WO2014061497A1

WO2014061497A1 - Film mirror, and reflecting apparatus for solar thermal power generation

Info

Publication number: WO2014061497A1
Application number: PCT/JP2013/077274
Authority: WO
Inventors: 鈴木　利継
Original assignee: コニカミノルタ株式会社
Priority date: 2012-10-16
Filing date: 2013-10-07
Publication date: 2014-04-24
Also published as: JPWO2014061497A1

Abstract

In order to provide a film mirror, which has high corrosion resistance even on a cut end surface after cutting, and a reflecting apparatus for solar thermal power generation, this film mirror having a metallic reflecting layer provided on a resin film-like supporting body is characterized in having an adhesive layer on the light input side of the reflecting layer or on the rear side of the reflecting layer, and in having the adhesive layer containing a corrosion inhibitor for a same kind of metal with which the reflecting layer is formed.

Description

Film mirror and reflector for solar power generation

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

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

Solar energy can be considered as one of the stable and abundant natural energies as alternative energy for fossil fuel. 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 of low energy density of solar energy by collecting solar energy with a huge concentrator.

Since the condensing device is exposed to ultraviolet rays, heat, wind and rain, sandstorms, etc. by sunlight, conventionally, a glass mirror has been used for the concentrating 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. pass 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 response to the above problems, resin mirrors using an acrylic film that blocks ultraviolet rays and has excellent light resistance have been proposed (for example, Patent Document 3 and Patent Document 4). However, in the layer structure proposed in Patent Document 3 and Patent Document 4, since the pressure-sensitive adhesive layer easily transmits various substances, contaminants invade from the interface between the pressure-sensitive adhesive layer and the silver reflective layer, and silver corrosion occurs. There were problems such as easy progress. In particular, corrosion of the end face obtained by cutting the mirror is remarkable, and it has been desired to prevent corrosion of the cut end face.

US Pat. No. 4,307,150 US Pat. No. 4,645,714 Special table 2009-520174 US Patent Application Publication No. 2012/0107609

In view of this point, an object of the present invention is to provide a film mirror and a solar power generation reflecting device having high corrosion resistance even at an end face after cutting (cut end face; cut end).

The above object of the present invention is achieved by the following configuration.

1. A film mirror in which a metal reflective layer is provided on a resin film-like support, having a pressure-sensitive adhesive layer on either the light incident side or the back side of the reflective layer, and the pressure-sensitive adhesive layer A film mirror comprising a corrosion inhibitor of the same kind of metal as the metal of the reflective layer.

2. 2. The film mirror as described in 1 above, wherein the metal reflective layer is a silver reflective layer.

3. 1 or 2 characterized in that the reflective layer has a pressure-sensitive adhesive layer on both the light incident side and the back side thereof, and contains a silver corrosion inhibitor in both or one side of the pressure-sensitive adhesive layer. 2. The film mirror according to 2.

4. Any of the above 1 to 3, wherein the reflective layer has an adhesive layer on both the light incident side and the back side thereof, and the adhesive layer contains a silver corrosion inhibitor. The film mirror as described in any one.

5. 5. The film mirror according to any one of 1 to 4, wherein the metal corrosion inhibitor is a silver corrosion inhibitor and is at least one of a mercapto compound and a benzotriazole compound. .

6. The film mirror according to any one of 1 to 5 described above is further subjected to a cutting treatment to extend a pressure-sensitive adhesive containing a metal corrosion inhibitor in the pressure-sensitive adhesive layer at the cut portion to cover the metal reflective layer on the cut end surface. A film mirror characterized by comprising:

7. A reflector for solar power generation, wherein the film mirror according to any one of 1 to 6 is formed by being attached to a support base material.

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 film mirror for solar power generation according to the present invention will be described in detail. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

<1. Film mirror>
A film mirror 20 for solar power generation according to an embodiment of the present invention includes, in order from the light incident side, an acrylic layer 5, an adhesive layer or an adhesive layer 4, a resin coating layer 8, a metal (silver) reflective layer 3, and a resin. It has a film-like support 1 and an adhesive layer 6. 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 pressure-sensitive adhesive layer 6.

In the case where another layer is interposed between the above-mentioned layers, or when another layer is provided on the acrylic layer 5 or the pressure-sensitive adhesive layer 6, preferred examples include the following.

A gas barrier layer (not shown) may be provided somewhere on the light incident side of the metal (silver) reflective layer 3. A transparent hard coat layer (not shown) may be provided on the light incident side of the acrylic layer 5. An anchor layer 2 may be provided between the metal (silver) reflective layer 3 and the resin film-like support 1. Moreover, you may provide the peeling layer 7 which covers the adhesive layer 6. FIG.

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

According to the film mirror of the present invention, the adhesive is cured after bonding, whereas the adhesive keeps the viscosity after bonding, so when the film mirror is cut with a cutter or scissors (a cutting device or a cutting device at the time of mass production), Part of the adhesive moves to the cut surface, covers the metal reflective layer of the cut surface, and can prevent the metal reflective layer from being exposed. By including a corrosion inhibitor for preventing corrosion of the metal reflection layer in the pressure-sensitive adhesive layer, the effect can be exhibited particularly remarkably.

The details of the configuration of each layer are described below.

<2. Acrylic layer>
The purpose of providing the acrylic layer 5 is to absorb and block ultraviolet rays to prevent deterioration and discoloration of the lower resin layer (resin coat layer 8, adhesive layer 4, resin film support 1 and the like), and film peeling. It is to provide excellent light resistance and weather resistance. Therefore, the acrylic layer 5 contains an ultraviolet absorber. The acrylic layer 5 may contain an antioxidant. Since the acrylic layer 5 is hard, it may contain plasticizer fine particles in order to obtain an acrylic layer 5 that is soft and difficult to break. Preferable examples of the plasticizer fine particles include butyl rubber and butyl acrylate fine particles. The thickness of the acrylic layer 5 is preferably 20 to 150 μm. More preferably, it is 40 to 100 μm. If the thickness of the acrylic layer 5 is 20 μm or more, an appropriate amount of the ultraviolet absorber is contained, so that the ultraviolet blocking function to the lower resin layer can be sufficiently exhibited. If the thickness of the acrylic layer 5 is 150 μm or less, the flexibility can be sufficiently maintained, so that cracks and cracks can be effectively prevented.

The acrylic layer 5 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. The methacrylic acid ester is 50% by mass or more and the other monomer is 50% by mass or less. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used. A particularly preferred methacrylic resin is polymethyl methacrylate resin (PMMA).

