JP2012232538A - Film mirror, solar light reflecting mirror, and reflection apparatus for generating solar power - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film mirror for generating solar power, the mirror having superior contamination resistance, scratch resistance and weather resistance, and being capable of maintaining a satisfactory specular reflectance to solar light, even if installed in a harsh environment for a long time, and to provide a solar power generation film mirror using the film mirror, and a reflection apparatus for generating solar power.SOLUTION: The solar power generation film mirror 20 having a reflection layer 3 on a resin substrate 1, includes a contamination-preventing layer 8 where inorganic particles having different particle diameters of, for example, 0.5-100 nm, are dispersed.

Description

  The present invention relates to a film mirror, a solar reflective mirror using a film mirror, and a solar power generation reflector using a solar reflective 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.

  As an alternative energy to fossil fuel, solar energy can be considered as one of the stable and abundant natural energy. In particular, the vast desert spreads near the equator, which is called the world's sun belt, and the solar energy that falls down here is truly inexhaustible. In this regard, it is believed that energy of as much as 7,000 GW can be obtained using only a few percent of the desert that extends to the southwestern United States. 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 light collecting device is exposed to ultraviolet rays, heat, wind and rain, sandstorms, and the like caused by sunlight, conventionally, a glass mirror has been used for the light collecting device. Glass mirrors are highly durable to the environment, but they are damaged during transportation and heavy, so that there is a problem that the construction cost of the plant is increased due to the strength of the mount on which the mirrors are installed.

  In order to solve the above problem, it has been considered to replace a glass mirror with a resin mirror (for example, Patent Document 1 and Patent Document 2). However, when a metal such as silver is used for the resin mirror, Oxygen, water vapor, hydrogen sulfide, etc. permeate through the resin layer and corrode silver, and the resin layer deteriorates due to ultraviolet rays, causing discoloration and film peeling. Application was difficult.

  In order to solve the above problems, a resin mirror that uses an acrylic film that blocks ultraviolet rays and has excellent light resistance on the surface has been proposed (for example, Patent Document 3). However, in the layer configuration proposed in Patent Document 3, since the adhesive layer easily transmits various substances, contaminants enter from the interface between the adhesive layer and the silver reflective layer, and the corrosion of the silver progresses. There arises a problem that the polyester film located on the light source side of silver is yellowed due to a problem that the color is lowered and exposure to ultraviolet rays for a long time. Furthermore, since the silver reflecting surface is in direct contact with the adhesive layer or through a very thin copper layer, the unevenness of the adhesive layer is transferred to the silver reflecting surface, and the reflected light is scattered and condensed. Since the problem that efficiency falls arises, it was not what can endure use as a mirror for condensing sunlight.

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

  In view of this point, the present invention can prevent deterioration due to ultraviolet rays and corrosion of silver while being lightweight, and has high scratch resistance, weather resistance and high reflectance that can withstand practical use as a mirror for solar light reflection. An object of the present invention is to provide a film mirror, a solar reflective mirror, and a solar thermal power reflector that can be maintained for a long period of time and have high productivity.

  The film mirror according to claim 1 is a film mirror in which a silver reflective layer is provided on a resin film-like support, in order from the light incident side, an acrylic layer, an adhesive layer, a resin coat layer, the silver reflective layer, It has a resin film-like support and an adhesive layer, and the acrylic layer contains an ultraviolet absorber.

  The film mirror according to claim 2 is the invention according to claim 1, wherein the resin coat layer and the silver reflective layer are adjacent to each other, and the resin coat layer contains a silver corrosion inhibitor. It is characterized by that.

  A film mirror according to a third aspect is the invention according to the first or second aspect, wherein a transparent hard coat layer is provided on the light incident side of the acrylic layer.

  A film mirror according to a fourth aspect is the invention according to any one of the first to third aspects, wherein the film mirror has a gas barrier layer on a light incident side with respect to the silver reflection layer.

  The mirror for sunlight reflection of Claim 5 has the film mirror in any one of Claims 1-4, and a self-supporting base material, The said film mirror is the said through the said adhesion layer. It is characterized by being bonded to a base material.

  The solar reflective mirror according to claim 6 is the invention according to claim 5, wherein the base material includes a pair of metal flat plates and an intermediate layer provided between the metal flat plates. The intermediate layer is a layer having a hollow structure or a resin layer.

  The solar reflective mirror described in claim 7 is the invention described in claim 5, wherein the substrate is made of a resin layer having a hollow structure.

  The solar power generation reflecting device according to an eighth aspect includes the solar light reflecting mirror according to any one of the fifth to seventh aspects.

  According to the present invention, while being lightweight, it can prevent deterioration due to ultraviolet rays and corrosion of silver, and not only has high scratch resistance, weather resistance and high reflectivity that can withstand practical use as a mirror for sunlight reflection, It is possible to provide a film mirror, a solar reflective mirror, and a solar power generation reflecting device that can be maintained for a long period of time and have high productivity.

Schematic sectional view showing an example of the configuration of a film mirror as a comparative example It is a schematic sectional drawing which shows an example of a structure of the film mirror for solar power generation of this invention. It is a schematic sectional drawing which shows an example of a structure of the film mirror for solar power generation of this invention. It is a schematic sectional drawing which shows an example of a structure of the film mirror for solar power generation of this invention. It is a schematic sectional drawing which shows an example of a structure of the film mirror for solar power generation of this invention.

  Hereinafter, the 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. Film mirror>
The film mirror 20 (20b to 20e) of the present invention has an acrylic layer 5, an adhesive layer 4, a resin coat layer 8 (11), a silver reflective layer 3, a resin film support 1, and an adhesive layer 6 in this order from the light incident side. At least. In addition, you may interpose another layer between these layers, and each layer may adjoin. Further, another layer may be provided on the acrylic layer 5 or the adhesive layer 6.

  In the case where another layer is interposed between the above-mentioned layers or another layer is provided on the acrylic layer 5 or the adhesive layer 6, the following examples are given as preferable examples.

The gas barrier layer 9 may be provided somewhere on the light incident side of the silver reflecting layer 3.
Further, the transparent hard coat layer 10 may be provided on the light incident side of the acrylic layer.

Further, the anchor layer 2 may be provided between the silver reflective layer 3 and the resin film-like support 1.
Moreover, you may provide the peeling layer 7 which covers the adhesion layer 6. FIG.

  The thickness of the entire film mirror according to the present invention is preferably 80 to 300 [mu] m, more preferably 80 to 200 [mu] m, still more preferably 80 to 170 [mu] m, from the viewpoints of prevention of bending, regular reflectance, and handling properties.

  Details of the configuration of each layer will be described below.

<2. Acrylic layer>
The acrylic layer contains an ultraviolet absorber. The acrylic layer may contain an antioxidant. Since the acrylic layer is hard, plasticizer fine particles may be contained in order to obtain an acrylic layer that is soft and difficult to break. Preferable examples of the plasticizer fine particles include butyl rubber and butyl acrylate fine particles. In addition, it is preferable that the thickness of an acrylic layer is 20-150 micrometers. More preferably, it is 40-100 micrometers.

