WO2011078157A1

WO2011078157A1 - Film mirror, method for producing same, and reflecting device for solar thermal power generator

Info

Publication number: WO2011078157A1
Application number: PCT/JP2010/072980
Authority: WO
Inventors: 丈範熊谷; 美佳本田
Original assignee: コニカミノルタオプト株式会社
Priority date: 2009-12-21
Filing date: 2010-12-21
Publication date: 2011-06-30
Also published as: JP5962014B2; JPWO2011078157A1

Abstract

Provided is a film mirror which does not cause an ultraviolet absorbing agent to bleed out even when used as a film mirror for a solar thermal power generator over a long period of time in harsh environments, can sufficiently minimize the drop in specular reflectance, is light weight and flexible, reduces manufacturing costs, can be increased in area and mass produced, exerts excellent adhesive properties and resistance to weather and thermal shock, and has a superior specular reflectance rate against sunlight. Also provided are a method for producing said film mirror, and a reflecting device for a solar thermal generator using said film mirror. The film mirror is provided, on a resin substrate, with an ultraviolet absorbing layer and a reflective layer comprising a metal, wherein: the ultraviolet absorbing layer is configured from an ultraviolet absorbing layer comprising a polymeric ultraviolet light absorber; or the reflective layer configured from the metal functions as the silver reflective layer, and the ultraviolet absorbing layer is configured from ultraviolet absorbing layer (1) containing an ultraviolet absorber, and ultraviolet absorbing layer (2) containing an ultraviolet absorber capable of preventing silver from corrosion.

Description

FILM MIRROR, METHOD FOR MANUFACTURING THE SAME, AND REFLECTOR FOR SOLAR THERMAL POWER GENERATION

The present invention relates to a film mirror having a good regular reflectance with respect to solar heat and excellent in adhesion, weather resistance and thermal shock resistance, a manufacturing method thereof, and a solar power generation reflecting device using the film mirror.

In recent years, biomass energy, nuclear energy, and natural energy such as wind energy and solar energy have been studied as alternative energy alternatives to fossil fuel energy such as oil and natural gas. In addition, natural energy with a large amount is considered to be solar energy.

However, although solar energy is a very powerful alternative energy, from the viewpoint of utilizing this, (1) the energy density of solar energy is low, and (2) it is difficult to store and transfer solar energy. However, this 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 reflector.

Since the reflection device is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, etc., glass mirrors have been used conventionally. While glass mirrors are highly durable to the environment, they have problems such as damage during transportation and heavy construction, which increases the construction cost of the plant due to the strength of the frame 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 reflection sheet (for example, see Patent Document 1). However, when used as a film mirror for solar thermal power generation, the film mirror is directly exposed to sunlight for a long time. Therefore, when the resin base material is deteriorated by the ultraviolet rays, there is a problem that the transmittance is lowered due to discoloration, and as a result, the reflectance as a mirror is lowered.

For the purpose of concentrating sunlight, from the viewpoint of obtaining a high reflectance, it is preferable that the metal layer is made of silver having a high reflectance in the visible light region as disclosed in Patent Document 2. However, by using silver for the reflective layer, it is possible to increase the initial reflectivity, but due to deterioration of the resin due to ultraviolet rays, it is possible to sufficiently suppress the decrease in reflectivity when used for a long time. It was difficult.

Therefore, Patent Document 3 proposes a technique of providing a layer containing a benzotriazole ultraviolet absorber on the surface layer of a film mirror. In Patent Document 3, by adding a crosslinkable monomer having a vinyl group to the surface layer, the compatibility of the benzotriazole-based ultraviolet absorber and the resin in the surface layer is improved, so that the amount of the ultraviolet absorber added The technology which suppresses the deterioration of the plastic base material by ultraviolet rays is proposed. However, even with such a technique, when used as a film mirror for solar power generation that is directly exposed to sunlight in an environment where the temperature and humidity changes drastically, it is contained in a large amount of 15% by mass or more. UV absorbers ooze out over time (referred to as blooming in Patent Document 3, generally called bleed-out), causing peeling problems due to poor adhesion between layers, and deformation of the reflective layer made of metal, as a film mirror The problem that caused a decrease in the regular reflectance of the surface became obvious.

