WO2012165460A1

WO2012165460A1 - Reflecting device for solar thermal power generation, film mirror, and method for producing film mirror

Info

Publication number: WO2012165460A1
Application number: PCT/JP2012/063882
Authority: WO
Inventors: 仁安達
Original assignee: コニカミノルタアドバンストレイヤー株式会社
Priority date: 2011-05-31
Filing date: 2012-05-30
Publication date: 2012-12-06
Also published as: JPWO2012165460A1

Abstract

The present invention addresses the problem of providing a reflecting device for solar thermal power generation having high reflectance and high scratch resistance and weather resistance for withstanding practical use for collecting solar light, and also having high productivity, as well as providing a film mirror and a method for producing a film mirror. This film mirror having at least a light-transmissive resin layer, a light-reflecting layer, a resin substrate, and an adhesive layer in the stated order from a light-incidence side is characterized in that the light-transmissive resin layer contains an ultraviolet absorber and the thickness of the light-transmissive resin layer is 10-150 μm.

Description

Reflector for solar power generation, film mirror, and method for manufacturing film mirror

The present invention relates to a solar power generation reflector, a film mirror, and a method of manufacturing a film mirror.

In recent years, global warming has developed into a more serious situation, and even the future survival of humankind may be threatened. The main cause is thought to be atmospheric carbon dioxide (CO ₂ ) released from fossil fuels that have been used in large quantities as an energy source in the 20th century. Therefore, it is considered that it will not be allowed to continue using fossil fuels in the near future. On the other hand, the depletion of oil and natural gas, once thought to be inexhaustible, has become a reality due to the increase in energy demand accompanying the rapid economic growth of so-called developing countries such as China, India and Brazil. Yes.

Solar energy is considered to be the most stable and abundant amount of natural energy as an alternative energy to fossil fuels. In particular, the vast desert spreads near the equator, which is called the world's sun belt, and the solar energy that falls there is truly inexhaustible. With regard to the use of solar energy, it is thought that 7,000 GW of energy can be obtained if only a few percent of the desert that extends to the southwestern United States is used. It is also believed that using only a few percent of the Arabian peninsula and the deserts of North Africa can cover all the energy used by all mankind.

Thus, although solar energy is a very powerful alternative energy, in order to utilize it in social activities, (1) the energy density of solar energy is low, and (2) solar energy storage. And the difficulty of transport is considered a problem. On the other hand, it has been proposed to solve the problem that the energy density of solar energy is low by collecting solar energy with a huge concentrator.

Since the condensing device is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, etc., conventionally, a glass mirror having good weather resistance has been used. However, the glass mirror has high environmental durability, but it is damaged during transportation, and because of its heavy mass, it is necessary to increase the strength of the frame on which the mirror is installed, which increases the construction cost of the plant. There was a problem.

In order to solve the above problems, it has been considered to replace a glass mirror with a resin reflecting mirror (for example, Patent Document 1 and Patent Document 2).

However, when a metal such as silver is used for the reflection layer of the resin reflection mirror, oxygen, water vapor, hydrogen sulfide, etc. are transmitted through the resin layer, and silver is corroded. Since it deteriorates and causes problems such as discoloration and film peeling, it is difficult to apply a resin reflection mirror to the light collecting device.

A technique using an acrylic film having excellent light resistance against ultraviolet rays on the surface of the resin reflecting mirror is known (for example, Patent Document 3).

However, in the layer configuration proposed in Patent Document 3, when the acrylic film and the polyester film are bonded together with an adhesive layer, bubbles and foreign substances may be mixed between the layers, resulting in a decrease in light reflectivity. There was a problem that there was. Further, there is a problem in that reflected light is scattered by the surface unevenness of the acrylic film formed by melt film formation and the like and the light collection efficiency is lowered.

In addition, contaminants may invade from the interface between the adhesive layer and the silver reflective layer, causing the silver reflective layer to corrode and lowering the reflectance. There was a problem that it peeled off or the polyester film on the light source side of the silver reflecting layer was yellowed.

Furthermore, since the silver reflective layer is in direct contact with the adhesive layer, the unevenness of the adhesive layer affects the silver reflective surface, and there is a problem that the reflected light is scattered and the light collection efficiency is lowered.

Since these problems occur, the resin reflecting mirror proposed in Patent Document 3 cannot be used as a mirror for collecting sunlight.

US Pat. No. 4,307,150 US Pat. No. 4,645,714 Special table 2009-520174

Therefore, the problem to be solved by the present invention is to provide a solar power generation reflecting device, a film mirror, and a film mirror that have high scratch resistance, weather resistance, high reflectance, and high productivity that can withstand the practical use of collecting sunlight. It is to provide a manufacturing method.

One aspect of the present invention is:
In order from the light incident side, a light transmitting resin layer, a light reflecting layer, a resin base material, and a film mirror having at least an adhesive layer,
The translucent resin layer contains an ultraviolet absorber, and the translucent resin layer has a thickness of 10 μm to 150 μm.

Preferably, the translucent resin layer is directly on the surface of the light reflecting layer on the light incident side or on the surface of the constituent layer provided on the light incident side of the light reflecting layer without using an adhesive layer. Is formed.

Preferably, the center line average roughness (Ra) of the surface of the translucent resin layer is 3 nm or more and 20 nm or less.

Preferably, a corrosion prevention layer is provided adjacent to the light incident side of the light reflecting layer.

Preferably, a hard coat layer is provided on the light incident side surface of the translucent resin layer.

Preferably, a gas barrier layer is provided on the light incident side of the light reflecting layer.

And the manufacturing method of the film mirror which manufactures an above-described film mirror,
By directly applying a material to be the translucent resin layer on the light incident side surface of the light reflecting layer or on the surface of the constituent layer provided on the light incident side with respect to the light reflecting layer, the light transmitting resin layer is directly applied. It is characterized by forming a light-sensitive resin layer.

Another aspect of the present invention is a solar power generation reflecting device,
The adhesive layer provided in the film mirror is formed by bonding to a support base material.

Preferably, the support base is made of a resin material having a hollow structure.

Preferably, the support substrate has a pair of metal flat plates and an intermediate layer interposed between the metal flat plates, and the intermediate layer is made of a material having a hollow structure or a resin material.

INDUSTRIAL APPLICABILITY According to the present invention, a solar thermal power generation reflector having high scratch resistance, weather resistance, high reflectance, and high productivity that can endure practical use for concentrating sunlight, a film mirror, and a film mirror manufacturing method Can be provided.

Schematic sectional view showing an example of the configuration of the film mirror for solar power generation of the present invention Schematic sectional view showing an example of the configuration of the solar power generation reflector of the present invention Schematic sectional view showing an example of the configuration of the film mirror for solar power generation of the present invention Schematic sectional view showing an example of the configuration of the solar power generation reflector of the present invention Schematic sectional view showing an example of the configuration of the film mirror for solar power generation of the present invention Schematic sectional view showing an example of the configuration of the solar power generation reflector of the present invention Schematic sectional view showing an example of the configuration of the film mirror for solar power generation of the present invention Schematic sectional view showing an example of the configuration of the solar power generation reflector of the present invention Schematic sectional view showing an example of the configuration of a film mirror for solar power generation as a comparative example Schematic cross-sectional view showing an example of the configuration of a solar power generation reflector as a comparative example Schematic sectional view showing an example of the configuration of a film mirror for solar power generation as a comparative example Schematic cross-sectional view showing an example of the configuration of a solar power generation reflector as a comparative example

Hereinafter, the film mirror for solar power generation according to the present invention will be described in detail. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.
(1) Outline of Configuration of Film Mirror for Solar Power Generation The film mirror of the present invention is, in order from the light incident side, a translucent resin layer 6 containing an ultraviolet absorber, a silver reflection layer 3 as a light reflection layer, and a resin film. The resin base material 1 and the pressure-sensitive adhesive layer 8 are included. In addition, another layer may be interposed between these layers, and each layer may be adjacent. Since the adhesive layer 8 and the silver reflective layer 3 are not in contact with each other, it prevents a problem that contaminants enter from the interface between the adhesive layer 8 and the silver reflective layer 3 to corrode the silver reflective layer 3 to reduce the reflectance. it can. Further, if the adhesive layer 8 and the silver reflective layer 3 are in contact with each other, the unevenness of the adhesive layer 8 is directly reflected on the silver reflective layer 3, scattering occurs in the silver reflective layer 3, and the light reflectivity is lowered. However, since the resin base material 1 is provided between the pressure-sensitive adhesive layer 8 and the silver reflective layer 3, the unevenness of the pressure-sensitive adhesive layer 8 is not reflected in the silver reflective layer 3, and the silver reflective layer 3 having high planarity. And high reflection performance can be obtained.

In addition, the translucent resin layer 6 containing an ultraviolet absorber in the film mirror of the present invention does not have an adhesive layer on the upper surface of the silver reflective layer 3 or the upper surfaces of other constituent layers provided on the silver reflective layer 3. It is preferable to be laminated. Since there is no need to bond the layers through the adhesive layer (11), bubbles and foreign substances are not mixed between the layers, and a decrease in light reflectivity can be prevented. Further, since the translucent resin layer 6 can be provided by coating, it is not necessary to attach a translucent resin film by melt film formation, and scattering of reflected light due to surface irregularities caused by melt film formation, etc. Problems can also be prevented.

For example, as the layer structure of the film mirror of the present invention, the UV-absorbing translucent resin layer 6 and the silver reflecting layer 3 are adjacent (see FIG. 1), the UV-absorbing translucent resin layer 6 and silver. A gas barrier layer 5 and a corrosion prevention layer provided with a corrosion prevention layer 4 between the reflection layers 3 (see FIGS. 2 and 3), a translucent resin layer 6 containing an ultraviolet absorber and the silver reflection layer 3. 4 is preferable (see FIG. 4).

Further, another constituent layer may be provided between the constituent layers described above or on the constituent layer.

For example, the anchor layer 2 may be provided between the resin base material 1 and the silver reflective layer 3. (See FIGS. 1, 2, 3, and 4)
For example, the corrosion prevention layer 4 may be provided adjacent to the light incident side of the silver reflective layer 3. (See FIGS. 2, 3, and 4)
For example, the gas barrier layer 5 may be provided closer to the light incident side than the silver reflective layer 3. (See Figure 4)
For example, the hard coat layer 7 may be provided on the light incident side surface of the translucent resin layer 6 containing an ultraviolet absorber. (See Figs. 3 and 4)
The thickness of the entire film mirror according to the present invention is preferably 80 to 300 μm, more preferably 80 to 200 μm, and still more preferably 80 to 170 μm from the viewpoints of prevention of bending, regular reflectance, handling properties, and the like. In addition, it is preferable that the center line average roughness (Ra) of the outermost surface layer on the light incident side of the film mirror is 3 nm or more and 20 nm or less from the viewpoint of preventing scattering of reflected light and increasing the light collection efficiency.

Here, an example of a preferable layer configuration of a film mirror for solar power generation will be described with reference to FIGS. 1A to 4A. Moreover, the outline | summary of the solar power generation reflective apparatus is demonstrated using FIG. 1B to FIG. 4B.

As shown in FIG. 1A, the film mirror 10a is provided by laminating an anchor layer 2, a silver reflection layer 3, and a translucent resin layer 6 in this order on a resin substrate 1. An adhesive layer 8 is provided on the opposite surface of the resin substrate 1 on the light incident side.

As shown in FIG. 1B, the solar power generation reflecting device 20a is a reflecting mirror formed by bonding the adhesive layer 8 in the film mirror 10a to the supporting base material 9 and bonding the film mirror 10a and the supporting base material 9 together.

As shown in FIG. 2A, the film mirror 10b is provided by laminating an anchor layer 2, a silver reflection layer 3, a corrosion prevention layer 4, and a translucent resin layer 6 in this order on a resin base material 1. An adhesive layer 8 is provided on the opposite surface of the resin substrate 1 on the light incident side.

As shown in FIG. 2B, the solar power generation reflecting device 20b is a reflecting mirror formed by bonding the adhesive layer 8 in the film mirror 10b to the supporting base material 9 and bonding the film mirror 10b and the supporting base material 9 together.