  The acrylic layer is preferably composed of a methacrylic resin as a base resin. The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of a methacrylic acid ester, or a methacrylic acid ester of 50% by weight or more and other monomers of 50% by weight 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 all monomers. More preferably, the methacrylic acid ester is 50 to 99.9% by weight, the acrylic acid ester is 0.1 to 50% by weight, and other monomers are 0 to 49% by weight.

  Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. 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 this monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, 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 acids, 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 methacrylic resin preferably has a glass transition temperature of 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.

<2-2. UV absorber>
Details of the ultraviolet absorber contained in the acrylic layer will be described below.

  Although there is no restriction | limiting in particular in an ultraviolet absorber, As an organic type, a benzophenone type, a benzotriazole type, a phenyl salicylate type, a triazine type, a benzoate type etc. are mentioned, and an inorganic type includes titanium oxide, zinc oxide, cerium oxide, Examples thereof include iron oxide. In order to reduce the problem of bleeding out when a large amount of ultraviolet absorber is contained, it is preferable to use a polymeric ultraviolet absorber having a molecular weight of 1000 or more. Preferably, the molecular weight is 1000 or more and 3000 or less.

  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 benzotriazole ultraviolet absorbers 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 phenylsulcylate, 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-triazi 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] (Tinuvin 1577FF, trade name, Ciba Specialty Chemicals) Product), [2- [4,6-bis (2,4dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol] (CYASORB UV-1164, trade name, For example, made by Cytec Industries).

  Examples of the benzoate ultraviolet absorber include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (molecular weight 438.7; examples of commercially available products) Sumisorb 400) from Sumitomo Chemical Co., Ltd.

  In addition to the above, as the ultraviolet absorber, a compound having a function of converting the energy held by ultraviolet rays into vibration energy in the molecule and releasing the vibration energy as heat energy or the like can be used. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers acting as a light energy conversion agent, called quenchers, can be used in combination. 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, the said ultraviolet absorber can also respectively use those 2 or more types as needed. 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, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, or the like can be contained.

The content of the ultraviolet absorber in the acrylic layer is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 10% by mass. The content of the ultraviolet absorber in the acrylic layer is 0.17 to 2.28 g / m ² per unit area of the film, and more preferably 0.4 to 2.2. 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.

<2-3. Antioxidant>
An antioxidant may be included in the acrylic layer in order to prevent the acrylic layer from being deteriorated during melt film formation or to capture radicals and prevent the acrylic layer from deteriorating. Examples of preferred antioxidants are listed below.

  As the antioxidant, it is preferable to use organic antioxidants such as phenolic antioxidants, hindered amine antioxidants, thiol antioxidants, and phosphite antioxidants.

  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-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-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) propio , Triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-di-methyl-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 , 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

  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-t-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-tetramethyl Piperidine, 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, the hindered amine light stabilizer is preferably a hindered amine light stabilizer containing only a tertiary amine, specifically, 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, Alternatively, a condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferable.

  Examples of the thiol 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.

  The above antioxidant and the following light stabilizer can be used in combination. As the light stabilizer, for example, a nickel-based UV stabilizer can also be used. As the nickel-based UV stabilizer, [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel ( II), nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl-dithiocarbamate and the like.

<3. Adhesive layer>
The adhesive layer is not particularly limited as long as it has a function of improving the adhesion between the layers. Adhesion or adhesion may be used. Preferably, it is a layer for bonding the acrylic layer and the resin coat layer. Adhesive layer has adhesion to adhere the layers, heat resistance that can withstand heat when the silver reflective layer is formed by vacuum deposition, etc., and smoothness to bring out the high reflective performance that the silver reflective layer originally has. It is preferable to have it.

  The adhesive layer may consist of only one layer or may consist of a plurality of layers. The thickness of the adhesive layer is preferably 1 to 10 μm, more preferably 3 to 8 μm, from the viewpoints of adhesion, smoothness, reflectance of the reflective material, and the like.

  When the adhesive layer is a resin, the resin is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness, polyester resin, urethane resin, acrylic resin, melamine Resin, epoxy resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, etc. can be used singly or as a mixed resin. From the viewpoint of weather resistance, polyester resin and melamine resin or polyester resin can be used. A mixed resin of a resin and a urethane-based resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is mixed such that an isocyanate is mixed with an acrylic resin is more preferable. As a method for forming the adhesive layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.

  When the adhesive layer is a metal oxide, it can be formed by various vacuum film forming methods such as silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, and lanthanum nitride. For example, there are 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.

<4. Resin coat layer>
The resin coat layer is provided between the acrylic layer and the silver reflective layer. When the resin coat layer is adjacent to the silver reflection layer, the resin coat layer preferably contains a silver corrosion inhibitor so that the resin coat layer prevents silver corrosion.

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

  As the binder of the resin coat layer, for example, the following resins can be preferably used. Cellulose ester, polyester, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyethylene terephthalate, polyethylene naphthalate, polyester, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose Acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene, polymethylpentene, polyether ketone, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, An acrylic resin etc. can be mentioned. Among these, an acrylic resin is preferable.

<4-2. Corrosion inhibitor>
The corrosion inhibitor preferably has an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which a metal (silver) is chemically or electrochemically eroded or deteriorated by an environmental material surrounding it (see JIS Z0103-2004).
The optimum content of the corrosion inhibitor varies depending on the compound used, but it is generally preferred that the content is 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-ethoxychrysidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolaminebenzoate, 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 the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, N-phenyl-3, 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

  Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy) 5′-tert-butylphenyl) benzotriazole, 2- (2′-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 commercial 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 Tinuvin 2 from Ciba Specialty Chemicals Co., Ltd. 4), 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 and the like. 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-phenyl Rumyl imidazole, 4-methyl-5-formyl imidazole, 2-ethyl-4-methyl-5-formyl imidazole, 2-phenyl-4-methyl-4-formyl imidazole, 2-mercaptobenzimidazole, etc., or these Of the mixture.

  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 the copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and 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 added to the above-described materials. -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, and the like, or a mixture thereof.

  Examples of the naphthalene type include thionalide.

<5. Silver reflective layer>
A silver reflective layer is a layer which has as a main component silver which has the function to reflect sunlight favorably. The surface reflectance of the silver reflective layer is preferably 80% or more, more preferably 90% or more. The thickness of the silver reflective layer is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectance and the like.

  As a method for forming this silver reflective 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 a silver reflection layer by silver vapor deposition.

<5-2. Silver complex compound having a ligand that can be vaporized and desorbed>
When forming a silver reflective layer, you may make it form a silver reflective layer by heat-baking the coating film containing the silver complex compound which a ligand can vaporize and detach | desorb.

“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 / desorbed, and only metallic silver remains.

Examples of such a complex are publicly known special table 2009-535661, special table 2010-5.
A silver compound represented by the following general formula (1) is reacted with an ammonium carbamate compound or an ammonium carbonate compound represented by general formulas (2) to (4). It is preferable that it is a silver complex compound obtained by doing this.