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

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

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

The monomer other than alkyl methacrylate and alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monofunctional monomer. Although it may be a monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used. Examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene, and alkenyl cyan compounds such as acrylonitrile and methacrylonitrile. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Alkenyl esters of unsaturated carboxylic acids such as allyl 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 glass transition temperature of the methacrylic resin is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat resistance of the film. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.

The methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity showing a formability to a suitable film, it is preferable to use a chain transfer agent during the polymerization. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.

<2-1. UV absorber>
Details of the ultraviolet absorber contained in the acrylic layer 5 will be described below.

The purpose of adding the ultraviolet absorber is to give the acrylic layer 5 a function of absorbing and blocking ultraviolet rays. 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 hindered amine type, a benzoate type, etc. are mentioned, Moreover, titanium oxide, zinc oxide, Examples include cerium oxide and iron oxide. In order to reduce the problem of bleeding out when a large amount of the ultraviolet absorber is contained, it is preferable to use a high molecular weight ultraviolet absorber having a weight average molecular weight of 1000 or more. The weight average molecular weight is preferably 1000 or more and 3000 or less.

Examples of benzophenone ultraviolet absorbers 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' -Tetrahydroxy-benzophenone and the like.

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 commercially available products are LA31 from ADEKA Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylethyl) phenol (molecular weight 447.6; examples of commercially available products include Tinuvin 234 from Ciba Specialty Chemicals)

Examples of the phenyl salicylate UV 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-to Azine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- 1,3,5-triazine, [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol] (Tinuvine 1577FF, trade name, Ciba Specialty) Chemicals), [2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol] (CYASORB UV-1164, commodity Name, manufactured by Cytec Industries).

Examples of the benzoate-based 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 vibrational energy in the molecule and releasing the vibrational energy as heat energy or the like can be used. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers acting as a light energy conversion agent, called quenchers, can be used in combination. However, when using the above-mentioned ultraviolet absorber, it is necessary to select one in which the light absorption wavelength of the ultraviolet absorber does not overlap with the effective wavelength of the photopolymerization initiator. When a normal ultraviolet absorber is used, it is effective to use a photopolymerization initiator that generates radicals with visible light.

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

The content of the ultraviolet absorber in the acrylic layer is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further 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, more preferably 0.4 to 2.2. 28 g / m ² . By setting the content within the above range, it is possible to prevent the roll and the film from being soiled by bleeding out of the ultraviolet absorber while sufficiently exhibiting the weather resistance.

<2-2. Antioxidant>
In order to prevent the acrylic layer 5 from being deteriorated during melt film formation or to capture the radicals and prevent the acrylic layer 5 from being deteriorated, the acrylic layer 5 may contain an antioxidant. 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-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate The Ethylene 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-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

Examples of the hindered amine antioxidant 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-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6- Tetramethi 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-based antioxidant is preferably a hindered amine-based antioxidant 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 1, A condensate of 2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.

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

Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol. Diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene- Examples thereof include diphosphonite and 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite.

In addition, the above antioxidant and the following light stabilizer can be used in combination. As the light stabilizer, for example, a nickel-based ultraviolet stabilizer can be used. As the nickel-based ultraviolet 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.

The content of the antioxidant in the acrylic layer 5 is preferably 0.1 to 10% by mass, more preferably 0.5 to 3% by mass. When the content of the antioxidant in the acrylic layer 5 is within the above range, an excellent antioxidant function can be exhibited without impairing the function (the purpose) required for the acrylic layer 5.

When the antioxidant and the light stabilizer are used in combination, the content of the light stabilizer in the acrylic layer 5 is preferably 0.1 to 10% by mass, more preferably 0.5 to 3% by mass. When the content of the light stabilizer in the acrylic layer 5 is within the above range, an excellent light stabilizing function can be effectively expressed without impairing the function (the purpose) required of the acrylic layer 5. .

<3. Adhesive layer>
The adhesive layer 4 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 5 and the resin coat layer 8 together. The adhesive layer 4 has an adhesion property that allows the layers to adhere to each other, heat resistance that can withstand heat when the metal (silver) reflective layer 3 is formed by a vacuum deposition method, and the metal (especially silver) reflective layer 3 is originally used. It is preferable to have smoothness to bring out the high reflection performance.

In the case where an adhesive layer containing a metal corrosion inhibitor of the same type as the metal of the reflective layer 3 is provided on the light incident side of the metal reflective layer 3, between the acrylic layer 5 and the metal (silver) reflective layer 3. It is desirable to provide an adhesive layer. Specifically, the adhesive layer 4 may be used as a pressure-sensitive adhesive layer as in the examples, or a new pressure-sensitive adhesive layer may be provided between the resin coat layer 8 and the metal (silver) reflective layer 3. Good. When the adhesive layer 4 is used as a pressure-sensitive adhesive layer containing the same type of metal corrosion inhibitor as the metal of the reflective layer 3, the same kind of metal (silver) as the metal of the reflective layer 3 is used for the adhesive layer 4 as well. Contains corrosion inhibitors. Such a metal (silver) corrosion inhibitor will be described in detail in the explanation section of the resin coat layer 8 to be described later. Here, when the adhesive layer 4 is used as an adhesive layer containing the same type of metal corrosion inhibitor as the metal of the reflective layer 3, the metal (silver) of the adhesive layer provided at the position of the adhesive layer 4. ) The corrosion inhibitor covers the cut surface of the metal (silver) reflective layer 3 at the time of cutting (cutting), prevents corrosion from the cut surface, and oxygen, water vapor, hydrogen sulfide through the resin layer (acrylic layer 5). Or the like can be transmitted, and the metal (silver) of the reflective layer 3 can be corroded. On the other hand, the metal (silver) corrosion inhibitor of the resin coat layer 8 close to (adjacent to) the metal (silver) reflective layer 3 is mainly permeable to oxygen, water vapor, hydrogen sulfide, etc. through the resin layer (acrylic layer 5). And it can contribute to solving the problem of the prior art that the metal (silver) of the reflective layer 3 is corroded. In addition, an adhesive layer containing a metal corrosion inhibitor is provided on the side (for example, when the cutter is inserted from the light incident side) at the time of cutting (cutting). Is desirable. When cutting, the adhesive containing the metal corrosion inhibitor protrudes due to the pressing force for fixing the film mirror, and the adhesive containing the metal corrosion inhibitor tends to cover the end face of the metal reflection layer on the cut section. It is. However, even if the pressure-sensitive adhesive layer containing the metal corrosion inhibitor is provided on the side opposite to the side where the cutting blade is inserted at the time of cutting (cutting), the effects of the present invention can be expressed (Table 1). (Refer to the comparison between Examples 4 to 7 (light incident side) and Examples 8 to 12 (on the side opposite to the light incident side)). More preferably, it has a pressure-sensitive adhesive layer on both the light incident side (for example, the adhesive layer 4 is used as a pressure-sensitive adhesive layer) and the back side (pressure-sensitive adhesive layer 6 described later) of the metal reflective layer 3. In addition, it is excellent that both the pressure-sensitive adhesive layers contain a metal (especially silver) corrosion inhibitor in that the above-described effects can be obtained more significantly (see Examples 13 to 16 in Table 1). )

The adhesive layer 4 may consist of only one layer or a plurality of layers. The thickness of the adhesive layer 4 is preferably 1 to 10 μm, more preferably 3 to 8 μm, from the viewpoints of adhesion, smoothness, reflectance of the reflecting material, and the like.