In addition, silver used as the metal in the reflective layer is a metal that is very susceptible to corrosion, so when it is installed outdoors, it will deteriorate due to complex factors such as water vapor, oxygen, and ultraviolet light present in the atmosphere. To do. Further, since silver transmits light having a wavelength of about 320 nm, it is necessary to form an ultraviolet absorbing layer for protecting the base material layer on the back surface of silver. Therefore, it is necessary to provide an ultraviolet absorption layer, a silver corrosion inhibitor layer, an oxygen or water vapor barrier layer, etc. in the layer configuration of the film mirror.

From the outermost layer, the film mirror for solar power generation disclosed in Patent Document 4 is (acrylic layer mixed with ultraviolet absorber) / (acrylic layer mixed with silver discoloration inhibitor) / (silver reflective layer) / (base The material is a PET layer) / (adhesive layer) / (release layer). When the inventor actually used the film mirror produced in this configuration for solar thermal power generation, because the ultraviolet absorption ability is insufficient, not only affects the silver when the film mirror is exposed to solar heat for a long time, It was found that the substrate deteriorated.

In Patent Document 5, in order to solve this problem, an outermost UV absorbing layer was provided with an adhesive layer and an acrylic resin layer containing a UV absorber. In this case, since the ultraviolet transmittance decreases to about 5%, a high reflectance can be maintained for a long time. However, when left in a harsh environment for a long time, the ultraviolet absorber itself is deteriorated by solar heat, so that the resin base material is deteriorated and the reflectance is deteriorated. Moreover, when a ultraviolet absorber is added in large quantities, the problem that a bleed-out and the transmittance | permeability fall will arise. Further, although an acrylic layer is used as a barrier layer for water vapor or oxygen, there is a problem that it cannot withstand long-term use because it cannot completely block water vapor or oxygen.

JP 2005-59382 A JP-A-6-38860 Special table 2007-525550 gazette JP 61-154942 A US Pat. No. 6,989,924

The present invention has been made in view of the above problems, and its purpose is to reduce the bleed-out of the ultraviolet absorber even when used as a film mirror for solar power generation for a long time in a harsh environment. It is possible to sufficiently suppress the decrease in reflectivity, it is lightweight and flexible, has a good regular reflectivity with respect to solar heat, which can reduce the manufacturing cost and increase the area and mass production, It is providing the film mirror which is excellent in adhesiveness, a weather resistance, and a thermal shock resistance, its manufacturing method, and the solar power generation reflective apparatus using the film mirror.

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

1. A film mirror having at least a reflective layer made of a metal and an ultraviolet absorbing layer on a resin substrate, wherein the ultraviolet absorbing layer is made of an ultraviolet absorbing layer containing a polymeric ultraviolet absorber, or made of the metal The reflection layer is a silver reflection layer, and the ultraviolet absorption layer is composed of an ultraviolet absorption layer (1) containing an ultraviolet absorber and an ultraviolet absorption layer (2) containing an ultraviolet absorber having an anticorrosive ability for silver. Characteristic film mirror.

2. 1. A film mirror having at least a reflective layer made of a metal and an ultraviolet absorbing layer on a resin substrate, wherein the ultraviolet absorbing layer comprises an ultraviolet absorbing layer containing a polymer type ultraviolet absorber. The film mirror described in 1.

3. 3. The film mirror as described in 1 or 2 above, wherein the resin substrate is a resin film containing polyester, polyethylene naphthalate, acrylic, polycarbonate, polyolefin, cellulose, or polyamide.

4. 4. The film mirror according to any one of 2 to 3, wherein the reflective layer made of metal contains gold, silver, copper, aluminum, or an alloy thereof.

5. 5. The film mirror according to any one of 2 to 4, wherein the reflective layer made of metal is produced by wet plating.

6. 5. The film mirror according to any one of 2 to 4, wherein the reflective layer made of metal is produced by dry plating.

7. 7. The film mirror as described in any one of 2 to 6, wherein the reflective layer made of metal is provided on the light incident side with respect to the resin base material.

8. 8. The film mirror according to any one of 2 to 7, wherein the layer containing the polymeric ultraviolet absorber is provided on the light incident side of the reflective layer made of the metal.

9. 8. The method according to any one of 2 to 7, wherein the layer containing the polymer type ultraviolet absorber is obtained by applying and drying a polymer type ultraviolet absorber liquid dispersed in an emulsion form. The film mirror described in 1.

10. The layer containing the polymer type ultraviolet absorber is obtained by adding a polymer type ultraviolet absorber to a resin solution dissolved in an organic solvent and evaporating and drying the solvent after coating. 9. The film mirror as described in any one of 2 to 8 above.