  Moreover, a silver complex compound is contained in a silver coating liquid composition, and the coating film containing the complex according to the present invention is formed on a support by coating this. That is, after forming a coating film on a film using a silver complex compound, it is preferable to form a silver reflective layer by heating and baking the coating film at a temperature in the range of 80 to 250 ° C. More preferably, it exists in the range of 100-220, Most preferably, it exists in the range of 120-200 degreeC. 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 compound or the ammonium carbonate compound represented by the general formulas (2) to (4) will be described.

Ag _n X (1)

(In the general formulas (1) to (4), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, It is a substituent selected from carboxylate and derivatives thereof, 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 fatty acid. These are substituents selected from cyclic alkyl groups, aryl groups or aralkyl groups, alkyl and aryl groups substituted with functional groups, heterocyclic compound groups, polymer compounds 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, triethylenedia , Pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and their derivatives, and polymers such as polyarylamine and polyethyleneamine Examples of the compound and derivatives thereof are not limited thereto.

  Examples of the compounds of the general formulas (2) to (4) include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n- Butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-si Noethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridiumethylhexylcarbamate, triethylenediaminiumisopropyl Bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, isopropylammonium bicarbonate, n-butyl Ammonium 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 dioctadecylcarbonate, dioctade Silammonium bicarbonate, methyldecylammonium methyldecylcarbonate, hexamethyleneimineammonium hexamethyleneiminecarbonate, morpholineammonium morpholinecarbonate, benzylammonium benzylcarbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate, pyridium bicarbonate, triethylenediaminium Examples thereof include, but are not limited to, one or a mixture of two or more selected from isopropyl carbonate, triethylenediaminium bicarbonate, and derivatives thereof.

  On the other hand, the kind and production method of the above-mentioned ammonium carbamate or ammonium carbonate compound need not be 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 thus produced ammonium carbamate or ammonium carbonate compound with a silver compound. For example, at least one silver compound represented by the general formula (1), at least one ammonium carbamate or ammonium carbonate derivative represented by the general formulas (2) to (4), and a mixture thereof. In a nitrogen atmosphere at normal pressure or under pressure without using a solvent, or when using a solvent, alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin Glycols such as ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane Of benzene, toluene Aromatic UNA, and chloroform and methylene chloride, and halogen-substituted solvents or a mixed solvent such as carbon tetrachloride can be used.

  For the production of the silver complex compound, in addition to the above method, a solution in which the silver compound of the general formula (1) and one or more amine compounds are mixed is reacted with carbon dioxide to produce a silver complex. Compounds can also be produced. 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.

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

Ag [A] _m (5)
(In General formula (5), A is a compound of General formula (2)-(4), and m is 0.5-1.5.)
The silver coating liquid composition used for forming a highly reflective and highly glossy reflective surface contains the above-mentioned silver complex compound, and if necessary, a solvent, a stabilizer, a leveling agent, a thin film Adjuncts, reducing agents, and additives for thermal decomposition reaction accelerators can be contained in the silver coating composition. Additives such as adjuvants, reducing agents and thermal decomposition reaction accelerators can be contained in the silver coating composition of the present invention.

  On the other hand, examples of the stabilizer include amine compounds such as primary amines, secondary amines, and tertiary amines, ammonium carbamates, ammonium carbonates, ammonium bicarbonate compounds, phosphines, and phosphites. And a phosphorus compound such as phosphate, a sulfur compound such as thiol and sulfide, and at least one mixture thereof. Specific examples of amine compounds include, for example, methyl Amine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octyl Ruamine, 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, Perazine, 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-based compounds include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, and 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, pyridiumethylhexyl Carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, isopropyl Ruammonium 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, dioctadecylammoni 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 bi Examples thereof include carbonate, triethylenediaminium 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 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, and octylthioglycolate.

  The amount of such a stabilizer used is not particularly limited as long as it matches the ink characteristics of the present invention. However, the content is preferably 0.1% to 90% in terms of molar ratio with respect to the silver compound.

  Moreover, as a thin film adjuvant, an organic acid and an organic acid derivative, or a mixture of at least one or more thereof can be used. Specifically, for example, acetic acid, butyric acid (valeric acid), pivalic 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, Os, Manganese oxalate, gold acetate, palladium oxalate, silver 2-ethylhexanoate containing metals such as Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th And organic acid metal salts such as silver octanoate, silver neodecanoate, cobalt stearate, nickel naphthalate and cobalt naphthalate. Although the usage-amount of the said thin film adjuvant is not specifically limited, 0.1-25% is preferable by molar ratio with respect to a 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, metal salts such as ferrous chloride and iron lactate, hydrogen, hydrogen iodide, carbon monoxide, aldehyde compounds such as formaldehyde, acetaldehyde and glyoxal, methyl formate, butyl formate, triethyl Examples thereof include a mixture of at least one formic compound such as o-formic acid, at least one reducing organic compound such as glucose, ascorbic acid, and hydroquinone.

  Specific examples of the thermal decomposition reaction accelerator include, for example, ethanolamine, methyldiethanolamine, triethanolamine, propanolamine, butanolamine, hexanolamine, hydroxyalkylamines such as dimethylethanolamine, piperidine, and N-methylpiperidine. , Piperazine, N, N'-dimethylpiperazine, 1-amino-4methylpiperazine, pyrrolidine, N-methylpyrrolidine, amine compounds such as morpholine, acetone oxime, dimethylglyoxime, 2-butanone oxime, 2,3-butane Alkyl oximes such as dione monooxime, glycols such as ethylene glycol, diethylene glycol, and triethylene glycol, methoxyethylamine, ethoxyethylamine, methoxypropyl Alkoxyalkylamines such as ruamine, 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 addition, a solvent may be required for adjusting the viscosity of the silver coating solution composition or for smooth thin film formation. 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, ethylene glycol, glycols such as 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.

<5-3. Nitrogen-containing cyclic compound in the adjacent layer of the silver reflective layer>
When forming a silver reflective layer by heating and baking a coating film containing a silver complex compound capable of vaporizing and desorbing a ligand when forming a silver reflective layer, a nitrogen-containing cyclic layer is formed adjacent to the silver reflective layer. It is preferable to contain a compound. As the nitrogen-containing cyclic compound, broadly, a corrosion inhibitor and an antioxidant having an adsorptive group for silver are preferably used.

  In a corrosion inhibitor having an adsorptive group for silver, a desired corrosion prevention effect can be obtained by using a nitrogen-containing cyclic compound. For example, it is desirable to be selected from at least one of 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.

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

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

  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 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-phenyl Rumyl imidazole, 4-methyl-5-formyl imidazole, 2-ethyl-4-methyl-5-formyl imidazole, 2-phenyl-4-methyl-4-formyl imidazole, 2-mercaptobenzimidazole, etc., or these Of the mixture.

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

<5-4. Antioxidant>
As a corrosion inhibitor for the silver reflective layer used in the film mirror, an antioxidant can also be used.