As shown in FIG. 3A, the film mirror 10 c is provided by laminating an anchor layer 2, a silver reflection layer 3, a corrosion prevention layer 4, a translucent resin layer 6, and a hard coat layer 7 in this order on the resin base material 1. ing. An adhesive layer 8 is provided on the opposite surface of the resin substrate 1 on the light incident side.

As shown in FIG. 3B, the solar power generation reflecting device 20 c is a reflecting mirror formed by bonding the adhesive layer 8 in the film mirror 10 c to the supporting base material 9 and bonding the film mirror 10 c and the supporting base material 9 together.

As shown in FIG. 4A, the film mirror 10d has an anchor layer 2, a silver reflection layer 3, a corrosion prevention layer 4, a gas barrier layer 5, a translucent resin layer 6, and a hard coat layer 7 in this order on the resin substrate 1. Laminated and provided. An adhesive layer 8 is provided on the opposite surface of the resin substrate 1 on the light incident side.

As shown in FIG. 4B, the solar power generation reflecting device 20 d is a reflecting mirror formed by bonding the adhesive layer 8 in the film mirror 10 d to the support base 9 and bonding the film mirror 10 d and the support base 9 together.

Details of each constituent layer will be described below.
(2) Translucent resin layer The translucent resin layer 6 is a resin layer made of a resin material having optical transparency and containing an ultraviolet absorber.

Although there is no restriction | limiting in particular in the resin material used for the translucent resin layer 6, Conventionally well-known various synthetic resins which can maintain transparency when a thin film is formed can be used. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, and cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose Cellulose esters such as acetate phthalate and cellulose nitrate or their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone (PES), polysulfones, polyether ketone imide, polyamide, fluorine Fat, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (trade name JSR Corp.) or APEL (trade name Mitsui Chemicals, Inc.).

As a method for forming the translucent resin layer 6, for example, a method by coating can be mentioned. When a coating film that becomes the translucent resin layer 6 is applied by a coating method, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

Then, on the surface on the light incident side of the silver reflective layer 3 or on the surface of the constituent layers (for example, the corrosion prevention layer 4 and the gas barrier layer 5) provided on the light incident side with respect to the silver reflective layer 3, light is transmitted. The translucent resin layer 6 can be formed by directly applying a material that becomes the transparent resin layer 6.

By forming the translucent resin layer 6 by such a coating method, the smoothness of the translucent resin layer 6 can be improved. Specifically, the center line average roughness (Ra) of the translucent resin layer 6 formed by a coating method can be 3 nm or more and 20 nm or less. In other words, if the center line average roughness satisfies this value, the translucent resin film produced by melt film formation is not a translucent resin layer provided by bonding with an adhesive layer, but the translucent resin film. It can be considered that the conductive resin layer 6 is provided by coating.

The thickness of the translucent resin layer 6 is preferably 10 to 150 μm. More preferably, the thickness is 20 to 100 μm, and still more preferably 40 to 100 μm. If the film thickness exceeds 150 μm, the coating speed must be greatly reduced in order to sufficiently evaporate the solvent during drying, which is not preferable because productivity is significantly impaired.
The center line average roughness (Ra), which is an index of smoothness of the translucent resin layer 6, can be determined by a measuring method based on JIS B0601-1982.

Among the resin materials exemplified above, acrylic can be suitably used as a material for forming the translucent resin layer 6.

When the translucent resin layer 6 is formed of acrylic, since the acrylic resin is hard, in order to obtain an acrylic translucent resin layer 6 that is soft and hardly damaged, plasticizer fine particles may be included. Preferable examples of the plasticizer include butyl rubber and butyl acrylate.

The acrylic translucent resin layer 6 is preferably mainly composed of methacrylic resin. The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of a methacrylic acid ester. The methacrylic acid ester is 50% by mass or more and the other monomer is 50% by mass or less. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used. A particularly preferred methacrylic resin is polymethyl methacrylate resin (PMMA).

The preferred monomer composition of the methacrylic resin is 50 to 100% by weight of methacrylic acid ester, 0 to 50% by weight of acrylic acid ester, and 0 to 49% by weight of other monomers based on the total monomers. More preferably, methacrylic acid ester is 50 to 99.9% by mass, acrylic acid ester is 0.1 to 50% by mass, and other monomers are 0 to 49% by mass.

Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. It is. Of these, methyl methacrylate is preferably used.

Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. is there.

The monomer other than alkyl methacrylate and alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monofunctional monomer. Although it may be a monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used. Examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene, and alkenyl cyan compounds such as acrylonitrile and methacrylonitrile. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Alkenyl esters of unsaturated carboxylic acids such as allyl acid, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene, etc. Can be mentioned.

In addition, as for said alkyl methacrylate, alkyl acrylate, and monomers other than these, respectively, you may use those 2 or more types as needed.

The glass transition temperature of the methacrylic resin is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat resistance of the film. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.

The methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity showing a formability to a suitable film, it is preferable to use a chain transfer agent during the polymerization. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.
(2-1) Ultraviolet Absorber The ultraviolet absorber contained in the translucent resin layer 6 is not particularly limited. For example, thiazolidone-based, benzotriazole-based, acrylonitrile-based, benzophenone-based, aminobutadiene-based, triazine-based, There are organic UV absorbers such as phenyl salicylate and benzoate, or fine powder UV blockers such as cerium oxide and magnesium oxide, titanium oxide, zinc oxide, iron oxide, etc., especially organic UV absorption Agents are preferred.

Examples of organic ultraviolet absorbers include JP-A-46-3335, JP-A-55-15276, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-310667, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent Nos. 711804A and JP-A-8-501291, U.S. Pat. Nos. 1,023,859, 2,685,512, 2,739,888, 2,784,087. No. 2,748,021, No. 3,004,896, No. 3,052,636, No. 3,215,530, No. 3,253,9 No. 1, No. 3,533,794, No. 3,692,525, No. 3,705,805, No. 3,707,375, No. 3,738,837, No. The compounds described in 3,754,919, British Patent 1,321,355 and the like can be used.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetra And hydroxy-benzophenone.

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1, 3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercial products are LA31 from ADEKA Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl- 1-Phenylethyl) phenol (molecular weight 447.6; examples of commercially available products include Tinuvin 234 from Ciba Specialty Chemicals) It is.

Examples of the phenyl salicylate ultraviolet absorber include phenylsalicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like. Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-) Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- 1,3,5-triazine, [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol] (Tinuvine 1577FF, trade name, Ciba Specialty Chemicals), [2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol] (CYASORB UV-1164, commodity Name, manufactured by Cytec Industries).

Examples of benzoate UV absorbers include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (molecular weight 438.7; Sumisorb 400).

Among these UV absorbers, UV absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high temperature molding, so that the weather resistance can be effectively improved with a relatively small amount of addition. it can.

In addition, since the ultraviolet absorber having a molecular weight of 400 or more has little transferability from the thin translucent resin layer 6 to other constituent layers and hardly deposits on the surface of the laminate, the amount of contained ultraviolet absorber is small. It is preferable from the viewpoints of being maintained for a long time and being excellent in the durability of the weather resistance improving effect.

Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine A hybrid system having both structures can be mentioned, and these can be used alone or in combination of two or more. Among these, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.

In addition to the above, as the ultraviolet absorber, a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational 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. However, when using the above-mentioned ultraviolet absorber, it is necessary to select one in which the light absorption wavelength of the ultraviolet absorber does not overlap with the effective wavelength of the photopolymerization initiator. When a normal ultraviolet absorber is used, it is effective to use a photopolymerization initiator that generates radicals with visible light.

In addition, each of the above ultraviolet absorbers may be used in combination of two or more thereof as necessary. Further, if necessary, an ultraviolet absorber other than the above-described ultraviolet absorber, for example, a salicylic acid derivative, a substituted acrylonitrile, a nickel complex, or the like can be contained.

The content of the ultraviolet absorber in the translucent resin layer 6 is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 10% by mass. In addition, the content of the ultraviolet absorber in the translucent resin layer 6 is 0.17 to 2.28 g / m ² per unit area of the film, more preferably, the content per unit area is 0.1. 4 to 2.28 g / m ² or more. By setting the content within the above range, it is possible to prevent the roll and the film from being soiled by bleeding out of the ultraviolet absorber while sufficiently exhibiting the weather resistance.
(2-2) Antioxidant In order to prevent deterioration of the translucent resin layer 6 containing the ultraviolet absorber, the translucent resin layer 6 may contain an antioxidant. Examples of preferred antioxidants are listed below.

As the antioxidant, it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, or a phosphite-based antioxidant.

Examples of phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t- Butylphenol), tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propi , Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- [β- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4 And 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

Examples of the thiol-based antioxidant include distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), and the like.

Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol. Diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene-diphosphonite 2,2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like.

In the present invention, the above antioxidant and the following light stabilizer can be used in combination.

Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl- 8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-Tetrame Lupiperidine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, triethylenediamine, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione.

In particular, as the hindered amine light stabilizer, a hindered amine light stabilizer containing only a tertiary amine is preferable. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) is preferable. ) -Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate, Alternatively, a condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferable.

In addition, nickel-based UV stabilizers can also be used as light stabilizers. Nickel-based UV stabilizers include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Examples thereof include hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, and the like.

It is also possible to add an antistatic agent to the translucent resin layer 6 to impart antistatic performance.

Further, a phosphorus-based flame retardant may be added to the translucent resin layer 6. Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.

Specific examples include triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris (β-chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
(3) Corrosion prevention layer The corrosion prevention layer 4 is a resin layer containing a corrosion inhibitor. For example, the corrosion prevention layer 4 is provided between the translucent resin layer 6 and the silver reflection layer 3, and in particular, the corrosion prevention layer. 4 is preferably adjacent to the silver reflective layer 3.

The corrosion prevention layer 4 may consist of only one layer or may consist of a plurality of layers. The thickness of the corrosion prevention layer 4 is preferably 1 to 10 μm, more preferably 2 to 8 μm.

Examples of the resin used for the corrosion prevention layer 4 include cellulose ester, polyester, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, and cellulose diester. Acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide , Polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic resin, etc. It can be mentioned. Among these, an acrylic resin is preferable.

The corrosion prevention layer 4 can be formed by applying and coating these resin materials (binders) on the silver reflective layer 3 or the like.
(3-1) Corrosion inhibitor The corrosion inhibitor preferably has an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which metal (silver) is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it (see JIS Z0103-2004).

The optimum content of the corrosion inhibitor varies depending on the compound used, but is generally preferably in the range of 0.1 to 1.0 / m ² .

Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, and having an imidazole ring It is desirable to be selected from a compound, a compound having an indazole ring, a copper chelate compound, a thiourea, a compound having a mercapto group, a naphthalene-based compound, or a mixture thereof. In compounds such as benzotriazole, the ultraviolet absorber may also serve as a corrosion inhibitor. It is also possible to use a silicone-modified resin. It does not specifically limit as a silicone modified resin.

Examples of amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, O-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2N- Dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysoidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite , Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexane carboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate, or mixtures thereof.

Examples of compounds having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, and N-phenyl-3. , 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy) -5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) Benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercially available products are LA31 from ADEKA Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis ( 1-methyl-1-phenylethyl) phenol (molecular weight 447.6; an example of a commercially available product is Chinu, manufactured by Ciba Specialty Chemicals Co., Ltd. Down 234), and the like. Alternatively, a mixture thereof can be mentioned.

Examples of the compound having a pyrazole ring include pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole, 4-aminopyrazole, and a mixture thereof.

Examples of the compound having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or a mixture thereof.

Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4 Formylimidazole, 4-methyl-5-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methyl-4-formylimidazole, 2-mercaptobenzimidazole, etc., or These mixtures are mentioned.

Examples of the compound having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.

Examples of copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and the like, or a mixture thereof.

Examples of thioureas include thiourea, guanylthiourea, and the like, or a mixture thereof.

As a compound having a mercapto group, mercaptoacetic acid, thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto can be used by adding the above-described materials. -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, etc., or a mixture thereof.