11. The above-mentioned layers 2 to 10 are characterized in that the layer containing the polymeric ultraviolet absorber is obtained by adding a polymeric ultraviolet absorber to an ultraviolet curable monomer resin solution and curing it after coating. The film mirror of any one of these.

12. 12. The film as described in any one of 2 to 11 above, wherein the layer containing the polymeric ultraviolet absorber has a thickness of 50 μm or less and an average value of light transmittance of 90% or more. mirror.

13. 13. The film mirror according to any one of 2 to 12, wherein a Cu layer is provided in contact with the reflective layer made of the metal.

14. A thioether-based, thiol-based, Ni-based organic compound-based, benzotriazole-based, imidazole-based, oxazole-based, tetrazaindene-based, pyrimidine-based or thiadiazole-based corrosion inhibitor layer is provided in contact with the reflective layer made of the metal. 14. The film mirror as described in any one of 2 to 13 above, wherein

15. A film mirror having at least a reflective layer made of a metal and an ultraviolet absorbing layer on a resin base material, the reflective layer made of the metal being a silver reflective layer, and having a silver corrosion preventing ability on the silver reflective layer 2. The film mirror according to 1 above, further comprising an ultraviolet absorbing layer (2) containing the ultraviolet absorber and further having an ultraviolet absorbing layer (1) containing the ultraviolet absorber.

16. 16. The film mirror as described in 15 above, wherein the ultraviolet absorber having corrosion inhibiting ability contained in the ultraviolet absorbing layer (2) has an adsorptive group for silver and has ultraviolet absorbing ability.

17. 17. The film mirror as described in 15 or 16 above, wherein the ultraviolet absorber contained in the ultraviolet absorbing layer (1) is an inorganic ultraviolet absorber.

18. Any of the above 15 to 17, wherein a metal layer containing a metal having a higher ionization tendency than silver is adjacent to the silver reflective layer between the ultraviolet absorbing layer (2) and the silver reflective layer. The film mirror according to item 1.

19. 19. The film mirror as described in any one of 15 to 18, wherein an adhesive layer is provided between the ultraviolet absorbing layer (2) and the silver reflecting layer or between the ultraviolet absorbing layer (2) and the metal layer.

20. 20. The film mirror as described in any one of 15 to 19, further comprising a gas barrier layer above the layer adjacent to the silver reflective layer.

21. 21. The film mirror as described in any one of 15 to 20, wherein a scratch preventing layer is provided as an outermost layer.

22. The film mirror according to any one of 15 to 21, wherein the entire layer including the resin base has a thickness of 75 to 250 μm.

23. 23. A film mirror manufacturing method for manufacturing the film mirror according to any one of 1 to 22, wherein the reflective layer made of the metal is formed by silver vapor deposition.

24. 23. A solar power generation reflector using the film mirror according to any one of 1 to 22 or the film mirror obtained by the method for producing a film mirror according to 23, wherein the resin base material is sandwiched between the reflectors. The film mirror is attached to a metal substrate through an adhesive layer coated on the side having the reflective layer made of metal and on the opposite side of the resin substrate. Reflector for solar power generation.

According to the present invention, even when used as a film mirror for solar power generation in a harsh environment for a long period of time, there is little bleeding out of the ultraviolet absorber, and it is possible to sufficiently suppress the decrease in regular reflectance. A film mirror that is lightweight, flexible, has a good regular reflectance to solar heat, has excellent adhesion, weather resistance, and thermal shock resistance, can be manufactured in large areas and mass-produced with reduced manufacturing costs The manufacturing method and the solar power generation reflective apparatus using the film mirror could be provided.

As a result of investigations in view of the above problems, the present inventors have found that when a film mirror having a reflective layer made of metal is used as a reflection device for solar power generation, the use is high due to the high reflectance of the reflective layer made of metal Although it is possible to obtain a reflectance, it has been revealed that the problem of a decrease in regular reflectance occurs when exposed to strong sunlight for a long time. One of the factors was considered that the reflective layer made of metal, particularly silver, has the property of transmitting ultraviolet light of 320 nm or less.

