fluid inside is provided as a heat collecting part in the vicinity of the film mirror, and the internal fluid is heated by reflecting sunlight to the cylindrical member.
  • a form generally referred to as a trough type, which generates heat by converting thermal energy, can be cited as one form.
  • mold is also mentioned as another form.
  • the tower type configuration has at least one heat collecting part and at least one solar power generation reflecting device for reflecting sunlight and irradiating the heat collecting part, and the heat collected in the heat collecting part. There is one that heats a liquid by using and rotates a turbine to generate electricity.
  • a plurality of solar power generation reflecting devices are arranged around the heat collecting section.
  • a plurality of solar power generation reflecting devices are arranged in a concentric circle shape or a concentric fan shape.
  • sunlight is reflected to the collector mirror by the sunlight reflecting mirrors installed around the support tower, and then reflected further by the collector mirror and sent to the heat collector and sent to the heat exchange facility. It is done.
  • the present invention can be used for both trough type and tower type. Of course, it can be used for various other types of solar thermal power generation.
  • the solar power generation reflection device includes a holding member that holds a solar light reflecting mirror.
  • the holding member preferably holds the solar reflective mirror in a state where the sun can be tracked.
  • maintains several places with a rod-shaped holding member is preferable so that the mirror for sunlight reflection can hold
  • the holding member preferably has a configuration for holding the sunlight reflecting mirror in a state where the sun can be tracked.
  • the holding member may be driven manually or a separate driving device may be provided to automatically It is good also as a structure which tracks.
  • UV curable acrylic resin liquid > 0.003% by weight of photoinitiator (trade name: Irgacure 184, manufactured by BASF) was uniformly added to 100% by weight of the total amount of raw material monomers consisting of 85% by weight of 2-ethylhexyl acrylate and 15% by weight of acrylic acid. .
  • the mixture was charged into a 300 ml Pyrex (registered trademark) separable flask equipped with a stirring blade, a cooling pipe, a nitrogen gas introduction pipe, and a thermometer, and nitrogen gas was introduced into the container for 20 minutes to air in the container. Was replaced with nitrogen gas, and the mixture was heated to 80 ° C. in a nitrogen stream.
  • the obtained ultraviolet curable acrylic resin liquid did not contain a solvent and had a viscosity of 320 poise. Moreover, about the partial polymer contained in this, the weight average molecular weight measured by GPC was 750,000, and the number average molecular weight was 230,000.
  • thermosetting acrylic resin > V-70 (10 hours half-life 30 ° C, manufactured by Wako Pure Chemical Industries, Ltd.) as a low-temperature pyrolytic polymerization initiator for 100% by weight of the total amount of raw material monomers consisting of 85% by weight of 2-ethylhexyl acrylate and 15% by weight of acrylic acid 0.5% by weight, V-40 (10-hour half-life 88 ° C., NOF Corporation) 0.5% by weight as a high-temperature pyrolytic polymerization initiator, cross-linking agent (trade name: Coronate HX, Polyurethane Industry ( 0.05% by weight) and 30% by weight of filler (PE particles having an average particle size of 20 ⁇ m) were added. The mixture was mixed at 30 ° C. for 5 hours. Thereafter, defoaming treatment was performed to prepare a thermosetting acrylic resin liquid.
  • V-70 hours half-life 30 ° C, manufactured by Wako Pure Chemical Industries, Ltd.
  • V-40 10-hour half-life 88
  • thermosetting acrylic resin liquid did not contain a solvent, and its viscosity was 1500 centipoise. Moreover, about the partial polymer contained in this, the weight average molecular weight measured by GPC was 500,000, and the number average molecular weight was 190,000.
  • Example 1 As the resin film-like support 1, a biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 ⁇ m) was used. Polyester resin (Polyester SP-181, manufactured by Nippon Gosei Kagaku) and TDI isocyanate (2,4-tolylene diisocyanate, manufactured by Tokyo Chemical Industry Co., Ltd.) using a gravure coater on one side of the polyester film roll. Were mixed at a resin solid content ratio of 10: 2, and methyl ethyl ketone was added as a solvent so that the resin solid content concentration was 20% by weight.