When the adhesive layer 4 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-based resins, epoxy-based resins, polyamide-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymer-based resins, etc. can be used singly or as a mixed resin. From the viewpoint of weather resistance, polyester-based resins and melamine-based resins or A mixed resin of a polyester-based 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 4, a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method or the like can be used.

Further, even when the adhesive layer 4 is a metal oxide or a metal nitride, there is no particular limitation as long as the above adhesiveness, heat resistance, and smoothness conditions are satisfied. For example, silicon oxide, It can be formed by various vacuum film forming methods such as 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. The adhesive layer 4 may be a single layer (film) of the above metal oxide or metal nitride, or may be a laminate (film) of two or more layers.

<4. Resin coat layer>
The resin coat layer 8 prevents intrusion of moisture and chemicals in the air into the metal reflective layer 3 (mirror surface) (and thus prevents corrosion of the metal material (for example, silver) of the reflective layer 3). It is provided for the purpose of protecting from external mechanical pressure, such as impact and scratching. For the above purpose, the resin coat layer 8 is provided between the acrylic layer 5 and the metal (preferably silver) reflective layer 3. When the resin coat layer 8 is adjacent to the metal (silver) reflective layer 3, the resin coat layer 8 is the same type of metal as the metal of the reflective layer 3 (so that the resin coat layer 8 prevents corrosion of the metal (silver) ( It is preferable to contain a silver) corrosion inhibitor. However, as long as the above object can be achieved, the metal (silver) reflection layer 3 may be provided apart from (without adjoining) the metal (silver) corrosion inhibitor. It is preferable to contain.

The resin coat layer 8 may consist of only one layer or a plurality of layers. The thickness of the resin coat layer 8 is preferably 1 to 10 μm, more preferably 2 to 8 μm. If the thickness of the resin coating layer 8 is 1 μm or more, intrusion of moisture and chemicals in the air into the metal reflection layer 3 (mirror surface), and mechanical pressure from the outside, such as impact and scratching, etc. Can be protected from. If the thickness of the resin coat layer 8 is 10 μm or less, the flexibility can be sufficiently maintained, and cracks and cracks can be effectively prevented.

The resin coat layer 8 is mainly composed of a binder (resin) so as to maintain high film adhesion with the metal reflective layer 3 even when installed over a long period of time in an outdoor environment, and to achieve the above object. And a metal (silver) corrosion inhibitor of the same type as the metal of the reflective layer 3. Among these, as the binder (resin) 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, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide, polyamide, fluororesin, nylon (registered trademark), polymethyl A methacrylate, an acrylic resin, etc. can be mentioned. Among these, an acrylic resin is preferable.

<4-2. Corrosion inhibitor>
As a metal (silver) corrosion inhibitor for the resin coat layer 8, from the viewpoint of preventing corrosion of the metal material of the reflective layer 3, the same type of metal as the metal of the reflective layer 3 (Al, Ag, Cr, Cu, Ni, Ti , Mg, Rh, Pt and Au, any element selected from the group of elements), preferably having an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which metal (silver) is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it (see JIS Z0103-2004). The optimum content of the corrosion inhibitor varies depending on the compound used, but is generally preferably in the range of 0.001 to 0.1 g / m ² .

As a corrosion inhibitor for the same type of metal as the metal of the reflective layer (any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt and Au), silicone It is desirable to be selected from a modified resin, a silane coupling agent, a compound containing a plurality of thiol groups, and a corrosion inhibitor having an adsorptive group for silver described below.

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 imidazole rings. It is desirable that the compound be selected from a compound having an indazole ring, a copper chelate compound, a thiourea, a mercapto group-containing compound, 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. The silicone-modified resin is not particularly limited.

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

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

Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy- '-Tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) benzotriazole 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercially available products are LA31 from ADEKA Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylethyl) phenol (molecular weight 447.6; examples of commercially available products are Tinuvin 234 from Ciba Specialty Chemicals) 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 compounds having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or a mixture thereof.

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

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

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

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

As a compound having a mercapto group, mercaptoacetic acid, thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto can be used by adding the above-described materials. -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, trimethylolpropane tris (β-thiopropionate) or the like Of the mixture.

Examples of naphthalene-based compounds include thionalide.

<5. Metal reflective layer>
The metal reflective layer 3 formed on the film mirror 20 according to the present invention is a layer made of metal or the like having a function of reflecting sunlight.

The surface reflectance of the reflective layer 3 is preferably 80% or more, more preferably 90% or more. The reflective layer 3 is preferably formed of a material containing any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt, and Au. Among these, it is preferable that Al or Ag is a main component from the viewpoint of reflectance and corrosion resistance, and two or more such metal thin films may be formed. In the present invention, the silver reflective layer 3 containing silver as a main component is particularly preferable.

Further, a layer made of a metal oxide such as SiO ₂ or TiO ₂ may be provided on the reflective layer 3 to further improve the reflectance.

As a method for forming the reflective layer 3 (for example, a silver reflective layer) in the present invention, for example, either a wet method or a dry method can be used.

The wet method is a general term for a plating method or a metal complex solution coating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction and silver layer formation by firing of a silver complex ink (specifically, firing of a coating film formed by applying a silver coating liquid composition containing a silver complex compound).

On the other hand, the dry method is a general term for a vacuum film forming method, and specifically includes a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, and a sputtering method. Etc. 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. That is, in the manufacturing method of the film mirror 20 of this invention, it is preferable to form the reflection layer 3 by vapor deposition of silver.

The thickness of the reflective layer 3 is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectivity and the like.

Among these, a particularly suitable silver reflecting layer 3 is a layer mainly composed of silver (preferably a layer made of silver) having a function of reflecting sunlight well. The surface reflectance of the silver reflective layer 3 is also preferably 80% or more, and more preferably 90% or more. The thickness of the silver reflective layer 3 is also preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectivity and the like. In addition, the surface reflectance of the metal (silver) reflective layer 3 can be measured using a commercially available spectrophotometer.