Examples of the naphthalene type include thionalide.
(4) Light reflecting layer The light reflecting layer is a layer made of metal or the like having a function of reflecting sunlight.

The surface reflectance of the light reflecting layer is preferably 80% or more, more preferably 90% or more. This light reflecting layer is preferably formed of a material containing any element selected from the group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt and Au. Among these, it is preferable that Al or Ag is a main component from the viewpoint of reflectance and corrosion resistance, and two or more such metal thin films may be formed. In the present invention, a light reflecting layer mainly composed of silver is used.

The thickness of the light reflecting layer is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectivity and the like.

Further, the reflectance may be further improved by providing a layer made of a metal oxide such as SiO ₂ or TiO ₂ in the light reflecting layer.

As a method for forming the light reflecting layer, either a wet method or a dry method can be used. The wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction. On the other hand, the dry method is a general term for a vacuum film-forming method. Specific examples include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, and an ion beam assisted vacuum deposition method. And sputtering method. In particular, a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. For example, in the manufacturing method of the film mirror for solar power generation, it is preferable that it is a manufacturing method which forms the silver reflection layer 3 by silver vapor deposition.
(4-1) Silver complex compound having a ligand that can be vaporized / desorbed In addition, when forming the silver reflective layer 3, a coating film containing a silver complex compound whose ligand can be vaporized / desorbed is heated and fired. By doing so, the silver reflective layer 3 may be formed.

“Silver complex compound having a ligand that can be vaporized / desorbed” has a ligand for stably dissolving silver in a solution, but the ligand is removed by removing the solvent and heating and firing. Is a silver complex compound that can be thermally decomposed into CO ₂ or a low molecular weight amine compound, vaporized and eliminated, and only metallic silver remains.

Examples of such complexes are described in known Japanese translations of PCT publication No. 2009-535661, Japanese translations of PCT publication No. 2010-500475, etc., and a silver compound represented by the following general formula (1): Silver complex compounds obtained by reacting ammonium carbamate compounds, ammonium carbonate compounds or ammonium bicarbonate compounds represented by (2) to (4) are preferred.

Further, the silver complex compound is contained in the silver coating solution composition, and by applying this, a coating film containing the complex according to the present invention is formed on the support to be a film mirror. That is, it is preferable to form the silver reflective layer 3 by forming a coating film on a film using a silver complex compound and then baking the coating film at a temperature in the range of 80 to 250 ° C. More preferably, it is in the range of 100 to 220, particularly preferably in the range of 120 to 200 ° C. There is no restriction | limiting in particular as a heat-firing means, What kind of heating means generally used can be applied.

Hereinafter, the silver compound represented by the following general formula (1) and the ammonium carbamate compounds, ammonium carbonate compounds, or ammonium bicarbonate compounds represented by the general formulas (2) to (4) will be described. .

Ag _n X (1)

In the above general formulas (1) to (4), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate. , Carboxylate, and a substituent selected from these derivatives, n is an integer of 1 to 4, and R ¹ to R ⁶ are independently of each other hydrogen, C1 to C30 aliphatic or It is a substituent selected from an alicyclic alkyl group, an aryl group or an aralkyl group, an alkyl and aryl group substituted with a functional group, a heterocyclic compound group, a polymer compound and derivatives thereof.

Specific examples of the general formula (1) include, for example, silver oxide, silver thiocyanate, silver sulfide, silver chloride, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, perchlorine. Examples include, but are not limited to, acid silver, silver tetrafluoroborate, silver acetylacetonate, silver acetate, silver lactate, silver oxalate and derivatives thereof.

In the general formulas (2) to (4), R ¹ to R ⁶ are specifically, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl. , Nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, aryl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxypropyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxy Ethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine , Pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and derivatives thereof, and polymer compounds such as polyarylamine and polyethyleneamine And derivatives thereof, but are not limited thereto.

Examples of compounds of the general formulas (2) to (4) include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n- Butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, t-butyl ammonium t-butyl carbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridiumethylhexylcarbamate, triethylenediaminium Isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium, triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, isopropylammonium bikerbo N-butylammonium n-butyl carbonate, isobutylammonium isobutyl carbonate, t-butylammonium t-butyl carbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2 -Methoxyethylammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecyl Carbonate, dioctadecyl ammonium bicarbonate, methyl decyl ammonium methyl decyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morpholine carbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbonate, pyridium bicarbonate, tri Examples thereof include, but are not limited to, ethylenediaminium isopropyl carbonate, triethylenediaminium bicarbonate, and one or a mixture of two or more selected from derivatives thereof.

On the other hand, the type and production method of the ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate compound are not particularly limited. For example, US Pat. No. 4,542,214 describes that ammonium carbamate compounds can be prepared from carbon dioxide and primary amines, secondary amines, tertiary amines, or at least one of these mixtures. When 0.5 mol of water is further added per 1 mol of the amine, an ammonium carbonate compound is obtained. When 1 mol or more of water is added, an ammonium bicarbonate compound can be obtained. At this time, it is produced directly without using a special solvent at normal pressure or under pressure, or when a solvent is used, alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, etc. Glycols, ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as methyl ethyl ketone, acetone, hydrocarbons such as hexane, heptane, Examples include aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride, or mixed solvents thereof. Is carbon dioxide bubbled in the gas phase? To be able to use the solid phase dry ice, it can be reacted in supercritical (supercritical) state. In addition to the above method, any known method may be used for the production of the ammonium carbamate or ammonium carbonate derivative as long as the structure of the final substance is the same. That is, it is not necessary to specifically limit the solvent, reaction temperature, concentration or catalyst for production, and the production yield is not affected.

An organic silver complex compound can be produced by reacting the ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate compound thus produced with a silver compound. For example, at least one silver compound represented by the general formula (1) and at least one ammonium carbamate, ammonium carbonate or ammonium bicarbonate represented by the general formulas (2) to (4) Reacting the compound and a mixture thereof directly under a nitrogen atmosphere at normal pressure or without using a solvent, or when using a solvent, alcohols such as water, methanol, ethanol, isopropanol, butanol, Ethylene glycol, glycols such as glycerin, ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as methyl ethyl ketone, acetone, hexane, heptane like Hydrocarbon-based, benzene, can be used aromatic, such as toluene, and chloroform and methylene chloride, and the like halogenated solvent or a mixed solvent such as carbon tetrachloride.

For the production of such a silver complex compound (a silver complex compound having a ligand that can be vaporized / desorbed), in addition to the above-described method, a silver compound of the general formula (1) and one or more amine compounds may be used. After producing a mixed solution, carbon dioxide can be reacted to produce a silver complex compound. As described above, the reaction can be performed directly without using a solvent in a normal pressure or pressurized state of a nitrogen atmosphere, or can be performed using a solvent. However, any known method may be used as long as the structure of the final material is the same. That is, it is not necessary to specifically limit the solvent for the production, the reaction temperature, the concentration, the presence or absence of the catalyst, and the production yield is not affected.

Such a silver complex compound has a production method described in JP-T-2008-530001, and is recognized by the structure of the following general formula (5).

Ag [A] _m (5)
(In the general formula (5), A is a compound of the general formulas (2) to (4), and m is 0.5 to 1.5.)
The silver coating liquid composition used for forming a highly reflective and highly glossy reflective surface on the silver reflective layer 3 contains the above silver complex compound, and optionally contains a solvent, a stabilizer, and a leveling agent ( Leveling agent), thin film auxiliary agents, reducing agents, thermal decomposition reaction accelerators and other additives.

Examples of the stabilizer include amine compounds such as primary amines, secondary amines and tertiary amines, ammonium carbamates, ammonium carbonates, ammonium bicarbonate compounds, phosphines, phosphites, and phosphates. A phosphorus compound such as (phosphate), a sulfur compound such as thiol or sulfide, and a mixture of at least one of them. Specific examples of the amine compound include methylamine, Ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octyla , Isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanol Amine, methoxyethylamine, 2-hydroxypropylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine , Dimethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, pipera , Ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxy Examples include silane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, benzylamine and derivatives thereof, and amine compounds such as polymer compounds such as polyarylamine and polyethyleneimine and derivatives thereof.

Specific examples of ammonium carbamate, carbonate and bicarbonate compounds include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, and n-butyl. Ammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2- Toxiethyl carbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridiumethylhexylcarbamate, Triethylenediaminium isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, isopropylammonium Bicarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2 -Methoxyethylammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecylcarbo , Dioctadecyl ammonium bicarbonate, methyl decyl ammonium methyl decyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morpholine carbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbonate, pyridium bicarbonate, tri Examples thereof include ethylenediaminium isopropyl carbonate, triethylenediaminium bicarbonate, and derivatives thereof.

As the phosphorus compounds of the general formula R ₃ P, include a phosphorus compound represented by (RO) ₃ P or (RO) ₃ PO. Here, R represents an alkyl or aryl group having 1 to 20 carbon atoms, and specific examples thereof include tributylphosphine, triphenylphosphine, triethyl phosphite, triphenyl phosphite, dibenzyl phosphate, triethyl phosphate and the like.

Specific examples of the sulfur compound include butanethiol, n-hexanethiol, diethyl sulfide, tetrahydrothiophene, aryl disulfide, 2-mercaptobenzoazole, tetrahydrothiophene, octylthioglycolate, and the like.

The amount of such a stabilizer used is not particularly limited. However, the content is preferably 0.1% to 90% in terms of molar ratio with respect to the silver compound.

Moreover, examples of the thin film auxiliary agent include organic acids and organic acid derivatives, or at least one mixture thereof. Specifically, for example, acetic acid, butyric acid (valeric acid), valeric acid (pivalic acid), hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid ( Lauric acid), stearic acid, naphthalic acid, and the like. Specific examples of organic acid derivatives include ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, and ammonium maleate. Organic acid ammonium salts such as ammonium oxalate and ammonium molybdate, Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, O Manganese oxalate, gold acetate, palladium oxalate, 2-ethylhexanoic acid containing metals such as Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th Examples thereof include organic acid metal salts such as silver, silver octoate, silver neodecanoate, cobalt stearate, nickel naphthalate and cobalt naphthalate. The amount of the thin film auxiliary used is not particularly limited, but is preferably 0.1 to 25% in terms of molar ratio with respect to the silver complex compound.

Examples of the reducing agent include Lewis acid or weak Bronsted acid, and specific examples thereof include hydrazine, hydrazine monohydrate, acetohydrazide, sodium borohydride or potassium borohydride, dimethylamine borane. , Amine compounds such as butylamine borane, ferrous chloride, metal salts such as iron lactate, hydrogen, hydrogen iodide, carbon monoxide, aldehyde compounds such as formaldehyde, acetaldehyde, glyoxal, methyl formate, butyl formate, triethyl Examples thereof include a mixture of at least one reducing organic compound such as formic acid compound such as o-formic acid, glucose, ascorbic acid and hydroquinone.

Specific examples of the thermal decomposition reaction accelerator include ethanolamine, methyldiethanolamine, triethanolamine, propanolamine, butanolamine, hexanolamine, hydroxyalkylamines such as dimethylethanolamine, piperidine, and N-methyl. Piperidine, piperazine, N, N'-dimethylpiperazine, 1-amino-4methylpiperazine, pyrrolidine, N-methylpyrrolidine, amine compounds such as morpholine, acetone oxime, dimethylglyoxime, 2-butanone oxime, 2,3- Alkyl oximes such as butadione monooxime, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, methoxyethylamine, ethoxyethylamine, methoxy Alkoxyalkylamines such as propylamine, alkoxyalkanols such as methoxyethanol, methoxypropanol and ethoxyethanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ketone alcohols such as acetol and diacetone alcohol, Examples thereof include hydric phenol compounds, phenol resins, alkyd resins, pyrroles, and oxidatively polymerizable resins such as ethylenedioxythiophene (EDOT).