  • glycol dimercaptoacetate manufactured by Wako Pure Chemical Industries, Ltd.
  • the mixture was coated by a gravure coating method to form an anchor layer 2 having a thickness of 60 nm.
  • a silver reflection layer 3 made of silver was formed on the anchor layer 2 by a vacuum deposition method so as to have a thickness of 80 nm.
  • a resin having a thickness of 60 nm is formed in the same manner except that TINUVIN 234 (manufactured by BASF) is used instead of glycol dimercaptoacetate as a corrosion inhibitor in forming the anchor layer 2 on the silver reflective layer 3. Coat layer 4 was formed.
  • the ultraviolet curable acrylic resin liquid is applied onto the resin coat layer 4 using a gravure coater so that the thickness after curing is 50 ⁇ m, and after drying, the illuminance is 100 mW / cm 2 , the light intensity
  • the acrylic layer 5 was formed by irradiating 150 mJ / cm ⁇ 2 > of ultraviolet rays and performing a curing treatment.
  • a hard coat solution Perma-New TM 6000 (manufactured by California Hardcoating Company) is coated on the acrylic layer 5 with a gravure coater, dried at 80 ° C. for 45 seconds, and then heat treated at 70 ° C. for 48 hours.
  • a hard coat layer 6 having a thickness of 3 ⁇ m was formed, and a film mirror 1 was produced. All these operations were created by the roll-to-roll method.
  • Example 2 A film mirror 2 was produced in the same manner as in Example 1 except that the acrylic layer 5 was formed by the following operation.
  • thermosetting acrylic resin liquid is applied onto the resin coat layer 4 using an applicator so that the cured thickness is 50 ⁇ m, dried at 80 ° C. for 60 seconds, and then at 50 ° C. for 1 hour.
  • the acrylic layer 5 was formed by performing a curing process.
  • Example 3 A film mirror 3 was produced in the same manner as in Example 1 except that 10% by weight of methyl ethyl ketone was added to the total amount of raw material monomers of 100% by weight in the ultraviolet curable acrylic resin liquid.
  • Example 4 A film mirror 4 was produced in the same manner as in Example 2 except that 20% by weight of methyl ethyl ketone was added to 100% by weight of the total amount of raw material monomers in the thermosetting acrylic resin liquid.
  • Example 5 Except that the UV curable acrylic resin liquid was mixed with 2.5% by weight of a UV absorber (trade name: Tinuvin 477, manufactured by BASF Japan) with respect to 100% by weight of the total amount of raw material monomers. In the same manner as in Example 1, a film mirror 5 was produced.
  • a UV absorber trade name: Tinuvin 477, manufactured by BASF Japan
  • Example 6 A film mirror 6 was produced in the same manner as in Example 5 except that the blending amount of the ultraviolet absorber was changed to 5% by weight.
  • Example 7 ⁇ Example 7> Implemented except that the ultraviolet curable acrylic resin liquid was further blended with an antioxidant (trade name: ADK STAB LA52, manufactured by ADEKA) 1% by weight based on 100% by weight of the total amount of raw material monomers. In the same manner as in Example 6, a film mirror 7 was produced.
  • an antioxidant trade name: ADK STAB LA52, manufactured by ADEKA
  • Example 8> A film mirror 8 was produced in the same manner as in Example 7 except that the thickness of the acrylic layer 5 was 75 ⁇ m.
  • Example 9 A film mirror 9 was produced in the same manner as in Example 8 except that the thickness of the acrylic layer 5 was 100 ⁇ m.
  • Example 10 A film mirror 10 was produced in the same manner as in Example 8, except that the blending amount of the ultraviolet absorber was 8% by weight.