<5-2. Metal (silver) complex compound having a ligand that can be vaporized / desorbed>
When the metal (silver) reflective layer 3 is formed, the metal (silver) reflective layer 3 is formed by heating and baking a coating film containing a metal (silver) complex compound from which a ligand can be vaporized and desorbed. It may be.

“Metal (silver) complex compound having a ligand that can be vaporized / desorbed” means that the metal (silver) is dissolved in a solution in a stable manner, but the solvent is removed and the mixture is heated and fired. This means a metal (silver) complex compound in which a ligand is thermally decomposed to become CO ₂ or a low molecular weight amine compound, which is vaporized / desorbed to leave only a metal simple substance (metal silver).

As for such a metal (silver) complex compound and a method for producing the same, for example, the silver complex compounds and methods for producing the same described in paragraphs “0064” to “0089” of JP-A-2012-137579 are appropriately used. be able to.

<5-3. Nitrogen-containing cyclic compound that can be used in adjacent layer of metal (silver) reflective layer>
When forming the metal (silver) reflective layer 3 by heating and baking a coating film containing a metal (silver) complex compound from which a ligand can be vaporized and desorbed when forming the metal (silver) reflective layer 3 It is preferable that the adjacent layer (resin coat layer 8, anchor layer 2, etc.) of the metal (silver) reflective layer 3 contains a nitrogen-containing cyclic compound. The content of the nitrogen-containing cyclic compound in the adjacent layer of the metal (silver) reflective layer 3 is preferably 0.001 to 5% by mass, more preferably 0.01 to 1% by mass. When the content of the nitrogen-containing cyclic compound in the adjacent layer of the metal (silver) reflective layer 3 is 0.001% by mass or more, the rust prevention and corrosion prevention functions of the metal (silver) can be effectively expressed. When the content of the nitrogen-containing cyclic compound in the adjacent layer of the metal (silver) reflective layer 3 is 5% by mass or less, the embrittlement preventing function of the adjacent layer can be effectively expressed without coloring. As the nitrogen-containing cyclic compound, roughly, a corrosion inhibitor and an antioxidant having an adsorptive group for metal (silver) are preferably used.

In the corrosion inhibitor having an adsorptive group for metal (silver), a desired corrosion prevention effect can be obtained by using a nitrogen-containing cyclic compound. The content of the corrosion inhibitor having an adsorptive group for the metal (silver) in the adjacent layer of the metal (silver) reflective layer 3 is preferably 0.001 to 5% by mass, more preferably 0.01%. To 1% by mass. If the content of the corrosion inhibitor having an adsorptive group for the metal (silver) in the adjacent layer of the metal (silver) reflective layer 3 is 0.001% by mass or more, the corrosion prevention function of the metal (silver) is effective. Can be expressed. If the content of the corrosion inhibitor having an adsorptive group for the metal (silver) in the adjacent layer of the metal (silver) reflective layer 3 is 5% by mass or less, the function of preventing the embrittlement of the adjacent layer is achieved without coloring. It can be expressed effectively. 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 <4-2. Among the compounds listed as corrosion inhibitors having an adsorptive group for silver among the metal (silver) corrosion inhibitors of the resin coating layer 8 of the corrosion inhibitor>, compounds specifically exemplified as “compounds having a pyrrole ring” Can be used.

Examples of the compound having a triazole ring include <4-2. Among the compounds listed as corrosion inhibitors having an adsorptive group for silver among the metal (silver) corrosion inhibitors of the resin coating layer 8 of the corrosion inhibitor>, compounds specifically exemplified as “compound having a triazole ring” Can be used.

Examples of the compound having an imidazole ring include <4-2. Among the compounds listed as corrosion inhibitors having an adsorptive group for silver among the metal (silver) corrosion inhibitors of the resin coating layer 8 of the corrosion inhibitor>, compounds specifically exemplified as “compounds having an imidazole ring” Can be used.

<5-4. Antioxidant>
As the nitrogen-containing cyclic compound contained in the adjacent layer (for example, the resin coat layer 8 or the anchor layer 2) of the metal (silver) reflective layer 3 used in the film mirror 20 according to the present invention, an antioxidant may be used. it can. When the content of the antioxidant in the adjacent layer of the metal (silver) reflective layer 3 is 0.001% by mass or more, the antioxidant function of the metal (silver) can be effectively expressed. When the content of the antioxidant in the adjacent layer of the metal (silver) reflective layer 3 is 5% by mass or less, the embrittlement preventing function of the adjacent layer can be effectively expressed without coloring.

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

As the phenolic antioxidant, <2-2. Among the various antioxidants listed as antioxidants to be contained in order to prevent deterioration of the acrylic layer 5 of antioxidant>, compounds specifically exemplified as “phenolic antioxidants” can be used. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

As the phosphite-based antioxidant, <2-2. Of the various antioxidants listed as antioxidants to be included in order to prevent deterioration of the acrylic layer 5 of the antioxidant>, compounds specifically exemplified as “phosphite antioxidants” can be used.

In addition, the above antioxidant and the following light stabilizer can be used in combination. When the content of the light stabilizer in the adjacent layer of the metal (silver) reflective layer 3 is 0.001% by mass or more, the light stabilizing function can be effectively expressed. If the content of the light stabilizer in the adjacent layer of the metal (silver) reflective layer 3 is 5% by mass or less, the embrittlement preventing function of the adjacent layer can be effectively expressed without coloring.

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-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6 -Tetramethi 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, etc. can also be used.

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

<6. Resin Film Support>
As the resin film-like support (film substrate) 1, various conventionally known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, norbornene resin film, polymethyl Penten film, polyetherketone Irumu, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, at least one selected from the group consisting of polycarbonate films, polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films is 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 1 is located farther from the light incident side than the metal (particularly silver) reflective layer 3, it is difficult for ultraviolet rays to reach the resin film-like support 1. In particular, when an ultraviolet absorber is contained in the acrylic layer 5 or the like that is closer to the light incident side than the resin film-like support 1, ultraviolet rays are less likely to reach the resin film-like support 1. Therefore, the resin film-like support 1 can be used even if it is a resin that easily deteriorates with respect to ultraviolet rays. From such a viewpoint, a polyester film such as polyethylene terephthalate can be used as the resin film-like support 1.

The thickness of the resin film-like support 1 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. The thickness is preferably 20 to 200 μm.