When a film mirror is used as a mirror for solar thermal power generation, sufficient self-supporting property cannot be obtained with the film mirror itself, so that it is used by being attached to a metal support such as aluminum metal. At this time, the ultraviolet light that has passed through the reflective layer made of metal passes through the layer below the reflective layer made of metal (on the side far from the light incident side), and then is reflected by the metal support and again from the reflective layer made of metal. The light enters the lower layer. Therefore, the lower layer of the reflective layer made of metal is deteriorated by ultraviolet rays, or the excitation between the reflective layer made of metal and the lower layer causes the deterioration of the reflective layer made of metal, and the reflective layer made of metal progresses. It was found that the regular reflectance was lowered.

Also, in the desert area close to the equator, which is the preferred location for installation of film mirrors for solar power generation, the daily temperature difference may be 30 ° C or higher. Under such severe conditions, ultraviolet rays added to the film mirrors due to thermal shock. It was found that the absorbent bleeds out (sucks out to the surface, agglomerates and solidifies as if powder is blown), causing a decrease in regular reflectance.

As a result of intensive studies in view of the above problems, the present inventor has found that a film mirror for solar power generation is provided on a resin substrate with a film mirror having at least a reflective layer made of a metal and a layer containing a polymer ultraviolet absorber. Even when used in harsh environments for a long period of time, it is possible to sufficiently suppress the decrease in regular reflectance, and it is lightweight and flexible, reducing the manufacturing cost and increasing the area and mass production. It was found that a film mirror having good regular reflectance with respect to solar heat and excellent in adhesion, weather resistance and thermal shock resistance can be obtained, and the present invention has been achieved.

The film mirror of the present invention is a film mirror in which at least a resin substrate, a reflective layer made of a metal, and an ultraviolet absorbing layer containing a polymer type ultraviolet absorber are provided as a constituent layer on a resin substrate. It is characterized by. In particular, the reflective layer made of metal is preferably made of silver or a silver alloy because sunlight can be efficiently reflected from the infrared region to the visible region. According to the embodiment of the present invention, the ultraviolet absorbing layer containing the polymer type ultraviolet absorber is disposed on the light incident side of the reflective layer made of metal, so that the reflective layer made of metal is influenced by external oxygen and water vapor. The surface accuracy is roughened because the resin base material and adhesive layer provided as the lower layer of the silver layer made of metal are deteriorated by ultraviolet rays that have passed through the reflective layer made of metal. It is possible to effectively suppress the problem that the regular reflectance decreases. Moreover, it discovered that the bleed-out of the ultraviolet absorber caused by a rapid thermal shock could be suppressed by using a polymer type ultraviolet absorber as the ultraviolet absorber.

The present inventor further conducted an intensive study in view of the above problems, and as a result, an ultraviolet ray containing an ultraviolet absorber having a silver reflection layer on a resin base material and having a silver corrosion prevention ability on the silver reflection layer. By providing an absorption layer (2), an ultraviolet absorption layer (1) containing an ultraviolet absorber on the absorption layer, and using an ultraviolet absorber having an anti-corrosion ability for preventing discoloration of silver in the ultraviolet absorption layer (2) Further, even when the ultraviolet absorber of the upper ultraviolet absorbing layer (1) is deteriorated over time, the ultraviolet absorber having the anticorrosive ability supplements the ultraviolet absorbing ability, so that the deterioration can be suppressed for a long period of time. It depends on you.

¡Organic corrosion inhibitors have high UV absorption ability, but their performance deteriorates over time. On the other hand, in the case of an inorganic corrosion inhibitor, the ultraviolet absorption ability is not so high, but the performance over time does not deteriorate. Therefore, a high reflectance can be maintained for a longer period by using an inorganic ultraviolet absorber as the ultraviolet absorber and further combining a corrosion inhibitor having ultraviolet absorbing ability.

In addition, although the inorganic barrier layer can almost completely block water vapor and oxygen, adhesion with an organic corrosion inhibitor layer may be problematic. Therefore, by providing an inorganic ultraviolet absorbing layer between them, an inorganic barrier layer can be provided, and a high reflectance can be maintained for a long period of time. By doing in this way, the solar reflective film mirror which can maintain a high reflectance over a long period of time can be developed.

The film mirror of the present invention comprises, on a resin substrate, at least a silver reflecting layer as a constituent layer, an ultraviolet absorbing layer (2) containing an ultraviolet absorber having an anticorrosive ability in an upper adjacent layer, and an ultraviolet absorber on the upper layer. It has the ultraviolet absorption layer (1) containing this, It is characterized by the above-mentioned.