In some cases, a solvent is required for adjusting the viscosity of the silver coating liquid composition and for forming a smooth thin film. Examples of the solvent that can be used in this case include water, methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, Ethyl hexyl alcohol, alcohols such as terpineol, glycols such as ethylene glycol and glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, acetates such as ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, diethyl Ethers such as ether, tetrahydrofuran and dioxane, methyl ethyl ketone, acetone, dimethylformamide, ketones such as 1-methyl-2-pyrrolidone, hexane, Hydrocarbons such as tan, dodecane, paraffin oil, mineral spirits, aromatics such as benzene, toluene, xylene, and halogen-substituted solvents such as chloroform, methylene chloride, carbon tetrachloride, acetonitrile, dimethyl sulfoxide, or these Or a mixed solvent thereof can be used.
(4-2) Nitrogen-containing cyclic compound When the silver reflective layer 3 is formed, when the coating film containing a silver complex compound capable of vaporizing and desorbing a ligand is heated and fired, It is preferable to contain a nitrogen-containing cyclic compound in the adjacent constituent layer. A nitrogen-containing cyclic compound having an adsorptive group for silver is preferably used as a corrosion inhibitor for the silver reflective layer 3.

By using a nitrogen-containing cyclic compound having an adsorptive group for silver as a corrosion inhibitor, a desired corrosion prevention effect for the silver reflection layer 3 can be obtained. For example, the nitrogen-containing cyclic compound as a corrosion inhibitor is a compound having a pyrrole ring, a compound having a triazole ring, a compound having a pyrazole ring, a compound having an imidazole ring, a compound having an indazole ring, or a mixture thereof. It is desirable to be selected.

Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, and N-phenyl-3. , 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy) -5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) Examples thereof include benzotriazole and a mixture thereof.

Examples of the compound having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.
(4-3) Antioxidant An antioxidant may be used for the purpose of preventing corrosion of the silver reflecting layer 3.

As the antioxidant of the silver reflection layer 3, it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, and a phosphite-based antioxidant.

In addition, the above antioxidant and the following light stabilizer can be used in combination.

Other nickel-based UV stabilizers include [2,2'-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, etc. can also be used.

In particular, as the hindered amine light stabilizer, a hindered amine light stabilizer containing only a tertiary amine is preferable. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) is preferable. Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate, or A condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.
(5) Resin Substrate As the resin substrate 1, various conventionally known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, polycarbonate films, polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable. In particular, it is preferable to use 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.

Since the resin base material 1 is located farther from the light incident side than the silver reflection layer 3, it is difficult for ultraviolet rays to reach the resin base material 1. In particular, when an ultraviolet absorber is contained in the translucent resin layer 6 or the like that is closer to the light incident side than the resin substrate 1, the ultraviolet rays are more difficult to reach the resin substrate 1. Therefore, the resin substrate 1 can be used even if it is a resin that easily deteriorates with respect to ultraviolet rays. From such a viewpoint, a polyester film such as polyethylene terephthalate can be used as the resin substrate 1.

The thickness of the resin substrate 1 is preferably set to an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 10 to 250 μm. The thickness is preferably 20 to 200 μm.
(6) Adhesive layer The adhesive layer 8 has adhesiveness that allows the film mirror to be attached to the support substrate 9, and the adhesive layer 8 joins the film mirror to the support substrate 9, It is a structure layer for forming the reflective apparatus for solar thermal power generation.

The adhesive layer 8 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 can be used. As the adhesive, for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used. The laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity. The thickness of the pressure-sensitive adhesive layer is usually preferably in the range of about 1 to 100 μm from the viewpoints of the pressure-sensitive adhesive effect, the drying speed, and the like.

The film mirror may include a release sheet (not shown) that covers the surface of the adhesive layer 8 opposite to the resin base material 1. When the film mirror has a release sheet, the film mirror can be attached to the support substrate 9 through the adhesive layer 8 after the release sheet is released from the adhesive layer 8.
(6-1) Release Sheet The release sheet is a member that covers the surface of the film mirror opposite to the light incident side of the adhesive layer 8.

For example, when the film mirror is shipped, the release sheet is stuck to the adhesive layer 8, and then the release sheet is released from the adhesive layer 8 of the film mirror, and the film mirror is attached to the support substrate 9 to achieve solar thermal power generation. A reflective device can be formed.

Any release sheet may be used as long as it can protect the adhesiveness of the adhesive layer 8. For example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, polyethylene terephthalate Plastic film or sheet such as film or sheet, fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., coating the resin kneaded with these, or metal such as aluminum A resin film or sheet subjected to surface processing such as metal vapor deposition is used.

The thickness of the release sheet is not particularly limited but is usually preferably in the range of 12 to 250 μm.
(7) Hard coat layer The hard coat layer 7 is provided for the purpose of preventing the film mirror surface from being scratched or contaminated. The transparent hard coat layer 7 is preferably the outermost layer on the light incident side or the second or third layer from the light incident side. Another thin layer (preferably 1 μm or less) may be provided on the hard coat layer 7.

Examples of the method for producing the hard coat layer 7 include conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method. In addition to applying and coating a predetermined material, various surface treatments and the like may be combined.

The thickness of the hard coat layer 7 is preferably 0.05 μm or more and 10 μm or less from the viewpoint of preventing the film mirror from being warped while obtaining sufficient scratch resistance. More preferably, they are 1 micrometer or more and 10 micrometers or less.

The material for forming the hard coat layer 7 is not particularly limited as long as transparency, weather resistance, hardness, mechanical strength, and the like can be obtained. The hard coat layer 7 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. In particular, silicone resins and acrylic resins are preferable in terms of hardness and durability. Further, in terms of curability, flexibility, and productivity, those made of an active energy ray-curable acrylic resin or a thermosetting acrylic resin are preferable.

The active energy ray-curable acrylic resin or thermosetting acrylic resin is a composition containing a polyfunctional acrylate, an acrylic oligomer, or a reactive diluent as a polymerization curing component. In addition, you may use what contains a photoinitiator, a photosensitizer, a thermal-polymerization initiator, a modifier, etc. as needed.

Acrylic oligomers include polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, etc., including those in which a reactive acrylic group is bonded to an acrylic resin skeleton, and rigid materials such as melamine and isocyanuric acid. A structure in which an acrylic group is bonded to a simple skeleton can also be used.

In addition, the reactive diluent has a function of a solvent in the coating process as a medium of the coating agent, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a copolymerization component.

Commercially available polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam (registered trademark)” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol (registered trademark)” series, etc. ), Shin-Nakamura Co., Ltd .; (trade name “NK Ester” series, etc.), Dainippon Ink and Chemicals Co., Ltd .; (trade name “UNIDIC (registered trademark)” series, etc.) "Aronix (registered trademark)" series, etc.), Nippon Oil and Fats Corporation; (trade name "Blemmer (registered trademark)" series, etc.), Nippon Kayaku Co., Ltd .; Kyoeisha Chemical Co., Ltd .; (Product name “Light Ester” series, “Light acrylate” series, etc.) Kill.

More specifically, for example, a resin curable by electron beam or ultraviolet irradiation, a thermosetting resin, or the like can be used. In particular, a thermosetting silicone hard coat composed of a partially hydrolyzed oligomer of an alkoxysilane compound, a heat A hard coat made of a curable polysiloxane resin, an ultraviolet curable acrylic hard coat made of an acrylic compound having an unsaturated group, and a thermosetting inorganic material are preferable. Examples of materials that can be used for the hard coat layer 7 include 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), and a water-based silicone compound as a binder. Resin film used as JP-A-2004-142161, silica film containing alumina or photocatalytic oxide such as titanium oxide, photocatalytic film such as titanium oxide or niobium oxide having a high aspect ratio (JP-A 2009-62216), Examples thereof include a photocatalyst-containing fluororesin coating (Pyrex Technologies), an organic / inorganic polysilazane film, and a film using a hydrophilization accelerator (AZ Electronics) on organic / inorganic polysilazane.

A partially hydrolyzed oligomer of an alkoxysilane compound synthesized by a known method can be used for the thermosetting silicone hard coat layer 7. 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. By this reaction, 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. Next, 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 | coated to the outer surface of a film mirror etc. by the coating method in a normal coating material, and a transparent hard-coat layer is formed by heat-hardening at the temperature of 80-140 degreeC. However, in this case, the setting of the curing temperature below the thermal deformation temperature of the film mirror is a prerequisite. In addition, by using di (alkyl or aryl) dialkoxysilane and / or mono (alkyl or aryl) trialkoxysilane instead of tetraalkoxysilane, a polysiloxane-based transparent hard coat layer is similarly produced. Is possible.

The ultraviolet curable acrylic hard coat layer 7 includes, for example, pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol as an acrylic compound having an unsaturated group. A polyfunctional (meth) acrylate mixture such as tetra (meth) acrylate or the like can be used, and a photopolymerization initiator such as benzoin, benzoin methyl ether, or benzophenone is blended and used. And this is apply | coated to the outer surface of a reflective film base material, and the transparent hard-coat layer 7 is formed by ultraviolet-curing.

Further, it is preferable to impart a hydrophilic property by subjecting the hard coat layer 7 to a surface treatment. Examples of the treatment for imparting hydrophilicity include corona treatment (Japanese Patent Laid-Open No. 11-172028), plasma surface treatment, ultraviolet / ozone treatment, surface protrusion formation (Japanese Patent Laid-Open No. 2009-226613), surface fine processing treatment, and the like. Can be mentioned.

When the hard coat layer 7 is made of an inorganic material, it can be formed, for example, by depositing silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like by a vacuum film forming method. Examples of 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.

Further, when the hard coat layer 7 is made of an inorganic material, it is preferably made of a film obtained by coating polysilazane and heat-curing it. When the precursor of the hard coat layer contains polysilazane, for example, after applying a solution to which a catalyst is added if necessary in an organic solvent containing polysilazane represented by the following general formula (6), the solvent is evaporated. To remove the polysilazane layer having a layer thickness of 0.05 to 3.0 μm on the film mirror. Then, a glass-like transparent hard coat film is formed on the film mirror by locally heating the polysilazane layer in the presence of oxygen, active oxygen, and in some cases nitrogen in an atmosphere containing water vapor. It is preferable to adopt the method.

-(SiR ¹ R ² -NR ³ ) _n- (6)
In general formula (6), R ¹ , R ² , and R ³ are the same or different and are independently of each other hydrogen, or optionally substituted alkyl, aryl, vinyl, or (trialkoxysilyl). ) From an alkyl group, preferably hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl) Represents a group selected from the group consisting of In this case, n is an integer, and n is determined so that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

As catalysts, preferably basic catalysts, in particular N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine or N-heterocyclic compounds are used. . The catalyst concentration is usually in the range of 0.1 to 10 mol%, preferably 0.5 to 7 mol%, based on polysilazane.

In one preferred embodiment, a solution containing perhydropolysilazane in which all of R ¹ , R ² and R ^{3 in} the general formula (6) are hydrogen atoms is used.

In another preferred embodiment, the hard coat layer 7 contains at least one polysilazane represented by the following general formula (7).

-(SiR ¹ R ² -NR ³ ) _n- (SiR ⁴ R ⁵ -NR ⁶ ) _p- (7)
In the general formula (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently of each other hydrogen, or an optionally substituted alkyl group, aryl group, vinyl group or ( Represents a trialkoxysilyl) alkyl group; In this case, n and p are integers, and in particular, n is determined so that polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

Particularly preferred are compounds in which R ¹ , R ³ and R ⁶ represent hydrogen and R ² , R ⁴ and R ⁵ represent methyl. A compound in which R ¹ , R ³ and R ⁶ represent hydrogen, R ² and R ⁴ represent methyl, and R ⁵ represents vinyl. In addition, R ¹ , R ³ , R ⁴ and R ⁶ represent hydrogen, and R ² and R ⁵ represent methyl.

Furthermore, in another preferred embodiment, the transparent hard coat layer contains at least one polysilazane represented by the following general formula (8).