  As the antioxidant, it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, and 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-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-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) propio , Triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-di-methyl-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 , 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

  Examples of the thiol 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 addition, the said antioxidant and the following light stabilizer can also be used together.

  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-t-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-tetramethyl Piperidine, 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.

  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 and the like can also be used.

  In particular, the hindered amine light stabilizer is preferably a hindered amine light stabilizer containing only a tertiary amine, specifically, 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, or A condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.

<6. Resin Film Support>
Various conventionally known resin films can be used as the resin film-like support. 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 film-like support is located farther from the light incident side than the silver reflecting layer, ultraviolet rays hardly reach the resin film-like support. In particular, when an ultraviolet absorber is contained in an acrylic layer or the like that is closer to the light incident side than the resin film-like support, ultraviolet rays are less likely to reach the resin film-like support. Therefore, the resin film-like support can be used even if it is a resin that easily deteriorates with respect to ultraviolet rays. From such a viewpoint, it becomes possible to use a polyester film such as polyethylene terephthalate as the resin film-like support.

  The thickness of the resin film-like support is preferably an appropriate thickness depending on the type and purpose of the resin. For example, it is generally in the range of 10 to 250 μm. Preferably it is 20-200 micrometers.

<7. Adhesive layer>
The adhesive layer of a film mirror is a layer for sticking a film mirror to a support base material by the said adhesive layer, and forming a mirror for sunlight reflection. The film mirror may have a release layer on the side opposite to the light incident side of the adhesive layer. When a film mirror has a peeling layer, after peeling a peeling layer from an adhesion layer, a film mirror can be affixed on a support base material through an adhesion layer.

  The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used. 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. Moreover, it is preferable that the thickness of an adhesion layer is the range of about 1-100 micrometers normally from viewpoints, such as an adhesion effect and a drying rate.

<8. Transparent hard coat layer>
A transparent hard coat layer may be provided on the light incident side of the acrylic layer. The transparent hard coat layer is provided for the purpose of preventing damage to the surface of the film mirror and adhesion of dirt. The transparent hard coat layer is preferably either the outermost layer, the second layer, or the third layer from the light incident side. Another thin layer (preferably 1 μm or less) may be provided on the transparent hard coat layer. The thickness of the hard coat layer is preferably 0.05 μm or more and 10 μm or less from the viewpoint of preventing the film mirror from warping while obtaining sufficient scratch resistance. More preferably, they are 1 micrometer or more and 10 micrometers or less.

  The material for forming the transparent hard coat layer is not particularly limited as long as transparency, weather resistance, hardness, mechanical strength, and the like can be obtained. The transparent hard coat layer can be composed of acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicone resin, and 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.), Toa Gosei Chemical Industry Co., Ltd .; "Aronix (registered trademark)" series, etc.), Nippon Oil and Fats Corporation; (trade name "Blemmer (registered trademark)" series, etc.), Nippon Kayaku Co., Ltd. (trade name "KAYARAD (registered trademark)" series, etc.), Kyoeisha Chemical Co., Ltd .; (Product name "Light Ester" series, "Light Acrylate" series, etc.) That.

  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. As materials that can be used for the transparent hard coat layer, an aqueous colloidal silica-containing acrylic resin (Japanese Patent Laid-Open No. 2005-66824), a polyurethane resin composition (Japanese Patent Laid-Open No. 2005-110918), and a water-based silicone compound are used as binders. Resin film (Japanese Patent Laid-Open No. 2004-142161) used as a photocatalytic oxide-containing silica film or alumina such as titanium oxide, photocatalytic film such as titanium oxide or niobium oxide having a high aspect ratio (Japanese Patent Laid-Open No. 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-based transparent hard coat layer. 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 an 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 a 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 outer surfaces, such as a film mirror, 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.

  For the ultraviolet curable acrylic hard coat layer, for example, an acrylic compound having an unsaturated group, such as pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra A polyfunctional (meth) acrylate mixture such as (meth) acrylate can be used, and a photopolymerization initiator such as benzoin, benzoin methyl ether, or benzophenone is blended and used. And this is apply | coated to outer surfaces, such as the reflective film 10, and a transparent hard-coat layer is formed by carrying out ultraviolet curing.

  Moreover, it is preferable to surface-treat to a transparent hard-coat layer and to provide hydrophilicity. For example, corona treatment (JP-A-11-172028), plasma surface treatment, ultraviolet ray / ozone treatment, surface projection formation (JP-A-2009-226613), surface fine processing treatment, and the like can be mentioned.

  As a method for producing the transparent hard coat layer, conventionally known coating methods such as a gravure coating method, a reverse coating method and a die coating method can be used.

  When the transparent hard coat layer 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.

Moreover, when a transparent hard-coat layer consists of inorganic substances, it is preferable to consist of the film | membrane which apply | coated polysilazane and heat-hardened. When the hard coat precursor 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. Thereby leaving a 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 an optionally substituted alkyl group, aryl group, vinyl group, 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 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 formula (6) are hydrogen atoms is used.

In another preferred embodiment, the transparent hard coat layer 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 general formula (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently of each other hydrogen, or 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. Further, R ¹ , R ³ , R ⁴ and R ⁶ represent hydrogen, and R ² and R ⁵ represent methyl.

Furthermore, in another preferable 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 ratio of polysilazane in the solvent is generally 1 to 80% by mass of polysilazane, preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass.

  As the solvent, water and a reactive group (for example, hydroxyl group or amine group) are not included, and an organic system which is inert to polysilazane and preferably an aprotic solvent is particularly 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 the polysilazane solution, further binders can be used, such as those conventionally used in the production of paints. 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 preparation, for example, an additive that affects the viscosity, wettability of the preparation, film forming property, lubricating action or exhaust property, or inorganic nanoparticles such as SiO ₂ TiO ₂ , ZnO, ZrO ₂ or Al ₂ O ₃ can be used.

  The polysilazane transparent hard coat layer 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, a hard coat layer 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.

<8-2. “A” component>
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 polyfunctional 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, a vinyl monomer, an allyl monomer, or a monofunctional monomer may be included. 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 1000 or more and less than 10,000 may be used. Is possible.

  Specific examples of the monofunctional (meth) acrylate monomer 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 ( 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 (meta 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, nonylphenoxy polypropylene glycol (Meth) acrylate, octafluoropentyl (meth) acrylate, Cutoxypolyethylene 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) a Relate, 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.

  Specifically, as the polyfunctional (meth) acrylate monomer, 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 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, Pentaerythri Tri (meth) acrylate, tri (meth) acrylate phosphate, trimethylolpropane tri (meth) acrylate, trimethylolpropanebenzoate 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.

  As a commercial item of "A" component which is such a polymeric organic compound, Toagosei Co., Ltd. Aronix M-400, M-408, M-450, M-305, M-309, M- 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, DPC manufactured by Nippon Kayaku Co., Ltd. -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, R- 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 weight based on the total composition of “A” + “B” being 100% by weight from the viewpoint of improving antifouling properties and light resistance. It is preferably 15 to 80% by weight.