According to the embodiment of the present invention, the ultraviolet absorbing layer (1) containing the ultraviolet absorber is formed on the ultraviolet absorbing layer (2) containing the ultraviolet absorber having a corrosion preventing ability, so that it is included in the solar heat. It can absorb ultraviolet rays and suppress deterioration of the silver reflecting layer and the resin base material layer. At this time, by using a material having an ultraviolet absorber having an ability to prevent silver corrosion, bleeding out and a decrease in transmittance caused by adding a large amount of the ultraviolet absorber to the outermost layer can be suppressed. Therefore, it is possible to develop a film mirror that can suppress deterioration of each layer of the film mirror and maintain a high reflectance over a long period even in a harsh environment.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.

(Outline of film mirror configuration)
The film mirror of the present invention is a film mirror in which at least a reflective layer made of metal as a constituent layer, an ultraviolet absorber layer containing a polymer type ultraviolet absorber is provided on a resin substrate, or a resin substrate. Further, it is characterized in that at least a silver reflection layer, a silver corrosion inhibitor layer having an ultraviolet absorbing ability, and a film mirror provided with an ultraviolet absorbing layer thereon are provided as constituent layers. In addition to these layers, a special functional layer such as an adhesive layer, a gas barrier layer, or a scratch-preventing layer is preferably provided as a constituent layer.

(Resin base material)
As the resin base material (support) according to the present invention, various publicly known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyester film such as polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, Cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene film, polymethylpentene film, polyether Le ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and a polyacrylic film, or the like. Among these, a polycarbonate film, a polyester film, a norbornene film, a cellulose ester film, a polymethyl methacrylate film, and a polyacryl film are preferable.

In particular, a resin film containing polyester, polyethylene naphthalate, acrylic, polycarbonate, polyolefin, cellulose, or polyamide is preferable. These films are manufactured by solution casting even if they are films manufactured by melt casting. It may be a film made. When these resin base materials are provided on the side far from the light incident side of the reflective layer made of metal, deterioration due to ultraviolet rays transmitted through the reflective layer made of metal and the accompanying decrease in regular reflectance become a problem. According to the configuration of the invention, such a problem can be effectively suppressed.

It is preferable that the thickness of the resin base material is an appropriate thickness depending on the type and purpose of the resin. For example, it is generally in the range of 10 to 300 μm, preferably 20 to 200 μm, more preferably 30 to 100 μm.

(Reflective layer made of metal)
The reflective layer made of metal is preferably provided on the light incident side of the resin base material.

As the reflective layer made of metal, for example, silver or a silver alloy, gold, copper, aluminum, or an alloy thereof can be used. In particular, it is preferable to use silver. Such a reflective layer serves as a reflective film that reflects light. By making the reflective layer a film made of silver or a silver alloy, the reflectance in the visible light region of the film mirror can be increased, and the dependence of the reflectance on the incident angle can be reduced. The visible light region means a wavelength region of 400 to 700 nm. The incident angle means an angle with respect to a line perpendicular to the film surface.

The silver alloy is composed of silver and one or more other metals selected from the group consisting of gold, palladium, tin, gallium, indium, copper, titanium and bismuth from the viewpoint of improving the durability of the reflective layer. Alloys are preferred. As the other metal, gold is particularly preferable from the viewpoint of high temperature humidity resistance and reflectance.

When the reflective layer is a film made of a silver alloy, 90 to 99.8 atomic percent of silver is preferable in the total (100 atomic percent) of silver and other metals in the reflective layer. Further, the other metal is preferably 0.2 to 10 atomic% from the viewpoint of durability.

The film thickness of the reflective layer is preferably 60 to 300 nm, particularly preferably 80 to 200 nm. If the thickness of the reflective layer is less than 60 nm, the film thickness is thin and light is transmitted, so that the reflectance in the visible light region of the film mirror may be reduced. When the thickness of the reflective layer exceeds 300 nm, irregularities are likely to occur on the surface of the reflective layer, which causes light scattering, which may reduce the reflectance in the visible light region.

The reflective layer made of metal is preferably formed by wet plating, dry plating, or silver deposition.

(Silver reflection layer)
As a method for forming the silver reflective layer according to the present invention, either a wet method or a dry method can be used.

The wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction.

On the other hand, the dry method is a general term for a vacuum film-forming method. Specifically, a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, a sputtering method, etc. There is. 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, as a film mirror manufacturing method for manufacturing the film mirror of the present invention, it is preferable to form the silver reflecting layer by silver vapor deposition.