-(SiR ¹ R ² -NR ³ ) _n- (SiR ⁴ R ⁵ -NR ⁶ ) _p- (SiR ⁷ R ⁸ -NR ⁹ ) _q- (8)
In general formula (8), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently of each other hydrogen or optionally substituted alkyl. Represents a group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, n, p and q are integers, and in particular, n is determined so that polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

Particularly preferred are R ¹ , R ³ and R ⁶ represent hydrogen and R ² , R ⁴ , R ⁵ and R ⁸ represent methyl, R ⁹ represents (triethoxysilyl) propyl and R ⁷ Is a compound in which represents alkyl or hydrogen.

The proportion of polysilazane in the solvent is generally 1 to 80% by mass, preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass.

As the solvent, in particular, an organic solvent which does not contain water and a reactive group (for example, a hydroxy group or an amine group) and is inert to polysilazane, preferably an aprotic solvent is suitable. This includes, for example, aliphatic or aromatic hydrocarbons, halogen hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and mono- and polyalkylene glycol dialkyl ethers (Diglymes) or a mixture of these solvents.

As an additional component of this polysilazane solution, further binders such as those conventionally used in the production of paints can be used. For example, cellulose ethers and cellulose esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose acetobutyrate, natural resins such as rubber or rosin resins, or synthetic resins such as polymerized resins or condensed resins such as aminoplasts, in particular Urea resins and melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, or polysiloxanes.

Further, as another component to be further added to the polysilazane formulation, for example, an additive that affects the viscosity of the formulation, wettability of the base, film forming property, lubricating action or exhaust property, or inorganic nanoparticles such as SiO ₂ it can be used TiO _2, ZnO, ZrO ₂ or Al ₂ O _3.

The transparent hard coat layer 7 of polysilazane thus formed can also be used as an oxygen / water vapor barrier film.

Moreover, as a particularly preferable example of the transparent hard coat layer 7, a hard coat layer 7 containing a polyfunctional acrylic monomer and a silicone resin can be given. The polyfunctional acrylic monomer is hereinafter referred to as “A” component, and the silicone resin is hereinafter referred to as “B” component.
(7-1) Component “A” The polyfunctional acrylic monomer “A” component preferably has an unsaturated group, particularly an active energy ray-reactive unsaturated group. The active energy ray referred to in this specification preferably means an electron beam or an ultraviolet ray. As the polyfunctional acrylic monomer having an active energy ray-reactive unsaturated group, a radical polymerization monomer is used, preferably a bifunctional or higher functional monomer having an α, β-unsaturated double bond in the molecule. A certain polyfunctional acrylate type or polyfunctional methacrylate type monomer may be mentioned. In addition, you may have a vinyl type monomer, an allyl type monomer, and a monofunctional monomer. Further, the radical polymerization monomer can be used alone or in combination of two or more kinds of monomers in order to adjust the crosslinking density. As the “A” component, in addition to these relatively low molecular weight compounds, for example, so-called narrowly-defined monomers having a molecular weight of less than 1000, oligomers and prepolymers having a somewhat high molecular weight, for example, a weight average molecular weight of 1,000 to 10,000 are also used. Is possible.

Specific examples of monofunctional (meth) acrylate monomers include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and 2- (meth) acryloyloxyethyl. Hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, butanediol mono (Meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate, cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, dipropylene glycol (meth) acrylate, phenyl (meth) acrylate, ethyl (Meth) acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (medium) ) Acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene Glycol (meth) acrylate, octafluoropentyl (meth) acrylate, Octoxy polyethylene glycol-polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, perfluorooctylethyl (meth) acrylate, phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, Phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, stearyl (meth) acrylate, succinic acid (meth) acrylate, t-butyl (meth) ) Acrylate, t-butylcyclohexyl (meth) acrylate, tetrafluoropropyl (meth) Chryrate, tetrahydrofurfuryl (meth) acrylate, tribromophenyl (meth) acrylate, tridecyl (meth) acrylate, trifluoroethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, ω-carboxy-polycaprolactone (meth) Examples thereof include acrylates, derivatives thereof, and modified products.

Specific examples of the polyfunctional (meth) acrylate monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, diethylene glycol di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, di (meth) acrylate phthalate Rate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate , Triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol Litol tri (meth) acrylate, phosphoric acid tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, di (meth) acrylic Isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and derivatives and modified products thereof It is done.

Examples of such commercially available “A” component that is a polymerizable organic compound include Aronix M-400, M-408, M-450, M-305, M-309, M-manufactured by Toagosei Co., Ltd. 310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO- 595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, KAYARAD D-310, D-330, DPHA, DPCA-20, DP manufactured by Nippon Kayaku Co., Ltd. A-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR- 444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, -551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. light acrylate PE -4A, DPE-6A, DTMP-4A and the like.

The content of the polymerizable organic compound “A” component is 10 to 90% by mass with the total composition of “A” + “B” being 100% by mass from the viewpoint of improving antifouling properties and light resistance. It is preferably 15 to 80% by mass.
(7-2) “B” Component The silicone resin “B” component is preferably a silicone resin having an active energy ray-reactive unsaturated group. The silicone resin contains a polyorganosiloxane, and is preferably a compound having a polyorganosiloxane chain having an active energy ray-curable unsaturated bond in the molecule. In particular, the monomer (a) having 1 to 50% by mass of a radically polymerizable double bond and a polyorganosiloxane chain, and a monomer other than (a) having a radically polymerizable double bond and a reactive functional group ( b) a polymer obtained by polymerizing a monomer containing 10 to 95% by mass and a monomer having a radical polymerizable double bond other than (a) and (b) (c) 0 to 89% by mass Activity which is a vinyl copolymer having a number average molecular weight of 5000 to 100,000, which is obtained by reacting (α) with a functional group capable of reacting with the above-mentioned reactive functional group and a compound (β) having a radical polymerizable double bond It is preferable that it is an energy beam curable resin composition.

Specific examples of the monomer (a) having a radical polymerizable double bond and a polyorganosiloxane chain include, for example, one end of Silaplane FM-0711, FM-0721, FM-0725, etc. manufactured by Chisso Corporation. Examples include (meth) acryloxy group-containing polyorganosiloxane compounds, AC-SQ SI-20 manufactured by Toagosei Co., Ltd., Hybrid Plastics POSS (Polyhydrogen Oligomeric Silsesquioxane) series acrylate, methacrylate-containing compounds, and the like.

The “B” component can be used alone or in combination of two or more depending on the required performance. The polymerization ratio is preferably 1 to 50% by mass, more preferably 10 to 35% by mass, based on the total mass of monomers constituting the polymer. When the copolymerization ratio of the “B” component is less than 1% by mass, it becomes difficult to impart antifouling properties and weather resistance to the upper surface of the cured product, and when it exceeds 50% by mass, scratch resistance is obtained. In addition, it is difficult to obtain compatibility with other components contained in the radiation curable composition, coating performance such as adhesion to a substrate, toughness, and solubility of a polymer in a solvent. It becomes. An appropriate amount of polysiloxane can also be contained in the above components, and depending on the chemical structure and quantitative ratio of the “B” component, the durability can be improved by adding polysiloxane.

The hard coat layer 7 is preferably flexible and does not warp. The transparent hard coat layer 7 on the outermost surface layer of the film mirror may form a dense cross-linked structure, so that the film may be bent or may be cracked due to lack of flexibility. Becomes difficult. In such a case, it is preferable to design so as to obtain flexibility and flatness by adjusting the amount of the inorganic substance in the hard coat layer composition.
(7-3) Additive The hard coat layer 7 may contain an ultraviolet absorber or an antioxidant. As the ultraviolet absorber or antioxidant, the ultraviolet absorber or antioxidant used in the above-described translucent resin layer 6 can be used.

Particularly, a preferable UV absorber in the hard coat layer 7 containing a polyfunctional acrylic monomer and a silicone resin is a benzotriazole-based UV absorber. By including the benzotriazole-based ultraviolet absorber in the hard coat layer 7, not only the weather resistance can be further improved, but also the excellent effect that the falling angle can be further reduced can be obtained. In particular, when the compound represented by the following general formula (9) is contained in the hard coat layer 7, the effect of lowering the falling angle is remarkable. 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, and measuring the minimum angle at which the water drop of a predetermined mass that has been stationary 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.

The amount of the ultraviolet absorber used in the hard coat layer 7 is preferably 0.1 to 20% by mass in order to improve the weather resistance while maintaining good adhesion. More preferably, it is 0.25 to 15% by mass, and more preferably 0.5 to 10% by mass.

As the antioxidant used for the hard coat layer 7, it is preferable to use organic antioxidants such as phenolic antioxidants, thiol antioxidants, and phosphite antioxidants. The falling angle can also be reduced by including an organic antioxidant in the hard coat layer 7. An antioxidant and a light stabilizer may be used in combination.

In addition, nickel-based UV stabilizers can be used as light stabilizers, and [2,2'-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II) can be used as nickel-based UV stabilizers. Nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, and the like.

The hard coat layer 7, particularly the hard coat layer 7 containing a polyfunctional acrylic monomer and a silicon resin, preferably contains an initiator for initiating polymerization. Photoinitiators of active energy ray-curable resins such as ultraviolet rays are preferably used. Examples include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Moreover, you may use an initiator with a photosensitizer. The above initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The initiator or photosensitizer is used in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the composition. Two types of initiators can be used in combination. In particular, in the case of radical initiators, at least two types of initiators, preferably radical initiators that absorb different wavelengths, are used. More preferably, two kinds of initiators having different ultraviolet absorption wavelengths are used. For example, with only an initiator that absorbs a shorter wavelength, the polymerization reaction of all the monomers may not be performed by the initiator. On the other hand, only an initiator that absorbs longer wavelengths improves the reactivity, but the initiator may be colored during long-term use. Therefore, it is preferable to use radical initiators that absorb different wavelengths in order to improve the weather resistance and also the polymerization reactivity without coloring even during long-term use.

In the hard coat layer 7, various additives can be further blended as necessary. For example, a surfactant, a leveling agent and an antistatic agent can be used.

The leveling agent is effective in reducing surface irregularities. As the leveling agent, for example, a dimethylpolysiloxane-polyoxyalkylene copolymer (for example, SH190 manufactured by Toray Dow Corning Co., Ltd.) is suitable as the silicone leveling agent.
(8) Gas Barrier Layer The gas barrier layer 5 is preferably provided on the light incident side with respect to the light reflecting layer. In particular, it is preferable to provide the gas barrier layer 5 between the translucent resin layer 6 and the light reflecting layer.

The gas barrier layer 5 is for preventing deterioration of the humidity, particularly deterioration of the resin base material 1 and each component layer supported by the resin base material 1 due to high humidity, but has a special function and application. As long as it has a function of preventing deterioration, various types of gas barrier layers can be provided.

As the moisture barrier property of the gas barrier layer 5, the water vapor permeability at 40 ° C. and 90% RH is preferably 1 g / m ² · day or less, more preferably 0.5 g / m ² · day or less, still more preferably Is 0.2 g / m ² · day or less.

The oxygen permeability of the gas barrier layer 5 is preferably 0.6 ml / m ² / day / atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.

Examples of the method for forming the gas barrier layer 5 include a method of forming an inorganic oxide by a method such as vacuum deposition, sputtering, ion beam assist, chemical vapor deposition, and the like. A method of forming an inorganic oxide film by applying a heat treatment and / or ultraviolet irradiation treatment to the coating film after coating the body is also preferably used.
(8-1) Inorganic oxide An inorganic oxide is formed by local heating from a sol using an organometallic compound as a raw material. For example, silicon (Si), aluminum (Al), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), indium (In) contained in the organometallic compound, An oxide of an element such as tin (Sn) or niobium (Nb), for example, silicon oxide, aluminum oxide, zirconium oxide, or the like. Of these, silicon oxide is preferable.