  • Example 11 First, the resin coating layer 4 was formed in the same manner as in Example 1. Next, the resin film-like support 1 was directed to the light incident side, and the acrylic resin layer 5 and the hard coat layer 6 were sequentially formed on the upper surface in the same manner as in Example 1 to produce a film mirror 11.
  • Example 12 First, the resin coating layer 4 was formed in the same manner as in Example 1. Next, the resin film-like support 1 is directed to the light incident side, and the entire resin solid content of an acrylic resin resin liquid (trade name: BR-95, manufactured by Mitsubishi Rayon Co., Ltd., resin solid content concentration: 25% by weight) is formed on the upper surface. 100% by weight, 5% by weight of UV absorber (trade name: Tinuvin 477, manufactured by BASF Japan) and 1% by weight of antioxidant (trade name: ADK STAB LA52, manufactured by ADEKA) Further, a coating solution to which 75% by weight of methyl ethyl ketone was added was applied and dried at 85 ° C. for 5 minutes to form an acrylic layer 5 having a thickness of 30 ⁇ m. Layer 6 was formed, and film mirror 12 was produced.
  • an acrylic resin resin liquid trade name: BR-95, manufactured by Mitsubishi Rayon Co., Ltd., resin solid content concentration: 25% by weight
  • 100% by weight 5% by weight of UV absorber (trade name: Tin
  • a film mirror 13 was produced in the same manner as in Example 1 except that the acrylic layer 5a was formed by the following operation instead of the acrylic layer 5.
  • An acrylic resin liquid (trade name: BR-95, manufactured by Mitsubishi Rayon Co., Ltd., resin solid content concentration: 25% by weight) was prepared, applied to a thickness of 120 ⁇ m, and dried to form an acrylic layer 5a. .
  • UV absorbers (trade names: Tinuvin 477, BASF Japan) with respect to 100% by weight of the total resin solid content of the acrylic resin liquid (trade name: BR-95, manufactured by Mitsubishi Rayon Co., Ltd.) in the acrylic resin liquid of Comparative Example 2.
  • Film mirror 15 was produced in the same manner as Comparative Example 2 except that 5% by weight (made by Co., Ltd.) and 1% by weight of antioxidant (trade name: ADK STAB LA52, made by ADEKA) were blended.
  • an adhesive TBS-730 (Dainippon Ink Co., Ltd.) is coated on the resin coat layer 4 with a wire bar so as to have a thickness of 5 ⁇ m.
  • Acrylic resin film S001 (manufactured by Sumitomo Chemical Co., Ltd.) was bonded by a roll method to form acrylic layer 5b.
  • a hard coat layer 6 was formed on the acrylic layer 5b in the same manner as in Example 1 to produce a film mirror 17.
  • a hard coat layer 6 was formed in the same manner as in Example 1 on the opposite side of the surface of the acrylic layer 5b having silver and copper, and a film mirror 18 was produced.
  • the production levels of the film mirrors 1 to 18 produced above are shown in Table 1.
  • a schematic side view of the layer configuration of the film mirrors 1 to 10 is shown in FIG. 1
  • a schematic side view of the film mirrors 11 and 12 is shown in FIG. 5
  • a schematic side view of the film mirrors 13 to 16 is shown in FIG. 2
  • a schematic side view of the film mirror 17 is shown in FIG. 3
  • a schematic side view of the film mirror 18 is shown in FIG. 4.
  • the formed acrylic layer is peeled off from the glass to prepare an acrylic resin film, and the weight change before and after being left in a thermostatic bath at 80 ° C. for 200 hours is confirmed.
  • the weight change is the residual solvent in each acrylic layer. Was measured as the amount of.
  • a regular reflectance was measured with an incident angle of incident light of 5 ° with respect to the normal of the reflective surface using a dedicated jig. Evaluation was similarly measured as an average reflectance from 400 nm to 2500 nm.