<7. Adhesive layer>
The pressure-sensitive adhesive layer 6 of the film mirror 20 according to the present invention is a layer for attaching the film mirror 20 to a supporting substrate with the pressure-sensitive adhesive layer 6 to form a solar light reflecting mirror. The film mirror 20 may have a release layer 7 on the side opposite to the light incident side of the pressure-sensitive adhesive layer 6. In the case where the film mirror 20 has the release layer 7, the film mirror 20 can be attached to the support substrate via the pressure-sensitive adhesive layer 6 after the release layer 7 is peeled from the pressure-sensitive adhesive layer 6.

As the corrosion inhibitor of the same metal (silver) as that of the reflective layer 3 contained in the pressure-sensitive adhesive layer 6, the above <4-2. Examples of the corrosion inhibitor described in the section <Corrosion inhibitor>. Preferably, it is at least one selected from the group consisting of a mercapto compound and a benzotriazole compound, and a mercapto compound is particularly preferable. By using these, corrosion of the metal reflective layer at the cut end after cutting can be more significantly prevented.

The content of the same kind of metal (silver) corrosion inhibitor as the metal of the reflective layer 3 in the pressure-sensitive adhesive layer 6 is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass. % Or more and 3% by mass or less. When the content of the metal (silver) corrosion inhibitor in the pressure-sensitive adhesive layer 6 is 0.01% by mass or more, a desired corrosion prevention function can be effectively exhibited. If the content of the metal (silver) corrosion inhibitor in the pressure-sensitive adhesive layer 6 is 10% by mass or less, the embrittlement prevention function that can prevent the pressure-sensitive adhesive layer 6 from becoming brittle without being colored is effective. Can be expressed.

Other configurations of the pressure-sensitive adhesive layer 6 are not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, a pressure-sensitive adhesive, a heat seal agent, a hot melt agent, and the like is used. Examples of the adhesive include polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, silicone resin (for example, addition reaction type silicone adhesive), nitrile rubber, and silicone rubber. It is done. The pressure-sensitive adhesive layer 6 may contain a curing accelerator such as a platinum-based catalyst. The method for producing the pressure-sensitive adhesive layer 6 is not particularly limited, and a laminating method (for example, a pressure-sensitive adhesive composition is applied on the film of the resin film-like support 1 and the film of the release layer 7 and heated for adhesion. The adhesive layer 6 is formed, and the film of the resin film-like support 1 and the film of the release layer 7 are laminated through the adhesive layer 6 and bonded to each other. The method can be applied. 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. In addition, the thickness of the pressure-sensitive adhesive layer 6 is usually preferably in the range of about 1 to 100 μm from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.

The hardness of the pressure-sensitive adhesive layer 6 is the effect of the present invention (the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 6 protrudes to the side (cut) at the time of cutting, and covers the metal reflective layer 3 at the end (cut). 3 can be effectively prevented), and is not particularly limited, but is preferably 10 ⁷ dyn / cm ² or less, more preferably 1 × 10 6. It is in the range of ⁴ to 10 ⁶ dyn / cm ² . If the hardness of the pressure-sensitive adhesive layer 6 is within the above range, the pressure-sensitive adhesive that protrudes to the side (cut end face) at the time of cutting is then applied to a solar power generation reflector for a long period of time during solar operation. Even when exposed, the metal reflective layer 3 at the end (cut end; end face of the cut) can be continuously covered without lowering (deteriorating) the viscosity.

<8. Transparent hard coat layer>
A transparent hard coat layer (not shown) may be provided on the light incident side of the acrylic layer 5. The transparent hard coat layer is provided for the purpose of preventing scratches on the surface of the film mirror 20 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 20 from being warped while obtaining sufficient scratch resistance. More preferably, they are 1 micrometer or more and 10 micrometers or less.

The material for forming the 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, a reactive diluent, and the like 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. The oligomer has a molecular weight that is somewhat large, for example, a weight average molecular weight of 1000 or more and less than 10,000.

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. (trade name) "Aronix (registered trademark)" series, etc.), Nippon Oil & Fats Co., Ltd .; (trade name "Blemmer (registered trademark)" series, etc.), Nippon Kayaku Co., Ltd. (product name, "KAYARAD (registered trademark)" series, etc.), Products such as Kyoeisha Chemical Co., Ltd. (trade name “Light Ester” series, “Light Acrylate” series, etc.) can be used.

More specifically, for example, a resin curable by electron beam or ultraviolet irradiation, a thermosetting resin, or the like can be used. In particular, a thermosetting silicone hard coat composed of a partially hydrolyzed oligomer of an alkoxysilane compound, a heat A hard coat made of a curable polysiloxane resin, an ultraviolet curable acrylic hard coat made of an acrylic compound having an unsaturated group, and a thermosetting inorganic material are preferable. Examples of materials that can be used for the transparent hard coat layer include 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 an aqueous silicone compound as a binder. Used as a resin film (Japanese Patent Laid-Open No. 2004-142161), a photocatalytic oxide-containing silica film such as titanium oxide or alumina, or a photocatalytic film such as titanium oxide or niobium oxide having a high aspect ratio (Japanese Patent Laid-Open No. 2009-62216) ), A photocatalyst-containing fluororesin coating film (Pierex Technologies), an organic / inorganic polysilazane film, a film using a hydrophilization accelerator (AZ Electronics Co., Ltd.) for organic / inorganic polysilazane, and the like.

For the thermosetting silicone-based transparent hard coat layer, a partially hydrolyzed oligomer of an alkoxysilane compound synthesized by a known method can be used. An example of the synthesis method is as follows. First, tetramethoxysilane or tetraethoxysilane is used as an alkoxysilane compound, and a predetermined amount of water is added to the alkoxysilane compound in the presence of an acid catalyst such as hydrochloric acid or nitric acid to remove by-produced alcohol from room temperature to 80 ° C. React with. By this reaction, the alkoxysilane is hydrolyzed, and further, a partially hydrolyzed oligomer of the alkoxysilane compound having an average polymerization degree of 4 to 8 having two or more silanol groups or alkoxy groups in one molecule is obtained by the condensation reaction. Next, a curing catalyst such as acetic acid or maleic acid is added to this and dissolved in an alcohol or glycol ether organic solvent to obtain a thermosetting silicone hard coat liquid. And this is apply | coated to the outer surface of a film mirror etc. by the coating method in a normal coating material, and a transparent hard-coat layer is formed by heat-hardening at the temperature of 80-140 degreeC. However, in this case, the setting of the curing temperature below the thermal deformation temperature of the film mirror is a prerequisite. In addition, by using di (alkyl or aryl) dialkoxysilane and / or mono (alkyl or aryl) trialkoxysilane instead of tetraalkoxysilane, a polysiloxane-based transparent hard coat layer is similarly produced. Is possible.