<8-3. “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, monomers (a) having a radically polymerizable double bond and a polyorganosiloxane chain (1) to 50% by weight, and monomers other than (a) having a radically polymerizable double bond and a reactive functional group ( b) a polymer obtained by polymerizing a monomer comprising 10 to 95% by weight and a monomer (c) having a radical polymerizable double bond other than (a) and (b) (c). Activity which is a vinyl copolymer having a number average molecular weight of 5,000 to 100,000, obtained by reacting (α) with a functional group capable of reacting with the 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 radically polymerizable double bond and a polyorganosiloxane chain include one end of, for example, Silaplane FM-0711, FM-0721, FM-0725 manufactured by Chisso Corporation. Examples include (meth) acryloxy group-containing polyorganosiloxane compounds, AC-SQ SI-20 manufactured by Toa Gosei Co., Ltd., POSS (Polyhydrogen Oligomeric Silsesquioxane) series acrylates and methacrylate-containing compounds manufactured by Hybrid Plastics.

  The “B” component can be used alone or in combination of two or more according to the required performance. Moreover, it is preferable that a polymerization ratio is 1 to 50 weight% on the basis of the total weight of the monomer which comprises a polymer, More preferably, it is 10 to 35 weight%. When the copolymerization ratio of the “B” component is less than 1% by weight, it becomes difficult to impart antifouling properties and weather resistance to the upper surface of the cured product, and when it exceeds 50% by weight, 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.

  This transparent hard coat layer is preferably flexible and does not warp. The transparent hard coat layer on the outermost surface layer of the film mirror may form a dense cross-linked structure, which may cause the film to warp or bend easily and may be difficult to handle. become. 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 transparent hard coat layer composition.

<8-4. Additives>
Further, the transparent hard coat layer may contain an ultraviolet absorber or an antioxidant. As an ultraviolet absorber and antioxidant, <2-2. UV absorber> and <2-3. Antioxidants> can be used.

In particular, a preferred UV absorber in a hard coat layer containing a polyfunctional acrylic monomer and a silicone resin is a benzotriazole-based UV absorber. By including a benzotriazole-based ultraviolet absorber in the hard coat layer, it is possible to obtain an excellent effect that not only the weather resistance is further improved, but also the falling angle can be further reduced. In particular, when the compound represented by the following general formula (9) is contained in the hard coat layer, the effect of lowering the sliding 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 weight that was 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.

  In addition, it is preferable that the usage-amount of the ultraviolet absorber in a transparent hard-coat layer is 0.1-20 mass% in order to make a weather resistance favorable, keeping adhesiveness favorable. More preferably, it is 0.25-15 mass%, More preferably, it is 0.5-10 mass%.

  As the antioxidant used for the transparent hard coat layer, it is preferable to use an organic antioxidant such as a phenol-based antioxidant, a thiol-based antioxidant, and a phosphite-based antioxidant. The falling angle can also be reduced by including an organic antioxidant in the hard coat layer. An antioxidant and a light stabilizer may 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-t-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-tetramethyl Piperidine, 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, the hindered amine light stabilizer is preferably a hindered amine light stabilizer containing only a tertiary amine, specifically, 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, 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, a nickel-based ultraviolet stabilizer can also be used as the light stabilizer, and [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II) can be used as the nickel-based ultraviolet stabilizer. Nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl-dithiocarbamate, and the like.

  The transparent hard coat layer, particularly the hard coat layer containing a polyfunctional acrylic monomer and a silicone 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 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass with respect to 100 parts by mass 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.

  Various additives can be further blended in the transparent hard coat layer 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 a leveling agent, for example, a dimethylpolysiloxane-polyoxyalkylene copolymer (for example, SH190 manufactured by Toray Dow Corning Co., Ltd.) is suitable as a silicone leveling agent.

<9. Gas barrier layer>
A gas barrier layer may be provided on the light incident side of the silver reflective layer. It is preferable to provide a gas barrier layer between the acrylic layer and the silver reflective layer. Furthermore, it is preferable to provide a gas barrier layer between the adhesive layer and the resin coat layer. The gas barrier layer is intended to prevent the deterioration of the humidity, especially the resin film-like support and the constituent layers supported by the resin film-like support due to high humidity, but it has special functions and applications. As long as it has the function of preventing deterioration, a gas barrier layer of various modes can be provided.

As the moisture resistance of the gas barrier layer, 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, and still more preferably 0. .2 g / m ² · day or less. In addition, the oxygen permeability of the gas barrier layer 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 include a method of forming an inorganic oxide by a method such as vacuum vapor deposition, sputtering, ion beam assist, chemical vapor deposition, and the like. An inorganic oxide precursor by a sol-gel method is used. A method of forming an inorganic oxide film by applying heat treatment and / or ultraviolet irradiation treatment to the coating film after coating is also preferably used.

<9-2. Inorganic oxide>
The 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.

<9-3. Inorganic Oxide Precursor>
The gas barrier layer can be formed by applying a general heating method after applying a precursor that forms an inorganic oxide by heating, but is preferably formed by local heating. This precursor is preferably a sol-shaped organometallic compound or polysilazane.

<9-4. Organometallic compound>
The organometallic compounds are silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), indium (In), It is preferable to contain at least one element of 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 alkyl groups having 4 or less carbon atoms, for example, a methyl group CH ₃ (hereinafter represented by Me), an ethyl group C ₂ H ₅ (hereinafter represented by Et), a propyl group. C ₃ H ₇ (hereinafter represented by Pr), isopropyl group i-C ₃ H ₇ (hereinafter represented by i-Pr), butyl group C ₄ H ₉ (hereinafter represented by Bu), isobutyl group i- Lower alkyl groups such as C ₄ H ₉ (hereinafter represented by i-Bu) are more preferred.

Examples of the metal alkoxide represented by the above 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 isopropoxide Ba (OPr-i) ₂ , triethoxyborane B (OEt) ₃ , zirconium propoxide Zn (OPr) ₄ , lanthanum propoxide La (OPr) ₃ , yttrium propoxide Y (OPr) ₃ , lead isopropoxide Pb ( OPr-i) _{2 and the} like are preferable. 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.

<9-5. Sol-gel method>
Here, the “sol-gel method” is to obtain a hydroxide sol by hydrolyzing an organometallic compound, etc., dehydrate it into a gel, and then heat the gel. It refers to a method for preparing a metal oxide glass having a certain shape (film, particle, fiber, etc.). A multi-component metal oxide glass can be obtained by a method of mixing a plurality of different sol solutions, a method of adding other metal ions, or the like. 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 lower. 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 above-described metal alkoxides. 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 liquid 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 water ratio is preferably in the range of 0.2 to 50 mol / L as the water concentration.

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. Preferred examples of the compound that gives boron ion B ³⁺ include trialkoxyborane B (OR) ₃ . Among these, triethoxyborane B (OEt) ₃ is more preferable. Moreover, as a B ^<3+ > ion density | concentration in a reaction liquid, the range of 1.0-10.0 mol / L is preferable.