As a method for forming the inorganic oxide, it is preferable to use a so-called sol-gel method or a polysilazane method. The sol-gel method is a method of forming an inorganic oxide from an organometallic compound that is a precursor of an inorganic oxide, and the polysilazane method is a method of forming an inorganic oxide from a polysilazane that is a precursor of an inorganic oxide.
(8-2) Inorganic Oxide Precursor The gas barrier layer 5 can be formed by applying a general heating method after applying a precursor for forming an inorganic oxide by heating. It is preferable to form by. This precursor is preferably a sol-shaped organometallic compound or polysilazane.
(8-3) Organometallic compound The organometallic compound includes silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium ( It is preferable to contain at least one element of Ba), indium (In), tin (Sn), lanthanum (La), yttrium (Y), and niobium (Nb). In particular, the organometallic compound contains at least one element of silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), zinc (Zn), and barium (Ba). It is preferable to contain. Furthermore, it is preferable to contain at least one element of silicon (Si), aluminum (Al), and lithium (Li).

The organometallic compound is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include metal alkoxides. This metal alkoxide is represented by the following general formula (10).

MR ² _m (OR ¹ ) _nm (10)
In the above general formula (10), M represents a metal having an oxidation number n. R ¹ and R ² each independently represents an alkyl group. m represents an integer of 0 to (n−1). R ¹ and R ² may be the same or different. R ¹ and R ² are preferably an alkyl group having 4 or less carbon atoms, such as a methyl group CH ₃ (hereinafter represented by Me), an ethyl group C ₂ H ₅ (hereinafter represented by Et), and a propyl group. C ₃ H ₇ (hereinafter represented by Pr), isopropyl group i-C ₃ H ₇ (hereinafter represented by i-Pr), butyl group C ₄ H ₉ (hereinafter represented by Bu), isobutyl group i- A lower alkyl group such as C ₄ H ₉ (hereinafter referred to as i-Bu) is more preferred.

Examples of the metal alkoxide represented by the general formula (10) include lithium ethoxide LiOEt, niobium ethoxide Nb (OEt) ₅ , magnesium isopropoxide Mg (OPr-i) ₂ , and aluminum isopropoxide. Al (OPr-i) ₃ , zinc propoxide Zn (OPr) ₂ , tetraethoxysilane Si (OEt) ₄ , titanium isopropoxide Ti (OPr-i) ₄ , barium ethoxide Ba (OEt) ₂ , barium isopropoxy Ba (OPr-i) ₂ , triethoxyborane B (OEt) ₃ , zirconium propoxide Zn (OPr) ₄ , lanthanum propoxide La (OPr) ₃ , yttrium propoxide Y (OPr) ₃ , lead isopropoxide Pb (OPr-i) _{2 and the} like are preferred. All of these metal alkoxides are commercially available and can be easily obtained. Moreover, the metal alkoxide is also commercially available as a low condensate obtained by partial hydrolysis, and it can be used as a raw material.
(8-4) Sol-gel method Here, the “sol-gel method” refers to a hydroxide sol obtained by hydrolyzing an organometallic compound, etc., and dehydrated to form a gel. It refers to a method for preparing a metal oxide glass having a certain shape (film, particle, fiber, etc.) by heat-treating the gel. A multi-component metal oxide glass can be obtained by a method of mixing a plurality of different sol solutions, a method of adding other metal ions, or the like. Specifically, it is preferable to produce an inorganic oxide by a sol-gel method having the following steps.

That is, in a reaction solution containing at least water and an organic solvent, the organometallic compound is hydrolyzed and dehydrated and condensed while adjusting the pH to 4.5 to 5.0 using a halogen ion as a catalyst in the presence of boron ion. Generation of micropores due to high-temperature heat treatment is produced by a sol-gel method having a step of obtaining a reaction product by heating and vitrifying the reaction product at a temperature of 200 ° C. or less. And is particularly preferable from the viewpoint that no deterioration of the film occurs.

In this sol-gel method, the organometallic compound used as a raw material is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include the metal alkoxides described above. It is done.

In the sol-gel method, the above-described organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction. The dilution solvent may be any solvent that can dissolve the organometallic compound and can be uniformly mixed with water. Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof. Further, a mixed solvent of butanol, cellosolve, and butyl cellosolve, or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.

In this organometallic compound, when the metal is Ca, Mg, Al, etc., it reacts with water in the reaction solution to form a hydroxide, or when carbonate ion CO ₃ ^2- is present, a carbonate is formed. Therefore, it is preferable to add an alcohol solution of triethanolamine as a masking agent to the reaction solution. The concentration of the organometallic compound when mixed and dissolved in the solvent is preferably 70% by mass or less, and more preferably diluted to a range of 5 to 70% by mass.

The reaction solution used in the sol-gel method contains at least water and an organic solvent. The organic solvent is not particularly limited as long as it can form a uniform solution with water, acid, and alkali. Usually, the same aliphatic aliphatic alcohols used for diluting the organometallic compound are preferably used. Among aliphatic lower alcohols, propanol, isopropanol, butanol, and isobutanol having a larger number of carbon atoms are preferable to methanol and ethanol. This is because the growth of the metal oxide glass film to be generated is stable. In this reaction solution, the ratio of water is preferably in the range of 0.2 to 50 mol / L as the concentration of water.

In the sol-gel method, an organometallic compound is hydrolyzed in a reaction solution in the presence of boron ions using a halogen ion as a catalyst. A preferred example of the compound that gives boron ion B ³⁺ is trialkoxyborane B (OR) ₃ . Among these, triethoxyborane B (OEt) ₃ is more preferable. The B ³⁺ ion concentration in the reaction solution is preferably in the range of 1.0 to 10.0 mol / L.

As a halogen ion, a fluorine ion and / or a chlorine ion are mentioned suitably. That is, fluorine ions alone, chlorine ions alone or a mixture thereof may be used. The compound to be used is not particularly limited as long as it generates fluorine ions and / or chlorine ions in the reaction solution described above. For example, as a fluorine ion source, ammonium hydrogen fluoride NH ₄ HF · HF, sodium fluoride NaF or the like is suitable. Preferred examples of the chloride ion source include ammonium chloride NH ₄ Cl.

The concentration of halogen ions in the reaction solution varies depending on the film thickness of the inorganic composition having the inorganic matrix to be produced and other conditions. A range of 0.001 to 2 mol / kg, particularly 0.002 to 0.3 mol / kg is preferable with respect to the total mass. If the halogen ion concentration is lower than 0.001 mol / kg, hydrolysis of the organometallic compound does not proceed sufficiently, and film formation becomes difficult. Moreover, since the produced | generated inorganic matrix (metal oxide glass) will become non-uniform easily when the density | concentration of a halogen ion exceeds 2 mol / kg, neither is preferable.

With respect to the boron used during the reaction, if to be contained as a B ₂ O ₃ component in the design the composition of the resulting inorganic matrix, by leaving product was added calculated amount of organic boron compound in accordance with the content of In addition, when it is desired to remove boron, boron can be removed by evaporation as boron methyl ester by heating after film formation in the presence of methanol as a solvent or by immersing in methanol.

In the step of obtaining a reaction product by hydrolysis and dehydration condensation of an organometallic compound, a main agent solution in which a predetermined amount of an organometallic compound is usually mixed and dissolved in a mixed solvent containing a predetermined amount of water and an organic solvent, and After mixing a predetermined amount of a reaction solution containing a predetermined amount of halogen ions at a predetermined ratio and stirring sufficiently to obtain a uniform reaction solution, the pH of the reaction solution is adjusted to a desired value with an acid or alkali, The reaction product is obtained by aging for several hours. A predetermined amount of the boron compound is previously mixed and dissolved in the main agent solution or reaction solution. Further, when alkoxyborane is used, it is advantageous to dissolve it in the main agent solution together with other organometallic compounds.

The pH of the reaction solution is selected according to the purpose, and when the purpose is to form a film (film) made of an inorganic composition having an inorganic matrix (metal oxide glass), for example, the measurement temperature is measured using an acid such as hydrochloric acid. It is preferable to age at 25 ° C. by adjusting the pH to the range of 4.5 to 5. In this case, for example, it is convenient to use a mixture of methyl red and bromocresol green as an indicator.

In the sol-gel method, the main component solution of the same component and the same concentration and the reaction solution (including B ³⁺ and halogen ions) are successively added at the same rate while adjusting to a predetermined pH. The reaction product can also be produced simply and continuously. The concentration of the reaction solution is in the range of ± 50% by mass, the concentration of water (including acid or alkali) is in the range of ± 30% by mass, and the concentration of the halogen ion is in the range of ± 30% by mass. Can be made.

Next, the reaction product (reaction solution after aging) obtained in the previous step is heated to a temperature of 200 ° C. or lower, dried and vitrified. In heating, it is preferable that the temperature is raised gradually while paying particular attention to a temperature range of 50 to 70 ° C., followed by a preliminary drying (solvent volatilization) step and further raising the temperature. This drying is important for forming a non-porous film in the case of film formation. The temperature for heating and drying after the preliminary drying step is preferably 70 to 150 ° C, more preferably 80 to 130 ° C.
(9) Anchor layer Anchor layer 2 consists of resin, and makes resin base material 1 and silver reflective layer 3 stick. Therefore, the anchor layer 2 has adhesiveness for closely adhering the resin substrate 1 and the silver reflective layer 3, heat resistance that can withstand heat when the silver reflective layer 3 is formed by a vacuum deposition method, and the silver reflective layer 3. Smoothness is required to bring out the high reflection performance inherent in

The resin material used for the anchor layer 2 is not particularly limited as long as it satisfies the above adhesiveness, heat resistance, and smoothness conditions, and polyester resin, acrylic resin, melamine resin, epoxy resin. , Polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, etc., or mixed resins thereof can be used. From the viewpoint of weather resistance, a polyester resin and a melamine resin mixed resin are preferable. It is more preferable to use a thermosetting resin mixed with a curing agent such as.

As a method for forming the anchor layer 2, a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method, or the like in which a predetermined resin material is applied and coated can be used.

The thickness of the anchor layer 2 is preferably 0.01 to 3 μm, more preferably 0.1 to 1 μm. If the thickness is less than 0.01 μm, the adhesion is poor and the effect of forming the anchor layer 2 is not obtained, and it is difficult to cover the unevenness on the surface of the resin substrate 1, resulting in poor smoothness and consequently silver. Since the reflectance of the reflective layer 3 becomes low, it is not preferable. Further, even if the thickness is greater than 3 μm, improvement in adhesion cannot be expected. On the contrary, smoothness is deteriorated due to occurrence of uneven coating, and the anchor layer 2 may be insufficiently cured, which is not preferable.
(10) Film mirror manufacturing method A film mirror for solar power generation can be manufactured by appropriately laminating the above-described constituent layers.

Here, the film mirror 10d shown in FIG. 4A will be described as an example.

For example, the anchor layer 2 is formed by applying a predetermined resin material on a polyethylene terephthalate film that is a resin base material 1 manufactured by melt film formation or the like.

Next, the silver reflection layer 3 is formed on the anchor layer 2 by vacuum deposition.

Next, the corrosion prevention layer 4 is formed on the silver reflection layer 3 by applying a resin material containing a corrosion inhibitor.

Next, a gas barrier layer 5 is formed on the corrosion prevention layer 4 by performing a sol-gel method and heating / UV treatment.

Next, a translucent resin layer 6 is formed on the gas barrier layer 5 by applying a resin material containing an ultraviolet absorber.

Next, a hard coat layer 7 is formed on the translucent resin layer 6 by applying a hard coat material.

Furthermore, a film mirror 10d is manufactured by applying an adhesive material to the back side of the resin substrate 1 to form an adhesive layer 2 and covering the adhesive layer 2 with a release sheet.

In addition, when manufacturing the film mirrors 10a, 10b, and 10c, the step of forming a constituent layer that is not included in the film mirror 10d is omitted, and the constituent layers necessary for each film mirror are laminated on the resin base material 1 in a predetermined order. Thus, a desired film mirror can be manufactured.

And in the film mirror of this invention, only the resin base material 1 is a resin film produced by melt film-forming etc., and the resin film is not used for the other component layers, The film mirror is manufactured by sequentially repeating film formation by coating, coating, vapor deposition or the like of the material of each constituent layer, and laminating predetermined constituent layers.