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 the light-incidence side of an acrylic layer (= the 2nd layer or 3rd layer from a light-incidence side besides the outermost layer of a light-incidence side), and a transparent hard-coat layer is formed by ultraviolet-curing.

Further, it is preferable to impart a hydrophilic property by subjecting the transparent hard coat layer to a surface treatment. Examples thereof include corona treatment (Japanese Patent Laid-Open No. 11-172028), plasma surface treatment, ultraviolet / ozone treatment, surface protrusion formation (Japanese Patent Laid-Open No. 2009-226613), and surface fine processing.

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.

As for the transparent hard coat layer, for example, the “layer for preventing adhesion of dirt” described in paragraph “0105” of JP-A-2012-137579 and the paragraphs “0110” to “0113” described in publicly known JP-A-2012-137579. A “scratch prevention layer” can be applied. Furthermore, what is described in paragraphs “0015” to “0031” of JP2011-128501A can also be applied.

Also, 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 functional monomer having an α, β-unsaturated double bond in the molecule. A certain polyfunctional acrylate type or polyfunctional methacrylate type monomer may be mentioned. In addition, 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 monofunctional (meth) acrylate monomers include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and 2- (meth) acryloyloxyethyl. Hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, butanediol mono (Meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate, cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, dipropylene glycol (meth) acrylate, phenyl (meth) acrylate, ethyl (Meth) acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (medium) ) Acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene Glycol (meth) acrylate, octafluoropentyl (meth) acrylate, Octoxy polyethylene glycol-polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, perfluorooctylethyl (meth) acrylate, phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, stearyl (meth) acrylate, succinic acid (meth) acrylate, t-butyl (Meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrafluoropropyl (meth) Chryrate, tetrahydrofurfuryl (meth) acrylate, tribromophenyl (meth) acrylate, tridecyl (meth) acrylate, trifluoroethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, ω-carboxy-polycaprolactone (meth) Examples thereof include acrylates, derivatives thereof, and modified products.

Specific examples of the polyfunctional (meth) acrylate monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, diethylene glycol di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, di (meth) acrylate phthalate Rate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, pentae Thritol tri (meth) acrylate, phosphoric acid tri (meth) acrylate, 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.

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

The content of the polymerizable organic compound “A” component is 10 to 90% by mass with the total composition of “A” + “B” being 100% by mass from the viewpoint of improving antifouling properties and light resistance. It is preferably 15 to 80% by mass.

<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, the monomer (a) having 1 to 50% by mass of a radically polymerizable double bond and a polyorganosiloxane chain, and a monomer other than (a) having a radically polymerizable double bond and a reactive functional group ( b) a polymer obtained by polymerizing a monomer containing 10 to 95% by mass and a monomer having a radical polymerizable double bond other than (a) and (b) (c) 0 to 89% by mass Activity which is a vinyl copolymer having a number average molecular weight of 5000 to 100,000, which is obtained by reacting (α) with a functional group capable of reacting with the above-mentioned reactive functional group and a compound (β) having a radical polymerizable double bond It is preferable that it is an energy beam curable resin composition. The number average molecular weight of the active energy ray-curable resin composition can be measured by a chromatography method (GPC method), a terminal group determination method, or the like.

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

The “B” component can be used alone or in combination of two or more depending on the required performance. In addition, the copolymerization ratio of the “B” component is determined based on the monomer constituting the polymer (the copolymer of the “A” component and the “B” component) (the “A” component of the polyfunctional acrylic monomer and the silicone resin “ It is preferably 1 to 50% by mass, more preferably 10 to 35% by mass, based on the total weight of component “B”. If the copolymerization ratio of the “B” component is 1% by mass or more, antifouling properties and weather resistance can be sufficiently imparted to the upper surface of the cured product, and if it is 50% by mass or less, scratch resistance is obtained. Compatibility with other components (“A” component) contained in the hard coat layer forming material (monomer “A” component + resin “B” component), substrate (acrylic layer, etc.) ) And coating film performance such as toughness, and solubility of the copolymer in a solvent can be sufficiently obtained. An appropriate amount of polysiloxane can also be contained in the “B” component, and depending on the chemical structure and quantity ratio of the “B” component, the durability can be improved by adding the 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. Examples of the ultraviolet absorber and the antioxidant include those described in <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 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.

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

As the antioxidant used in 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. As a light stabilizer that can be used in combination with an antioxidant, a nickel-based ultraviolet stabilizer can be used in addition to the hindered amine light stabilizer exemplified below.

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

In addition, nickel-based UV stabilizers can also be used as light stabilizers, and [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II) can be used as a nickel-based UV 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 amount of the initiator or photosensitizer used is 0.1 to 15 parts by mass with respect to 100 parts by mass of the composition (material for forming a transparent hard coat layer containing a polyfunctional acrylic monomer and a silicone resin), preferably Is 1 to 10 parts by mass, more preferably 2 to 5 parts by mass. Two or more kinds of initiators can be used in combination, and particularly in the case of radical initiators, at least two kinds of initiators, preferably radical initiators that absorb different wavelengths, are used. More preferably, two kinds of initiators having different ultraviolet absorption wavelengths are used. For example, with only an initiator that absorbs a shorter wavelength, the polymerization reaction of all the monomers may not be performed by the initiator. On the other hand, only an initiator that absorbs longer wavelengths improves the reactivity, but the initiator may be colored during long-term use. Therefore, it is preferable to use radical initiators that absorb different wavelengths in order to improve the weather resistance and also the polymerization reactivity without coloring even during long-term use.

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

¡Leveling agents are effective in reducing surface irregularities. As the leveling agent, for example, a dimethylpolysiloxane-polyoxyalkylene copolymer (for example, SH190 manufactured by Toray Dow Corning Co., Ltd.) is suitable as the silicone leveling agent.

<9. Gas barrier layer>
A gas barrier layer may be provided on the light incident side of the metal (particularly silver) reflective layer. A gas barrier layer is preferably provided between the acrylic layer and the metal (especially 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. For details of the gas barrier layer, for example, paragraphs “0044” to “0096” of the publicly known international publication number WO2011 / 096151 A1 can be applied.

<10. Anchor layer>
The anchor layer 2 is made of a resin, and is a layer provided to bring the resin film-like support 1 and the metal (particularly silver) reflective layer 3 into close contact. Accordingly, the anchor layer 2 is resistant to the adhesion between the resin film-like support 1 and the metal (especially silver) reflective layer 3, and can withstand heat when the metal (especially silver) reflective layer 3 is formed by vacuum deposition or the like. The heat resistance to obtain and the smoothness for extracting the high reflective performance which the metal (especially silver) reflective layer 3 originally has are required.