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 the fluorine ion source, ammonium hydrogen fluoride NH ₄ HF · HF, sodium fluoride NaF and the like are suitable. Preferred examples of the chlorine 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), the pH is adjusted using an acid such as hydrochloric acid. It is preferable to ripen after adjusting to the range of 4.5-5. 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 concentration of the same component and the reaction liquid (including B ³⁺ and halogen ions) are added to each other at the same rate while adjusting to a predetermined pH. The reaction product can also be produced 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 to raise the temperature gradually after paying attention to a temperature range of 50 to 70 ° C., followed by a preliminary drying (solvent volatilization) step. 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.

<10. Anchor layer>
An anchor layer is a layer which consists of resin and is provided in order to adhere | attach a resin film-like support body and a silver reflection layer. Therefore, the anchor layer has an adhesive property that allows the resin film-like support and the silver reflective layer to be in close contact, heat resistance that can withstand heat when the silver reflective layer is formed by a vacuum deposition method, and the silver reflective layer that is inherently high. Smoothness is required to bring out the reflection performance.

  The resin used for the anchor layer is not particularly limited as long as it satisfies the above adhesiveness, heat resistance, and smoothness conditions. Polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide Resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, etc. can be used singly or as a mixed resin. From the viewpoint of weather resistance, polyester resin and melamine resin mixed resin or polyester resin and acrylic resin can be used. A resin mixed resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable.

  The thickness of the anchor layer is preferably 0.01 to 3 μm, more preferably 0.1 to 2 μm. By satisfying this range, the unevenness of the resin film-like support surface can be covered while maintaining the adhesion, the smoothness can be improved, and the anchor layer can be sufficiently cured. The reflectance can be increased.

  Further, the anchor layer has the above-described <4-2. It is preferable to contain the corrosion inhibitor described in <Corrosion inhibitor>.

  In addition, the formation method of an anchor layer can use conventionally well-known coating methods, such as a gravure coat method, a reverse coat method, and a die coat method.

<11. Release layer>
The film mirror may have a release layer on the side opposite to the light incident side of the adhesive layer. For example, when a film mirror is shipped, it is shipped with the release layer attached to the adhesive layer, the film mirror having the adhesive layer is peeled off from the release layer, and is bonded to another substrate to form a solar reflective mirror. be able to.

  The release layer may be any layer that can impart protection to the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, a polyethylene terephthalate film or Plastic film or sheet such as sheet, fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., coating the resin kneaded with these, metal deposition such as aluminum, etc. A resin film or sheet subjected to the above surface treatment is used.

  Although there is no restriction | limiting in particular in the thickness of a peeling layer, Usually, it is preferable that it is the range of 12-250 micrometers.

  Moreover, it may be bonded after providing a concave portion or a convex portion before being bonded to these release layer film mirrors, or may be formed to have a concave portion or a convex portion after being bonded. Or forming so as to have a convex portion.

<12. Sunlight reflection mirror>
The mirror for sunlight reflection has a film mirror and a self-supporting base material, and the film mirror is joined to the base material via an adhesive layer.

<12-2. Self-supporting substrate>
The self-supporting substrate preferably has one of the following structures A and B.

A: A pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is a layer having a hollow structure or a layer made of a resin material.

  B: A resin material layer having a hollow structure.

  In the case of “self-supporting substrate”, “self-supporting” means supporting the opposite edge portions when cut to a size that can be used as a substrate for a solar reflective mirror. This means that the substrate has rigidity enough to support the substrate. The base material of the solar reflective mirror has a self-supporting property, so that it is easy to handle when installing the solar reflective mirror, and the holding member for holding the solar reflective mirror has a simple configuration. Therefore, it is possible to reduce the weight of the reflection device, and it is possible to suppress power consumption during solar tracking.

  As in Configuration A, the self-supporting base material is composed of a pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is formed of a layer having a hollow structure or a resin material. By having a layer that has high flatness due to a metal flat plate, and the intermediate layer is a layer having a hollow structure or a layer composed of a resin material, the base material is configured only by a metal flat plate. Compared to the case, the weight of the substrate can be greatly reduced, and the rigidity can be increased by the relatively lightweight intermediate layer, so that it can be a lightweight and self-supporting support. Become. Even in the case where a layer made of a resin material is used as the intermediate layer, it is possible to further reduce the weight by using a resin material layer having a hollow structure.

  In addition, 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 back side is prevented from being transmitted to the film mirror, preventing condensation and deterioration due to heat. Can be suppressed.

  As the metal flat plate forming the surface layer of the configuration A, 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 high metal material 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.

  When the intermediate layer of Configuration A has a hollow structure, a material such as a metal, an inorganic material (glass or the like), or a resin can be used. As the hollow structure, a cellular structure made of a foamed resin, a three-dimensional structure having a wall surface made of a metal, an inorganic material, or a resin material (such as a honeycomb structure), a resin material to which hollow fine particles are added, or the like can be used. The cellular structure of the foamed resin refers to a material in which a gas is finely dispersed in a resin material and formed into a foamed or porous shape, and a known foamed resin material can be used as the material. Polyurethane, polyethylene, polystyrene and the like are preferably used. The honeycomb structure represents a general three-dimensional structure composed of a plurality of small spaces surrounded by side walls. When the hollow structure is 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. Acrylic derivatives such as polyolefin (for example, polypropylene, high density polyethylene), polyamide, polystyrene, polyvinyl chloride, polyacrylonitrile, ethylene-ethyl acrylate copolymer, vinyl acetate copolymers such as polycarbonate, ethylene-vinyl acetate copolymer Terpolymers such as ionomers and 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.

  In addition, the intermediate layer can 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 support for the film mirror described above. Can do.

  The intermediate layer does not need to be provided in all regions of the base material, and may be provided in a part of the region as long as the flatness of the metal flat plate and the self-supporting property as the base material can be ensured. 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.

  As in the configuration B, the self-supporting base material can be a layer made of a resin material having a hollow structure. When the base material is made of a resin-only layer, the thickness required to obtain rigidity sufficient to provide self-supporting properties increases, and as a result, the weight of the base material increases, but the resin base material has a hollow structure. By providing the weight, it is possible to reduce the weight while providing a self-supporting property. In the case of a layer made of a resin material having a hollow structure, a resin sheet having a smooth surface is provided as a surface layer, and the resin material having a hollow structure is used as an intermediate layer from the viewpoint of increasing the regular reflectance of the film mirror. preferable. As the material of this resin sheet, the same material as that constituting the above-mentioned film mirror support can be preferably used, and as the resin material constituting the hollow structure, it is used for the above-mentioned foamed material and three-dimensional structure. The same resin material as that obtained can be preferably used.

<13. Holding member>
The solar power generation reflection device includes a holding member that holds a solar light reflecting mirror. The holding member preferably holds the sunlight reflecting mirror in a state where the sun can be tracked. Although there is no restriction | limiting in particular as a form of a holding member, For example, the form which hold | maintains several places with a rod-shaped holding member is preferable so that the mirror for sunlight reflection can hold | maintain a desired shape. The holding member has a configuration for holding the sunlight reflecting mirror in a state in which the sun can be tracked. However, when the sun is tracked, it may be driven manually, or a separate driving device is provided to automatically track the sun. It is good also as a structure.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.