  • UV irradiation test Each of the film mirrors was irradiated with 150 mW / ⁇ of UV light in an environment of 65 ° C. for 600 hours using an i-super UV tester (Iwasaki Electric Co., Ltd.), and the UV resistance of each film mirror was improved. evaluated.
  • the film mirror produced according to the present invention maintains high reflectance without being colored in the silver reflective layer even after production or after performing high-temperature and long-time ultraviolet irradiation or wet heat test. It was shown that. Furthermore, it has been found that it has excellent adhesion. That is, the film mirror of the present invention was found to be a film mirror having both excellent smoothness and durability and high reflectivity.
  • the acrylic layer 5a of Comparative Examples 1 to 3 is formed by dissolving an acrylic resin with a solvent and applying and drying it, as shown in Table 2, the solvent penetrates into the silver layer and the silver layer is purple or It was confirmed that the color was pale purple, and further, after the ultraviolet irradiation test, the color became stronger, and as a result, the reflectance was greatly reduced.
  • the film mirror provided by the present invention has high smoothness, durability, reflectance, and adhesion.

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  • Optical Elements Other Than Lenses (AREA)

Abstract

L'invention concerne : un miroir en film qui a un excellent caractère lisse et une excellente durabilité en même temps, tout en ayant une réflectance élevée ; et un réflecteur pour la conversion thermodynamique solaire. L'invention concerne un miroir en film qui comprend un corps de support de type film de résine, une couche réfléchissante d'argent et une couche acrylique qui est formée par revêtement sur la surface d'incidence de lumière de la couche réfléchissante d'argent, et qui est caractérisé en ce que la couche acrylique a une épaisseur comprise entre de 10 et 100 μm et la quantité d'un solvant restant dans la couche acrylique est 0,1 % en poids ou moins par rapport au poids total de la couche acrylique.
PCT/JP2014/050217 2013-01-11 2014-01-09 Miroir en film et réflecteur pour la conversion thermodynamique solaire WO2014109354A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019020484A (ja) * 2017-07-12 2019-02-07 株式会社クラレ ディスプレイ用スクリーン、及びその製造方法
CN109870753A (zh) * 2018-12-21 2019-06-11 宁波激智科技股份有限公司 一种超高亮高可靠性抗指污银反射膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096151A1 (fr) * 2010-02-04 2011-08-11 コニカミノルタオプト株式会社 Miroir à film, procédé de production de celui-ci et miroir de recueil de lumière solaire
JP2012137579A (ja) * 2010-12-27 2012-07-19 Konica Minolta Advanced Layers Inc フィルムミラー、その製造方法、および太陽光反射用ミラー
JP2012220708A (ja) * 2011-04-08 2012-11-12 Konica Minolta Advanced Layers Inc フィルムミラー及び太陽熱発電用反射装置
JP2012232538A (ja) * 2011-05-09 2012-11-29 Konica Minolta Advanced Layers Inc フィルムミラー、太陽光反射用ミラー及び太陽熱発電用反射装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096151A1 (fr) * 2010-02-04 2011-08-11 コニカミノルタオプト株式会社 Miroir à film, procédé de production de celui-ci et miroir de recueil de lumière solaire
JP2012137579A (ja) * 2010-12-27 2012-07-19 Konica Minolta Advanced Layers Inc フィルムミラー、その製造方法、および太陽光反射用ミラー
JP2012220708A (ja) * 2011-04-08 2012-11-12 Konica Minolta Advanced Layers Inc フィルムミラー及び太陽熱発電用反射装置
JP2012232538A (ja) * 2011-05-09 2012-11-29 Konica Minolta Advanced Layers Inc フィルムミラー、太陽光反射用ミラー及び太陽熱発電用反射装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019020484A (ja) * 2017-07-12 2019-02-07 株式会社クラレ ディスプレイ用スクリーン、及びその製造方法
CN109870753A (zh) * 2018-12-21 2019-06-11 宁波激智科技股份有限公司 一种超高亮高可靠性抗指污银反射膜

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