The resin used for the anchor layer 2 is not particularly limited as long as it satisfies the above adhesiveness, heat resistance, and smoothness conditions, and is a polyester resin, an acrylic resin, a melamine resin, an 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 mixed resin of a 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 2 is preferably 0.01 to 3 μm, more preferably 0.1 to 2 μm. By satisfying this range, it is possible to cover the unevenness of the surface of the resin film-like support 1 while maintaining the adhesion, to improve the smoothness and to sufficiently cure the anchor layer 2, and as a result, the film The reflectance of the mirror 20 can be increased.

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

In addition, the formation method of the anchor layer 2 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 20 according to the present invention may have a release layer 7 on the side opposite to the light incident side of the pressure-sensitive adhesive layer 6. For example, when the film mirror 20 is shipped, the film is shipped with the release layer 7 attached to the pressure-sensitive adhesive layer 6, and the film mirror 20 having the pressure-sensitive adhesive layer 6 is peeled off from the release layer 7 and bonded to another substrate. A mirror for reflecting sunlight and a reflecting device for solar thermal power generation can be formed.

The release layer 7 may be any layer that can impart protection to the metal (particularly silver) reflective layer 3, such as an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet. , Polyethylene terephthalate film or sheet, plastic film or sheet such as fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc. A resin film or sheet in which a metal is subjected to surface processing such as metal deposition is used.

The thickness of the release layer 7 is not particularly limited but is usually preferably in the range of 12 to 250 μm.

In addition, a concave portion or a convex portion may be provided before the release layer 7 is bonded to the film mirror 20 (excluding the release layer 7), and may be pasted. Molding may be performed, and bonding and molding so as to have a concave portion or a convex portion may be performed at the same time.

In the present invention, the pressure-sensitive adhesive layer 6 is further cut (by a shear stress at the time of cutting) by further cutting the film mirror 20 described above (to a predetermined size, for example, a size to be attached to a supporting substrate). (Or adhesive layer 4 using an adhesive containing a metal (especially silver) corrosion inhibitor) The metal (especially silver) of the cut end face (cut edge) by extending the adhesive containing the metal (especially silver) corrosion inhibitor It is good also as a film mirror formed by covering the reflective layer. Thereby, the intended object of the present invention (providing a film mirror having high corrosion resistance even at the cut end face after cutting) can be achieved. Such a form is usually used by cutting the film mirror 20 (product) into a predetermined size at the production stage of the solar reflective mirror, but a film mirror product obtained by cutting the film mirror 20 into a predetermined size in advance. This is because it may be sold (provided).

<12. Sunlight reflection mirror>
The solar reflective mirror has a film mirror and a self-supporting base material (supporting base material), and the film mirror is bonded to the self-supporting base material (supporting base material) via an adhesive layer. ing. Here, as described above, the film mirror is cut into a predetermined size (for example, a size for attaching to a support base material). Specifically, the film mirror is cut to a predetermined size, and the metal reflective layer on the cut end face (cut edge) is covered with an adhesive containing a metal corrosion inhibitor. Thereby, the intended object of the present invention can be achieved.

<12-2. Self-supporting substrate>
The self-supporting base material (supporting base material) preferably has one of the following configurations A and B.

A: It has 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 base material”, “self-supporting” means the opposite edge when cut to a size used as a base material (support base material) for a mirror for sunlight reflection By supporting the portion, it indicates that the substrate has rigidity enough to support the substrate. Since the base material (support base material) of the mirror for sunlight reflection has self-supporting properties, it is excellent in handleability when installing the mirror for sunlight reflection, and a holding member for holding the mirror for sunlight reflection Therefore, it is possible to reduce the weight of the solar power generation reflecting device, and it is possible to suppress power consumption during solar tracking.

As in configuration A, the self-supporting base material (support 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 a layer having a hollow structure. By having a layer composed of a resin material, the metal flat plate has high flatness, and the intermediate layer is a layer having a hollow structure or a layer composed of a resin material. Compared with the case of constituting the base material, the base material can be significantly reduced in weight, and the rigidity can be increased by the relatively lightweight intermediate layer. It becomes possible to do. 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 the 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 cell 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. As the material, a known foamed resin material can be used, but polyethylene or the like can be used. Polyolefin resins, polyurethane resins, 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 resins, polyolefin oxides and polyacetals 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, polypropylene resins or resins mainly composed of polypropylene resins, such as olefin resins or resins mainly composed of olefin resins, have an excellent balance of mechanical strength and moldability. Is preferable. 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 may be a layer made of a resin plate as a layer made of a resin material. In this case, as the resin material forming the intermediate layer, the above-described resin film support (for a film mirror) The same material as that constituting the (film substrate) can be preferably used.

The intermediate layer need not be provided in all regions of the base material (support base material), and 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. It may be. When the intermediate layer has the above-described three-dimensional structure, it is preferable to provide the three-dimensional structure in a region of about 90 to 95% with respect to the area of the metal flat plate. It is preferable to provide it.

As in the above configuration B, the self-supporting base material (supporting base material) can be a layer made of a resin material having a hollow structure. When the base material (supporting base material) is made of a resin-only layer, the thickness required to obtain rigidity sufficient to provide self-supporting properties increases, resulting in an increase in the weight of the base material. By providing the base material with a hollow structure, 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 resin film-like support of the above-mentioned film mirror can be preferably used, and as the resin material constituting the hollow structure, the above-mentioned foamed material or three-dimensional material can be used. The same resin material as that used for the structure can be preferably used.

<13. Holding member>
The solar power generation reflecting device includes a solar light reflecting mirror and a holding member that holds the 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.

[Comparative Example 17]
(Production of film mirror)
An outline of the layer structure of Comparative Example 17 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, polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), melamine resin (Super Becamine J-820, manufactured by DIC Corporation), TDI isocyanate (2,4-tolylene) Isocyanate), HDMI-based isocyanate (1,6-hexamethylene diisocyanate) in a resin solid content ratio of 20: 1: 1: 2 (mass ratio) and a solid content concentration of 10% by mass in toluene. Is coated by a gravure coating method to form an anchor layer 2 having a thickness of 0.1 μm, and a silver reflecting layer 3 made of silver having a thickness of 100 nm is formed on the anchor layer 2 as a silver reflecting layer 3 by a vacuum deposition method. Formed. Furthermore, a resin in which a polyester resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 (mass ratio) is coated on the silver reflective layer 3 by a gravure coating method, A resin coat layer 8 having a thickness of 3.0 μm was formed.