That is, the film mirror manufacturing method of the present invention includes a resin film having at least a silver reflective layer and a layer (for example, a translucent resin layer containing an ultraviolet absorber) disposed on the light incident side of the silver reflective layer. The resin film and the resin film are manufactured separately, and thereafter the step of bonding the two resin films with an adhesive (adhesive layer) is not included.
(11) Reflector for solar power generation The reflector for solar power generation includes a film mirror and a self-supporting support base material 9, and the film mirror is bonded to the support base material 9 through an adhesive layer 8. It is a reflector.

In addition, "self-supporting property" said here is that the support base material 9 supports the edge part of a film mirror in the state cut | judged to the magnitude | size used as a support base material of the reflective apparatus for solar thermal power generation. This means that the film mirror has rigidity enough to support the film mirror. Since the support base material 9 of the solar power generation reflecting device has self-supporting properties, it is easy to handle when installing the solar power generation reflecting device, and the holding member for holding the solar power generation reflecting device is simple. Since it becomes possible to make it into a structure, it becomes possible to reduce the weight of the reflecting device itself, and it becomes possible to suppress the power consumption at the time of solar tracking.
(11-1) Support base material The self-supporting support base material 9 has a pair of metal flat plates and an intermediate layer interposed between the metal flat plates (type A), or a resin material having a hollow structure. It is preferable that it consists of (type B).
(11-2) Support base type A
The support base 9 has a pair of metal flat plates and an intermediate layer interposed between the metal flat plates, and the intermediate layer is made of a material having a hollow structure or a resin material, whereby a support base The material 9 has high flatness due to the metal flat plate, and can significantly reduce the weight of the support base material itself as compared with the case where the support base material is constituted by only the metal flat plate. In addition, since the rigidity can be increased by the metal flat plate while using a relatively lightweight intermediate layer, it is possible to function as a support substrate that is lightweight and has a self-supporting property.

Furthermore, even when the intermediate layer is made of a resin material, further weight reduction can be achieved by using a resin material layer having a hollow structure.

Further, when the intermediate layer has a hollow structure, the intermediate layer functions as a heat insulating material, so that the temperature change of the metal flat plate on the side opposite to the adhesive layer 8 is suppressed from being transmitted to the film mirror, and dew condensation occurs. It is possible to prevent or suppress deterioration due to heat.

As a metal flat plate used as the surface layer on both sides of the support base 9, heat conduction such as steel plate, copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin plated steel plate, chrome plated steel plate, stainless steel plate, etc. A metal material having a high rate can be preferably used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate or the like having good corrosion resistance.

As the intermediate layer of the support base 9, a material such as a metal, an inorganic material (glass or the like), or a resin material can be used.

When this intermediate layer has a hollow structure, a cellular structure made of foamed resin, a three-dimensional structure having a wall surface made of metal, an inorganic material or a resin material (honeycomb structure, etc.), a resin material to which hollow fine particles are added, etc. are applied. be able to.

The cellular structure of the foamed resin refers to a foamed or porous shape formed by finely dispersing gas in the resin material. A known foamed resin material can be used as the material, but polyolefin resin, 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.

When the intermediate layer has a three-dimensional structure having a wall surface made of a resin material, the resin material constituting the wall surface is a homopolymer or copolymer of olefins such as ethylene, propylene, butene, isoprene pentene, and methylpentene. Polyolefin (eg, polypropylene, high density polyethylene), polyamide, polystyrene, polyvinyl chloride, polyacrylonitrile, acrylic derivatives such as ethylene-ethyl acrylate copolymer, polycarbonate, vinyl acetate such as ethylene-vinyl acetate copolymer Copolymers, ionomers, terpolymers such as ethylene-propylene-dienes, and thermoplastic resins such as ABS resin, polyolefin oxide, and polyacetal are preferably used. In addition, these may be used individually by 1 type, or may mix and use 2 or more types. In particular, among 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. Examples of 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.

The intermediate layer may be a layer made of a resin plate. In this case, the resin material constituting the intermediate layer is preferably the same as the material constituting the resin substrate 1 of the film mirror described above. Can be used.

The intermediate layer does not need to be provided in all regions of the support base 9, and is provided in some regions as long as the flatness of the metal flat plate and the self-supporting property as the support base can be ensured. It may be. When the intermediate layer has the above-described three-dimensional structure, it is preferable to provide the three-dimensional structure in a region of about 90 to 95% with respect to the area of the metal flat plate. It is preferable to provide it.
(11-3) Support base material type B
It is also possible for the support substrate 9 to be a layer made of a resin material having a hollow structure.

When the support base material 9 is made of a resin material only, the thickness required to obtain rigidity sufficient to provide self-supporting properties increases, and as a result, the mass of the support base material 9 increases. By providing the material with a hollow structure, the support substrate 9 can be reduced in weight while providing self-supporting properties.

When the support substrate 9 is made of a resin material having a hollow structure, it is possible to use a resin material having a hollow structure as an intermediate layer and to provide a resin sheet having smooth surfaces as both surface layers thereof. This is preferable from the viewpoint of increasing the reflectance. As the material of the resin sheet, the same material as that constituting the resin substrate 1 of the film mirror described above can be preferably used. As the resin material having a hollow structure, the above-described foamed material and the resin material having a three-dimensional structure (honeycomb structure) can be preferably used.
(11-4) Holding Member The solar power generation reflecting device has a holding member that holds the reflecting device itself.

It is preferable that the holding member holds the reflecting surface (film mirror) of the solar power generation reflecting device in a state where the sun can be tracked. The form of the holding member is not particularly limited, but, for example, a plurality of points on the support base 9 on the back side of the solar power generation reflecting device are rod-shaped so that the solar power generating reflection device can hold a desired shape and posture. The form held by the columnar member or the beam-shaped member is preferable.

The holding member has a configuration for holding the solar power generation reflecting device in a state in which the sun can be tracked. However, in the case of solar tracking, the holding member may be driven manually, or a separate driving device may be provided to automatically track the sun. It is good also as composition to do.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The film mirror of this example is an embodiment shown in FIGS. 1A to 4A. However, the present invention is not limited to these. In the following examples and comparative examples, “part” or “%” is used, and “part by mass” or “% by mass” is expressed unless otherwise specified.

[Comparative Example 1]
(Preparation of film mirror of Comparative Example 1)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate 1 of the resin film support. A silver reflecting layer 3 having a thickness of 100 nm was formed as a light reflecting layer on one surface of the resin substrate 1 by a vacuum deposition method.

Next, on the side opposite to the silver reflecting layer 3 in the resin base material 1, a transparent acrylic film (transparent resin layer 6 made of Mitsubishi Rayon Acryprene HBS010P thickness) is formed by a dry lamination process. 75 μm) was bonded at a laminating temperature of 60 ° C. via the adhesive layer 11.

Further, 100 parts of an addition reaction type silicone adhesive having a weight average molecular weight of 500,000 was added with 1 part of a platinum catalyst to form a 35 mass% toluene solution, and applied to one side of a 25 μm thick polyester separate film. After heating at 120 ° C. for 5 minutes to form an adhesive layer 8 (Si-based) having a thickness of 25 μm, it was laminated on the silver reflective layer 3 of the polyethylene terephthalate film, and the film mirror 10e of Comparative Example 1 (see FIG. 5A) Got.

(Preparation of solar power generation reflector)
A support base material 9 made of an aluminum plate having a thickness of 0.1 mm, a length of 4 cm and a width of 5 cm, and the film mirror 10 e of Comparative Example 1 are bonded together via the adhesive layer 8, and the solar power generation reflection device 20 e (A -1) was obtained (see FIG. 5B).

In the same manner, solar power generation reflectors were respectively produced using the film mirrors of the following examples and comparative examples.

[Comparative Example 2]
(Preparation of film mirror of Comparative Example 2)
A silver reflective layer 3 having a thickness of 100 nm was formed as a light reflective layer on one side of a resin base material 1 made of a transparent acrylic film (Acryprene HBS010P, thickness 75 μm manufactured by Mitsubishi Rayon) containing an ultraviolet absorber.

Further, 100 parts of an addition reaction type silicone adhesive having a weight average molecular weight of 500,000 was added with 1 part of a platinum catalyst to form a 35 mass% toluene solution, and applied to one side of a 25 μm thick polyester separate film. After heating at 120 ° C. for 5 minutes to form an adhesive layer 8 (Si-based) having a thickness of 25 μm, it was laminated on the silver reflective layer 3 of the transparent acrylic film to obtain 10f of Comparative Example 2 (see FIG. 6A). It was.

Further, a solar power generation reflection device 20f (B-1) was produced by using the film mirror 10f of Comparative Example 2 in the same manner as the solar power generation reflection device 20e (A-1) (see FIG. 6B).

[Example 1]
(Preparation of film mirror of Example 1)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate 1 of the resin film support. Polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), melamine resin (manufactured by Super Becamine J-820 DIC), TDI (tolylene diisocyanate) isocyanate (2,4-tri Diisocyanate) and HMDI (hexamethylene diisocyanate) -based isocyanate (1,6-hexamethylene diisocyanate) were mixed in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10%. Resin was coated by a gravure coating method to form an anchor layer 2 having a thickness of 0.1 μm, and a silver reflecting layer 3 having a thickness of 100 nm was formed as a light reflecting layer on the anchor layer 2 by a vacuum deposition method. .

Further, an acrylic resin (Acrypet VH made by Mitsubishi Rayon) and UV absorber (Tinuvin 477 made by BASF) were dissolved at a solid content ratio of 95: 5 at a solid content of 20% in MEK, and then the above silver reflective layer was formed by an extrusion coater. 3 was coated and dried (90 ° C., 1 minute) so as to have a film thickness of 30 μm, thereby forming a translucent resin layer 6.

Next, 100 parts of an addition reaction type silicone adhesive having a weight average molecular weight of 500,000 was added with 1 part of a platinum catalyst to form a 35 mass% toluene solution, and applied to one side of a 25 μm thick polyester separate film. After heating at 120 ° C. for 5 minutes to form a 25 μm thick adhesive layer 8 (Si-based), the film was laminated on the side opposite to the silver reflective layer 3 of the polyethylene terephthalate film, and the film mirror 10a of Example 1 was Obtained (see FIG. 1A).

Further, a solar power generation reflection device 20a (C-1) was produced by using the film mirror 10a of Example 1 by the same method as the solar power generation reflection device 20e (A-1) (see FIG. 1B).

[Example 2]
(Preparation of film mirror of Example 2)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate 1 of the resin film support. Polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), melamine resin (manufactured by Super Becamine J-820 DIC), TDI-based isocyanate (2,4-tolylene diisocyanate), HDMI on one side of the resin base material 1 A resin in which toluene-based isocyanate (1,6-hexamethylene diisocyanate) was mixed in toluene at a resin solid content ratio of 20: 1: 1: 2 to a solid content concentration of 10% was coated by a gravure coating method. Then, an anchor layer 2 having a thickness of 0.1 μm was formed, and a silver reflecting layer 3 having a thickness of 100 nm was formed on the anchor layer 2 as a light reflecting layer by a vacuum deposition method.

Further, 2-mercaptobenzothiazole as a silver corrosion inhibitor is 10% of the resin in which polyester resin and TDI isocyanate are mixed at a resin solid content ratio of 10: 2 on the silver reflection layer 3. The coating solution, which was added so as to be in mass% and the solid content was adjusted to 5% by MEK, was coated by a gravure coating method to form a corrosion prevention layer 4 having a thickness of 3.0 μm.

Next, after dissolving acrylic resin (Mitsubishi Rayon Acrypet VH) and UV absorber (BASF Tinuvin 477) at a solid content ratio of 95: 5 and 20% solid content in MEK on the corrosion prevention layer 4 Then, coating and drying (90 ° C., 1 minute) were performed on the silver reflective layer with an extrusion coater so as to have a film thickness of 30 μm, thereby forming a translucent resin layer 6 containing a UV absorber.

Next, 100 parts of an addition reaction type silicone adhesive having a weight average molecular weight of 500,000 was added with 1 part of a platinum catalyst to form a 35 mass% toluene solution, and applied to one side of a 25 μm thick polyester separate film. After heating at 120 ° C. for 5 minutes to form a 25 μm thick adhesive layer 8 (Si-based), the film was laminated on the opposite side of the polyethylene terephthalate film from the silver reflecting layer 3, and the film mirror 10b of Example 2 was Obtained (see FIG. 2A).