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

In the present invention, the silver reflective layer may be on the light incident side or on the opposite side with respect to the resin base material (support), but since the support is a resin, resin degradation due to light rays is prevented. For the purpose of preventing, it is preferable to be positioned on the light incident side.

(UV absorber layer)
One of the present invention has an ultraviolet absorbing layer (2) containing an ultraviolet absorber having an ability to prevent silver corrosion on the silver reflecting layer, and further on it for the purpose of preventing deterioration due to solar heat and ultraviolet rays, It is characterized by having an ultraviolet absorbing layer (1) containing an ultraviolet absorber.

UV absorbers contained in the UV absorbing layer (1) are roughly classified into inorganic UV absorbers and organic UV absorbers.

Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and zirconium oxide. Titanium oxide, zinc oxide, and cerium oxide are preferably used, and cerium oxide is more preferably used.

Examples of organic ultraviolet absorbers include benzophenone, benzotriazole, phenyl salicylate, and triazine.

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

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.

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

Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- 1,3,5-triazine and the like.

In addition to the above, the ultraviolet absorber includes 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 thermal energy. 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. In the case of using a normal ultraviolet ray inhibitor, it is effective to use a photopolymerization initiator that generates radicals with visible light.

The amount of the ultraviolet absorber used is 0.1 to 20% by mass, preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the amount is more than 20% by mass, the adhesion is deteriorated.

(UV absorbing layer containing polymer UV absorber)
One aspect of the present invention is characterized by having an ultraviolet absorbing layer containing a polymeric ultraviolet absorber.

<Polymer type UV absorber>
The polymer type ultraviolet absorber used in the present invention means an ultraviolet absorber having a weight average molecular weight of 500 or more. The weight average molecular weight can be measured with a gel permeation chromatography (GPC) apparatus.

As the polymer type ultraviolet absorber used in the present invention, a compound represented by the following general formula (1) is preferable.

(Wherein R represents a hydrogen atom or a methyl group, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group, R ₃ represents a benzophenone group or a benzotriazole group. L, m and n are 1) The above integers are represented, and the sum of l, m, and n is 100.)
Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and 1-methylbutyl. Group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, heptyl group, octyl group, nonyl , Decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, straight-chain such cyclodecyl group, an alkyl group, branched chain or cyclic and the like.

Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a benzyl group, and a phenethyl group.

Examples of other polymer type ultraviolet absorbers include compounds described in JP-A-2004-42614. Specifically, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2 -Hydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4 -(Methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy- 4- (Metak Royloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (Methacryloyloxybenziloxy) benzophenone] -methyl methacrylate copolymer, [2,2-dihydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′, 4-tri Hydroxy-4 '-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2', 4-trihydroxy-4 '-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [ 2,2 ', 4-trihydroxy- '-(Methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2', 4-trihydroxy-4 '-(methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2 , 2 ', 4-Trihydroxy-4'-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 '-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer [4-hydroxy-4 ′-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [4 -Hydroxy-4 '-(methacryl Royl oxide decyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 '-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4 -(Methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4 ' -Methyl-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [ 2-hydroxy-4'-me 4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2- (2'-hydroxy-4'-methacryloyloxyethoxy) benzotriazole] -methyl methacrylate copolymer, [2- (2′-hydroxy-4′-methacryloyloxyethoxy) -5-chlorobenzotriazole] -methyl methacrylate copolymer and the like. In addition, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and other high molecular weight ultraviolet absorptions of 500 or more Agents are also suitable.

In the present invention, a compound in which an ultraviolet absorption unit is graft-polymerized on an acrylic polymer can also be used as a polymer ultraviolet absorber. This is a compound having a structure in which an ultraviolet absorbing unit having an ultraviolet absorbing ability is introduced into a polymer chain of an acrylic polymer by graft polymerization.

Acrylic monomers constituting this acrylic polymer include acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylamide, methacrylamide, and vinyl compounds having a double bond copolymerizable with these acrylic monomers. And a copolymerized polymer.

Examples of the copolymerizable vinyl compound include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; alkyl vinyl esters such as vinyl acetate, ethyl vinyl and 2-ethylhexyl vinyl; styrene and maleic anhydride. These acrylic polymers have a number average molecular weight of 20,000 to 200,000, preferably 50,000 to 200,000.