(Preparation of silver complex compound-containing coating solution A)
In a 500 ml Schlenk flask equipped with a stirrer, 65.0 g (215 mmol) of 2-ethylhexylammonium 2-ethylcarbamate was dissolved in 150.0 g of isopropanol, and then 20.0 g (86.2 mmol) of silver oxide. Was added and reacted at room temperature. The reaction solution was initially reacted with a black suspension (Slurry), and as the complex compound was formed, it was observed that the color gradually faded and changed to transparent. Solution was obtained. To this solution was added 2.5 g of 2-hydroxy-2-methylpropylamine as a stabilizer, 85.0 g of n-butanol and 50.0 g of amyl alcohol as a solvent and stirred, and then a 0.45 micron membrane filter. As a result of filtering using a membrane filter and thermal analysis (TGA), a silver complex compound-containing coating solution A having a silver content of 4.87% by mass was produced.

[Comparative Example 1]
(Preparation of film mirror of Comparative Example 1)
An outline of the layer structure of Comparative Example 1 is shown in FIG. As the resin film-like support 1, a biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used. On one side of the polyethylene terephthalate film, a polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Super Becamine J-820 DIC), a TDI-based isocyanate (2,4-tolylene diisocyanate), an HDMI-based A resin mixed with isocyanate (1,6-hexamethylene diisocyanate) in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10% was coated by a gravure coating method, An anchor layer 2 having a thickness of 0.1 μm was formed, and a silver reflective layer having a thickness of 100 nm was formed on the anchor layer 2 as a silver reflective layer 3 by a vacuum deposition method. Next, an adhesive layer 4 and a transparent acrylic film (acrylic HBS010P thickness 100 μm, manufactured by Mitsubishi Rayon Co., Ltd.) as an acrylic layer 5 were bonded onto the silver reflective layer 3 at a lamination temperature of 60 ° C. by a dry lamination process. Further, one side of a 25 μm thick polyester separate film as a release layer 7 was prepared by adding 1 part of a platinum catalyst to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 to form a 35 mass% toluene solution. After forming a silicone adhesive layer 6 (Si system) having a thickness of 25 μm by heating at 130 ° C. for 5 minutes, it is laminated on the side opposite to the anchor layer and the silver reflecting layer of the polyethylene terephthalate film, A film mirror of Comparative Example 1 was obtained.

(Production of solar reflective mirror)
The release layer 7 is peeled off from the reflective film of Comparative Example 1 above, and a 0.1 mm thick aluminum plate measuring 4 cm × 5 cm wide and a film mirror are bonded via the adhesive layer 6 to reflect sunlight. A mirror (A-1) was obtained. Similarly, mirrors for sunlight reflection were produced using the film mirrors of the following examples.

[Example 1]
(Preparation of film mirror of Example 1)
An outline of the layer structure of Example 1 is shown in FIG. As the resin film-like support 1, a biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used. On one side of the polyethylene terephthalate film, a polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Super Becamine J-820 DIC), a TDI-based isocyanate (2,4-tolylene diisocyanate), an HDMI-based A resin mixed with isocyanate (1,6-hexamethylene diisocyanate) in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10% was coated by a gravure coating method, An anchor layer 2 having a thickness of 0.1 μm was formed, and a silver reflective layer 3 having a thickness of 100 nm was formed on the anchor layer 2 as a silver reflective layer 3 by a vacuum deposition method. Further, a resin in which a polyester resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 is coated on the silver reflective layer 3 by a gravure coating method to obtain a thickness of 3.0 μm. The resin coat layer 8 was formed. Next, a transparent acrylic film (Acryprene HBS010P, thickness 100 μm, manufactured by Mitsubishi Rayon Co., Ltd.) containing an ultraviolet absorber as the acrylic layer 5 is laminated on the resin coating layer 8 by a dry lamination process. Bonding was performed at ° C. Furthermore, 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, which was a release layer 7 of a polyester separate film having a thickness of 25 μm. After coating on one side and heating at 130 ° C. for 5 minutes to form a silicone adhesive layer 6 (Si system) with a thickness of 25 μm, laminating on the opposite side of the polyethylene terephthalate film anchor layer and silver reflective layer, The film mirror of Example 1 was obtained.

  Moreover, the mirror for sunlight reflection (B-1) was produced using the film mirror of Example 1 by the method similar to the mirror for sunlight reflection (A-1).

[Example 2]
(Preparation of film mirror of Example 2)
The outline of the layer structure of Example 2 is the same as that of Example 1 shown in FIG. In the same manner as in Example 1 except that 2-mercaptobenzothiazole was added to the resin coat layer 4 of Example 1 as a silver corrosion inhibitor so as to be 10% by mass with respect to the resin. 2 film mirrors were obtained.

  Moreover, the mirror for sunlight reflection (C-1) was produced using the film mirror of Example 2 by the method similar to the mirror for sunlight reflection (A-1).

[Example 3]
(Preparation of film mirror of Example 3)
An outline of the layer structure of Example 3 is shown in FIG. On the resin coating layer 8 of Example 2, a 3% perhydropolysilazane solution in dibutyl ether (NL120 manufactured by Clariant) was bar-coated so that the thickness of the dried film was 100 nm, and the coating was performed for 3 minutes. After natural drying, a film mirror of Example 3 was obtained in the same manner as in Example 2 except that annealing was performed in an oven at 90 ° C. for 30 minutes to provide the gas barrier layer 8.

  Moreover, the mirror for sunlight reflection (D-1) was produced using the film mirror of Example 3 by the method similar to the mirror for sunlight reflection (A-1).

[Example 4]
(Preparation of film mirror of Example 4)
An outline of the layer structure of Example 4 is shown in FIG. On the transparent acrylic film of Example 3, a commercially available hard coat agent (Opster (registered trademark) Z7534 manufactured by JSR) was diluted with methyl ethyl ketone so that the solid content concentration became 50% by mass, and the average particle size was 1.5 μm. Acrylic fine particles (Chemisnow (registered trademark) MX series, manufactured by Soken Chemical Co., Ltd.) were added in an amount of 1% by mass based on the solid content of the hard coating agent to prepare a coating for a scratch-preventing layer. After coating the above-mentioned paint, it was dried at 80 ° C., further cured by irradiation with ultraviolet light 1.0 J / cm ² , and the same as in Example 3 except that a 6 μm thick transparent hard coat layer 10 was provided. The film mirror of Example 4 was obtained by the method.

  Moreover, the mirror for sunlight reflection (E-1) was produced using the film mirror of Example 4 by the method similar to the mirror for sunlight reflection (A-1).