Further, a solar thermal power generation reflection device 20b (D-1) was produced by using the film mirror 10b of Example 2 in the same manner as the solar power generation reflection device 20e (A-1) (see FIG. 2B).

[Example 3]
(Preparation of film mirror of Example 3)
The same method as in Example 2 except that a UV curable transparent hard coat layer 7 (Ryoduras TYZ manufactured by Toyo Ink Co., Ltd .: 5 μm thick) is applied on the UV-absorbing translucent resin layer 6 of Example 2. Thus, a film mirror 10c of Example 3 was obtained (see FIG. 3A).

Further, a solar power generation reflection device 20c (E-1) was produced using the film mirror 10c of Example 3 by the same method as that of the solar power generation reflection device 20e (A-1) (see FIG. 3B).

[Example 4]
(Preparation of film mirror of Example 4)
A 3% perhydropolysilazane solution in dibutyl ether (NL120 manufactured by Clariant) was bar-coated on the corrosion prevention layer 4 of Example 3 so that the film thickness after drying was 100 nm, and 3 minutes. After natural drying, a film mirror 10d of Example 4 was obtained by the same method as Example 3 except that annealing was performed in an oven at 90 ° C. for 30 minutes to provide the gas barrier layer 5 (see FIG. 4A).

Further, a solar power generation reflection device 20d (F-1) was produced by using the film mirror 10d of Example 4 by a method similar to that of the solar power generation reflection device 20e (A-1) (see FIG. 4B).

Further, when the solar power generation reflectors (C-1) to (F-1) are produced, each film is replaced with a supporting base material made of an aluminum plate having a thickness of 0.1 mm, a length of 4 cm and a width of 5 cm. A reflective device for solar thermal power generation was produced, in which a mirror adhesive layer 8 and a support base material 9 having a sandwich structure were bonded together ((C-2) to (F-2)).

The support substrate 9 having a sandwich structure refers to, for example, a material in which a resin layer having a hollow structure is sandwiched between metal flat plates. Here, a supporting substrate 9 having a sandwich structure of 2 mm in thickness formed by sandwiching a foamed polyethylene resin layer having a thickness of 1.76 mm as an intermediate layer between a pair of metal flat plates using aluminum having a thickness of 0.12 mm. It was used.

Further, when the solar power generation reflectors (C-1) to (F-1) are produced, each film is replaced with a supporting substrate made of an aluminum plate having a thickness of 0.1 mm, a length of 4 cm and a width of 5 cm. A reflective device for solar thermal power generation was produced in which the adhesive layer 8 of the mirror and the support substrate 9 having a hollow structure were bonded together ((C-3) to (F-3)). The hollow structure is a case where the support base 9 described above is a layer made of a resin material having a hollow structure. Specifically, a polypropylene layer having a honeycomb structure and a thickness of 3 mm is formed from an aluminum plate having a thickness of 0.3 mm. A resin honeycomb plate sandwiched from both sides was used.

As a result of measuring the weight and driving power consumption rate of the solar power generation reflector manufactured using the above support substrate, it can be significantly reduced in weight compared to the conventional solar power generation reflector, and as a result, the transport efficiency is The work has been shortened and the work has been shortened, contributing to cost reduction.

In the production of the film mirrors of Examples 1 to 4, as a result of measuring the center line average roughness of the translucent resin layer, it was confirmed that the center line average roughness (Ra) was 3 nm or more and 20 nm or less. On the other hand, Comparative Examples-1 and 2 in which the silver reflective layer and the adhesive layer contact each other had centerline average roughness (Ra) of 50 nm and 65 nm, respectively.

The centerline average roughness (Ra) was measured based on JIS B0601-1982. The measuring apparatus measured the area of 2 square mm using WYCO VISION32 by Veeco.

[Evaluation]
About the reflective apparatus for solar power generation (mirror for sunlight reflection) obtained above, the regular reflectance, weather resistance, light resistance, etc. were measured by the following methods, respectively.

<Measurement of regular reflectance>
A spectrophotometer “UV265” manufactured by Shimadzu Corporation was modified with an integrating sphere reflection accessory, and the incident angle of incident light was adjusted to 5 ° with respect to the normal of the reflecting surface. The regular reflectance at a reflection angle of 5 ° was measured. Evaluation was measured as an average reflectance from 350 nm to 700 nm.

<Weather resistance test for regular reflectance>
The specular reflectance of the solar power generation reflecting device (sunlight reflecting mirror) after being left for 30 days at a temperature of 85 ° C. and a humidity of 85% RH is measured by the same method as the above-mentioned light reflectance measurement, before forced deterioration. From the regular reflectance of the solar reflective mirror and the regular reflectance of the film mirror after forced deterioration, the decrease rate of the regular reflectance was calculated. The evaluation criteria for the weather resistance test are described below.
5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Regular reflectance decrease rate is 20% or more <Yellow change of solar reflective mirror>
The obtained sample was irradiated with ultraviolet rays for 7 days in an environment of 65 ° C. using an I-super UV tester manufactured by Iwasaki Electric Co., Ltd., and then the yellow color was visually changed.
○: The difference in color is not visible.
Δ: A slight difference in color is visually observed.
X: The difference in color is clearly visible.

<Anti-fouling test>
A solar reflective mirror was cut into a 10 cm wide x 10 cm long test piece, fixed to an aluminum frame, and exposed to the outdoors at an angle of 45 ° (January to June 2010, location: Hachioji City, Tokyo) ). The degree of contamination after 6 months of outdoor exposure was visually observed and evaluated in three stages (◯: no dust adhesion, Δ: little dust adhesion, ×: much dust adhesion).

<Pencil hardness test>
Based on JIS-K5400, the pencil hardness of each sample at 45 ° inclination and 1 kg load was measured.

<Mass>
Table 3 shows the result of measuring the 1.0 m ² size mass of the obtained sunlight reflecting mirrors F-1 and F-2.

<Drive power consumption rate>
Table 3 shows the ratio when the driving power applied to one tracking unit incorporating the solar thermal power generation reflection device F-1 is 100 when the solar thermal power generation reflection device is incorporated in the solar tracking type device.

Table 1 shows the contents of the various film mirrors obtained (layer structure), and Table 2 shows the results of evaluation of the characteristics.

As is clear from the evaluation results shown in Tables 2 and 3, it can be seen that the various characteristics of the examples according to the present invention are superior to the comparative examples. That is, by the above means of the present invention, it is possible to prevent a decrease in regular reflectance due to deterioration of the silver reflective layer 3, and to be light and flexible, light resistance that can reduce the manufacturing cost, increase the area and mass-produce, It can be seen that a film mirror having excellent weather resistance, antifouling property, and scratch resistance and having good regular reflectance with respect to sunlight, a production method thereof, and a solar power generation reflector using the film mirror can be provided.

That is, according to the present invention, it is possible to prevent a decrease in regular reflectance due to deterioration of the silver reflective layer 3, and to be lightweight and flexible, to reduce the manufacturing cost, to increase the area and to mass-produce, scratch resistance, Film mirror for solar power generation (10a, 10b) having excellent anti-fouling properties and excellent weather resistance that can maintain good regular reflectance for sunlight for a long time even when installed in a harsh environment for a

long time

10c, 10d) and a solar power generation reflection device (20a, 20b, 20c, 20d) can be provided.

In particular, the film mirror (10a, 10b, 10c, 10d) according to the present invention is a material of each constituent layer sequentially with respect to the resin substrate 1 without bonding the resin films together with an adhesive layer using an adhesive. Since the coating, coating, and film formation are repeated and a predetermined constituent layer is laminated, there is no possibility that bubbles or foreign matters are mixed between constituent layers. Therefore, in the film mirror of this invention, the malfunction which causes the fall of light reflectivity by a bubble and a foreign material mixing in between constituent layers does not arise.

Moreover, by forming the translucent resin layer 6 by a coating method, the smoothness of the translucent resin layer 6 can be improved. Specifically, the center line average roughness of the translucent resin layer 6 ( Since Ra) can be 3 nm or more and 20 nm or less, unlike the prior art, the reflected light is not scattered by the surface unevenness of the resin film, and the film mirror of the present invention has suitable light reflectivity. Have

[Example 5]
(Preparation of solar thermal power generation reflector G-1)
In the production of the film mirror 10c of Example 3, the film mirror was produced so that the thickness of the translucent resin layer of 30 μm was changed only by the flow rate of the extrusion coater, and the film thickness was 5 μm. Thereafter, a solar power generation reflector (G-1) was produced using this film mirror in the same manner as the solar power generator reflector 20e (A-1).

(Preparation of solar power generation reflectors H-1 and I-1)
In the production of the solar power generation reflection device G-1, only the thickness of the translucent resin layer was changed as shown in Table 4 to produce a film mirror. Using this film mirror, solar power generation reflectors H-1 and I-1 were respectively produced by the same method as solar power generation reflector 20e (A-1). In addition, although the production of the film mirror which changed only the thickness of the translucent resin layer into 170 micrometers similarly was tried, in order to fully evaporate a solvent at the time of drying, you have to reduce a coating speed. It was. This resulted in a significant reduction in productivity.

For these solar power generation reflectors and the solar power generation reflector (E-1) produced in Example 3, the specular reflectance weather resistance test and the solar reflection mirror yellow change test and evaluation were performed respectively. This was done by the method described above. The results are shown in Table 4.

From the results of Table 4, when the thickness of the translucent resin layer is in the range of 10 to 150 μm, in addition to the weather resistance test and the yellowing change test of the solar reflective mirror, good productivity is obtained. You can see that

The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the gist of the present invention.

The film mirror of the present invention has high scratch resistance, weather resistance and high reflectivity that can withstand the practical use of collecting sunlight, and can be suitably used for a solar power generation reflector.

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Anchor layer 3 Silver reflection layer (light reflection layer)
DESCRIPTION OF SYMBOLS 4 Corrosion prevention layer 5 Gas barrier layer 6 Translucent resin layer 7 Hard coat layer 8 Adhesive layer 9 Support base material 11

Adhesive layer

10a, 10b, 10c,

10d Film mirror

20a, 20b, 20c, 20d Solar power generation reflective apparatus

Claims

In order from the light incident side, a light transmitting resin layer, a light reflecting layer, a resin base material, and a film mirror having at least an adhesive layer,
The translucent resin layer contains an ultraviolet absorber, and the translucent resin layer has a thickness of 10 μm to 150 μm.
The translucent resin layer is formed directly on the surface of the light reflecting layer on the light incident side or on the surface of the constituent layer provided on the light incident side of the light reflecting layer without an adhesive layer. The film mirror according to claim 1.
The film mirror according to claim 1 or 2, wherein a center line average roughness (Ra) of the surface of the translucent resin layer is 3 nm or more and 20 nm or less.
The film mirror according to any one of claims 1 to 3, wherein a corrosion prevention layer is provided adjacent to the light incident side of the light reflecting layer.
5. The film mirror according to claim 1, wherein a hard coat layer is provided on a light incident side surface of the translucent resin layer.
The film mirror according to any one of claims 1 to 5, wherein a gas barrier layer is provided on a light incident side of the light reflection layer.
A film mirror manufacturing method for manufacturing the film mirror according to any one of claims 1 to 6,
By directly applying a material to be the translucent resin layer on the light incident side surface of the light reflecting layer or on the surface of the constituent layer provided on the light incident side with respect to the light reflecting layer, the light transmitting resin layer is directly applied. A method for producing a film mirror, comprising forming a light-sensitive resin layer.
A solar power generation reflecting device, wherein the adhesive layer of the film mirror according to any one of claims 1 to 6 is formed by bonding to a support base material.
The solar power generation reflecting device according to claim 8, wherein the supporting substrate is made of a resin material having a hollow structure.
The said support base material has a pair of metal flat plate and the intermediate | middle layer interposed between the said metal flat plates, The said intermediate | middle layer consists of a material or resin material which has a hollow structure, It is characterized by the above-mentioned. The solar power generation reflective apparatus described.