Next, a transparent acrylic film (Acryprene HBS010P, thickness 100 μm, manufactured by Mitsubishi Rayon Co., Ltd.) is laminated on the resin coat layer 8 by a dry lamination process as an acrylic layer 5 at a lamination temperature of 60 ° C. did.

Furthermore, 100 parts by mass of addition reaction type silicone adhesive X-40-3103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts by mass of toluene, platinum catalyst, CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of the product name) was added and mixed uniformly to prepare a silicone pressure-sensitive adhesive composition, which was applied to one side of a 25 μm-thick polyester separate film as the release layer 7 and 30 ° C. at 30 ° C. After heating for 2 seconds to form a 25 μm thick silicone-based pressure-sensitive adhesive layer 6 (Si-based), the polyethylene terephthalate film was laminated on the side opposite to the anchor layer 2 and the silver reflective layer 3, and the film of Comparative Example 17 I got a mirror.

The formation method of the adhesive layer 4 is as follows.

Polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Melamine resin (Super Becamine J-820, manufactured by DIC Corporation), TDI isocyanate (2,4-tolylene diisocyanate), HDMI isocyanate A resin in which (1,6-hexamethylene diisocyanate) is mixed in toluene at a resin solid content ratio of 20: 1: 1: 2 (mass ratio) to a solid content concentration of 10% by mass is added to the resin coating layer 8. Was coated by a gravure coating method to form an adhesive layer 4 having a thickness of 8 μm.

[Comparative Examples 18 and 19, Examples 1 to 16, 20, and 21]
(Production of film mirror)
In Comparative Examples 18 and 19, and Examples 1 to 16, 20, and 21, the film mirror was formed in the same manner as Comparative Example 17 except that the adhesive layer 4 and the pressure-sensitive adhesive layer 6 in FIG. Produced.

When a pressure-sensitive adhesive layer is used instead of the adhesive layer 4 of Comparative Example 17 (Examples 3 to 16, 20, and 21), an addition reaction type silicone pressure-sensitive adhesive X-40- having a weight average molecular weight of 500,000 is used. 3103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by weight of platinum catalyst, CAT-PL-50T (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts by weight, and “Adhesion” in Table 1 as necessary. A predetermined amount of the silver corrosion inhibitor described in the column “Change the agent layer 4 to the following content” was added to form a 35 mass% toluene solution on the resin coating layer 8, and the coating was applied at 80 ° C. for 30 seconds. A silicone pressure-sensitive adhesive layer (Si-based) having a thickness of 18 μm was formed by heating.

When an adhesive layer is used instead of the pressure-sensitive adhesive layer 6 of Comparative Example 17 (Comparative Examples 18 to 19), polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), melamine resin ( Super Becamine J-820 (manufactured by DIC Corporation), TDI isocyanate (2,4-tolylene diisocyanate), HDMI isocyanate (1,6-hexamethylene diisocyanate) in a resin solid content ratio of 20: 1: 1: 2 (Mass ratio) and a predetermined amount of silver corrosion inhibitor described in the column of “Change the pressure-sensitive adhesive layer 6 to the following content” in Table 1 is added, so that the solid content concentration is 10% by mass in toluene. Is coated on the opposite surface side of the polyethylene terephthalate film from the anchor layer 2 and the silver reflecting layer 3 by a gravure coating method, To form an adhesive layer of 5 [mu] m, to obtain a film mirror. In this case, the release layer 7 was not provided on the adhesive layer.

[Evaluation]
About the film mirror obtained above, the corrosion resistance of the cut end face was evaluated by the following method (acceleration life test).

(1) Cut the produced film mirror into 5cm □ (5cm × 5cm square) with scissors, put it in a sealed vial tube together with sulfur powder, and heat it in a 110 ° C oven for 48 hours. Damage to the end face of the silver reflective layer 3 was visually confirmed.

The visual evaluation criteria for damage (particularly corrosion from the cut end face) of the silver reflecting surface in the evaluation test (1) are as follows.

◎; No damage or discoloration of the reflection surface at the end face ○: Slight damage or discoloration is seen when the end face is viewed from the side, but no damage is seen when viewed from the reflection face direction ○ △: Reflection Slight damage is seen from the surface direction (less than 0.5mm from the edge)
Δ: Slightly damaged when viewed from the reflective surface (0.5 mm or more and less than 1 mm from the edge)
×: Obviously damaged when viewed from the reflecting surface direction (1 mm or more from the edge)

(2) The produced film mirror was cut into 5 cm □ (5 cm × 5 cm square) with scissors, then immersed in an aqueous ammonium sulfide solution (ammonium sulfide concentration: 1% by mass), and a silver reflecting surface (silver reflecting layer after 10 days) The damage on the cut end face 3) was confirmed visually.

The visual evaluation criteria for damage (particularly corrosion from the cut end face) of the silver reflecting surface in the evaluation test (2) are as follows.

Table 1 shows the contents and evaluation results of each comparative example and example.

This application is based on Japanese Patent Application No. 2012-228936 filed on October 16, 2014, the disclosure of which is incorporated by reference as a whole.

1 resin film-like support,
2 anchor layer,
3 Metal (silver) reflective layer,
4 Adhesive layer or adhesive layer,
5 Acrylic layer (with UV absorber),
6 adhesive layer,
7 release layer,
8 resin coating layer,
20 Film mirror.

Claims

A film mirror in which a metal reflective layer is provided on a resin film support,
It has an adhesive layer on either the light incident side or the back side of the reflective layer, and the adhesive layer contains a corrosion inhibitor of the same kind of metal as the metal of the reflective layer. Film mirror.
The film mirror according to claim 1, wherein the metal reflective layer is a silver reflective layer.
2. The adhesive layer according to claim 1, further comprising a pressure-sensitive adhesive layer on both the light incident side and the back side of the reflective layer, and a silver corrosion inhibitor contained in both or one of the pressure-sensitive adhesive layers. 2. The film mirror according to 2.
The adhesive layer according to any one of claims 1 to 3, further comprising a pressure-sensitive adhesive layer on both the light incident side and the back side of the reflective layer, and containing a silver corrosion inhibitor in both of the pressure-sensitive adhesive layers. The film mirror of any one.
5. The film according to claim 1, wherein the metal corrosion inhibitor is a silver corrosion inhibitor and is at least one of a mercapto compound and a benzotriazole compound. mirror.
The film mirror according to any one of claims 1 to 5, further comprising a pressure-sensitive adhesive containing a metal corrosion inhibitor in the pressure-sensitive adhesive layer at the cut portion, and covering the metal reflective layer on the cut end face by a cutting treatment. The film mirror characterized by comprising.
A reflector for solar power generation, wherein the film mirror according to any one of claims 1 to 6 is formed on a supporting substrate.