[Example 5]
(Preparation of film mirror of Example 5)
Instead of the silver reflection layer 3 of Example 4, the silver complex compound-containing coating solution A was applied onto the anchor layer 2 so that the film thickness after drying of the heat-dried silver was 100 nm. A film mirror of Example 5 was obtained by drying by heating in a dry oven at 150 ° C. for 2 minutes to form a silver reflective layer 3.

  Moreover, the mirror for sunlight reflection (F-1) was produced using the film mirror of Example 5 by the method similar to the mirror for sunlight reflection (A-1).

[Example 6]
(Preparation of film mirror of Example 6)
An outline of the layer structure of Example 6 is shown in FIG. As the resin film-like support 1, a biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used. On one side of the polyethylene terephthalate film, a polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Super Becamine J-820 DIC), a TDI-based isocyanate (2,4-tolylene diisocyanate), an HDMI-based A resin mixed with isocyanate (1,6-hexamethylene diisocyanate) in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10% was coated by a gravure coating method, An anchor layer 2 having a thickness of 0.1 μm was formed, and a silver reflective layer 3 having a thickness of 100 nm was formed on the anchor layer 2 as a silver reflective layer 3 by a vacuum deposition method. Further, an acrylic resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 on the silver reflective layer 3, and Ciba Specialty Chemicals is used as a silver corrosion inhibitor and ultraviolet absorber. Resin in which Tinuvin 234 from Co., Ltd. was added to 25% by mass with respect to the resin was coated by a gravure coating method to form a resin coating layer 8 having a thickness of 1.0 μm. Further, the resin coating layer 8 was coated by an acrylic resin gravure coating method to form a second resin coating layer 11 having a thickness of 3.0 μm. Next, on the second resin coat layer 11, an adhesive layer 4 and a transparent acrylic film (acrylic HBS010P thickness 100 μm made by Mitsubishi Rayon) containing an ultraviolet absorber as the acrylic layer 5 are laminated by a dry lamination process. Bonding was performed at a temperature of 60 ° C. On the acrylic layer 5, a commercially available hard coat agent (Opster (registered trademark) Z7534 manufactured by JSR) is diluted with methyl ethyl ketone so that the solid content concentration becomes 50% by mass, and acrylic fine particles having an average particle size of 1.5 μm. A coating for a scratch-preventing layer was prepared by adding 1% by mass of Chemisnow (registered trademark) MX series manufactured by Soken Chemical Co., Ltd. to the solid content of the hard coat agent. After applying the above-mentioned paint, it was dried at 80 ° C. and further irradiated with ultraviolet rays 1.0 J / cm ² to be cured, thereby providing a transparent hard coat layer 10 having a thickness of 6 μm. Furthermore, 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, which was a release layer 7 of a polyester separate film having a thickness of 25 μm. After coating on one side and heating at 130 ° C. for 5 minutes to form a silicone adhesive layer 6 (Si system) with a thickness of 25 μm, laminating on the opposite side of the polyethylene terephthalate film anchor layer and silver reflective layer, The film mirror of Example 6 was obtained.

  Moreover, the mirror for sunlight reflection (G-1) was produced by the method similar to the mirror for sunlight reflection (A-1) using the film mirror of Example 6.

  Moreover, when producing the said solar reflective mirrors (B-1)-(G-1), it replaced with the aluminum plate of thickness 4mm x width 5cm by thickness 0.1mm, and adhesion of each film mirror. A layer and a self-supporting base material made of double-sided material were attached facing each other to produce a solar reflective mirror ((B-2) to (G-2)). A self-supporting substrate having a thickness of 2 mm was used. Double-sided material refers to a material that sandwiches layers having a hollow structure. The thickness of the metal flat plate was 0.12 mm on one side, and the intermediate resin layer was filled with a foamed polyethylene resin having a thickness of 1.76 mm. As a result of measuring the weight and driving power consumption rate, it was possible to significantly reduce the weight compared to the conventional solar reflective mirror, resulting in improved transport efficiency, shortened work, and contributed to cost reduction. .

[Evaluation]
About the solar reflective mirror obtained above, regular reflectance, weather resistance, and light resistance were measured by the following methods.

<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 regular reflectance of the film mirror after being left for 30 days under the conditions of a temperature of 85 ° C. and a humidity of 85% RH is measured by the same method as the above-mentioned light reflectance measurement, and the regular reflectance and forced degradation of the film mirror before forced degradation. From the regular reflectance of the subsequent film mirror, the decrease rate of 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: Decrease rate of regular reflectance is 20% or more

<Yellow change of sunlight collecting 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 tilted at 45 ° (January-June 2010, location: Hachioji, 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. The measurement results are shown in Table 2.

  The contents of the various film mirrors obtained are shown in Table 1 below, and the results of evaluation of the characteristics are shown in Table 2 below.

<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 required for one tracking incorporating the solar reflective mirror L-1 is 100 when the solar reflective mirror is incorporated in the solar tracking type solar power generation reflector. Show.

  The contents of the various film mirrors obtained are shown in Table 1 below, and the results of evaluating the characteristics are shown in Tables 2 and 3 below.

  As is apparent 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-mentioned means of the present invention, while preventing a decrease in regular reflectance due to the deterioration of the silver reflective layer, it is lightweight and flexible, light resistance and weather resistance that can be reduced in production cost and can be increased in area and mass-produced. It can be seen that it is possible to provide a film mirror having excellent specularity, antifouling property, and scratch resistance, and having a good regular reflectance with respect to sunlight, a method for producing the same, and a solar reflective mirror using the film mirror.

DESCRIPTION OF SYMBOLS 1 Resin film-like support body 2 Anchor layer 3 Silver reflection layer 4 Adhesive layer 5 Acrylic layer 6 Adhesive layer 7 Peeling layer 8 Resin coat layer 9 Gas barrier layer 10 Transparent hard coat layer 11 2nd resin coat layer 20 (20b-20e) film mirror

Claims (8)

A film mirror in which a silver reflective layer is provided on a resin film support,
In order from the light incident side, an acrylic layer, an adhesive layer, a resin coat layer, the silver reflective layer, the resin film-like support and an adhesive layer,
The film mirror, wherein the acrylic layer contains an ultraviolet absorber. The resin coat layer and the silver reflective layer are adjacent to each other,
The film mirror according to claim 1, wherein the resin coat layer contains a silver corrosion inhibitor.   The film mirror according to claim 1, further comprising a transparent hard coat layer on a light incident side of the acrylic layer.   The film mirror according to claim 1, further comprising a gas barrier layer on a light incident side with respect to the silver reflection layer. The film mirror according to any one of claims 1 to 4 and a self-supporting base material,
The solar reflective mirror, wherein the film mirror is bonded to the substrate via the adhesive layer.   The said base material has a pair of metal flat plate and the intermediate | middle layer provided between the said metal flat plates, The said intermediate | middle layer is a layer or resin layer which has a hollow structure, It is characterized by the above-mentioned. The solar reflective mirror described.   The solar reflective mirror according to claim 5, wherein the substrate is made of a resin layer having a hollow structure.   A solar power generation reflecting device comprising the solar light reflecting mirror according to claim 5.

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