The ultraviolet absorption unit introduced into the acrylic polymer may be a compound having ultraviolet absorption ability, and examples thereof include the above-described benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, benzoate compounds, and the like. These compounds are introduced into the polymer chain of the acrylic polymer by graft polymerization. In this case, the proportion of the ultraviolet absorbing unit introduced into the acrylic polymer is 40 to 90% by mass, preferably 50 to 80% by mass, based on the total mass of the ultraviolet absorber.

As a layer containing a polymer type ultraviolet absorber, in addition to a compound obtained by graft polymerization of an ultraviolet absorption unit to these acrylic polymers, a polymer type ultraviolet absorber may be added to a binder as described below. .

<binder>
Examples of the binder include those containing at least one of polymethacrylic acid ester, polymethacrylic acid, polyacrylic acid ester, polyacrylic acid, and copolymers thereof, and more specifically, dialnal. BR-80 (Mitsubishi Rayon Co., Ltd.) etc. are mentioned. Here, Dialnal BR-80 (manufactured by Mitsubishi Rayon Co., Ltd.) is polymethyl methacrylate.

The ratio of the mass of the polymeric ultraviolet absorber to the mass of the binder (the mass of the polymeric ultraviolet absorber / the mass of the binder) is preferably 0.25 to 0.60. More preferably, it is 30 to 0.60, and particularly preferably 0.40 to 0.55. When the ratio of the mass of the polymer type ultraviolet absorber to the mass of the binder (the mass of the ultraviolet absorber / the mass of the binder) is 0.25 or more, the cost is reduced and 0.60 or less. When it exists, it will become difficult for a ultraviolet absorber to bleed out.

<Polymethacrylate>
As the monomer component of the polymethacrylic acid ester, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, full Furyl methacrylate, tetrahi Rofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2- Ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω -Methoxypolyethyleneglycol methacrylate (added mole number n = 6), acrylic methacrylate, dimethylaminoethylmethyl chloride methacrylate salt and the like.

<Polyacrylic acid ester>
Examples of the monomer component of the polyacrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, and hexyl acrylate. 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxy Benzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexane Sil acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy Acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole) Number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate and the like.

The formation of the layer containing the polymeric ultraviolet absorber is preferably obtained by applying and drying a polymeric ultraviolet absorbent liquid dispersed in an emulsion, and the polymeric ultraviolet absorbent is dissolved in a resin liquid dissolved in an organic solvent. It can also be obtained by adding an absorbent and evaporating and drying the solvent after coating.

Also, the layer containing the polymeric UV absorber is preferably cured after being applied by adding the polymeric UV absorber to the UV curable monomer resin solution.

The layer containing a polymer type ultraviolet absorber preferably has a film thickness of 50 μm or less and an average value of light transmittance of 90% or more.

(Corrosion inhibitor)
The film mirror of the present invention preferably contains a corrosion inhibitor for the reflective layer made of metal. Here, the term “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).

In the film mirror of the present invention, the adhesive layer preferably contains an antioxidant, and the adjacent layer of the reflective layer made of metal contains a corrosion inhibitor having an adsorptive group for silver.

The optimum amount of the corrosion inhibitor varies depending on the compound to be used, but generally it is preferably within the range of 0.1 to 1.0 g / m ² .

As the corrosion inhibitor for the silver reflective layer, broadly speaking, a corrosion inhibitor and an antioxidant having an adsorptive group for silver are preferably used.

<Corrosion inhibitor having an adsorptive group for silver>
Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole It is desirable to select from a compound having a ring, a copper chelate compound, a thiourea, a compound having a mercapto group, at least one kind of naphthalene, or a mixture thereof.

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

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

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

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

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

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

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

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

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

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

Examples of naphthalene-based compounds include thionalide.

<Antioxidant>
As the corrosion inhibitor for the reflective layer made of a metal used in the film mirror of the present invention, an antioxidant can also be used.

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

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

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

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

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

Examples of the hindered amine light stabilizer 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-Tetrame Lupiperidine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, triethylenediamine, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione.

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

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

In addition, in order to prevent corrosion of the reflective layer made of metal, Cu is in contact with the reflective layer made of metal, Cu is a layer, thioether, thiol, Ni organic compound, benzotriazole, imidazole, oxazole, It is preferable to provide a tetrazaindene-based, pyrimidine-based or thiadiazole-based corrosion inhibitor layer.

(Ultraviolet absorbing layer containing an ultraviolet absorber with anti-corrosion ability)
The present invention is characterized by having an ultraviolet absorbing layer containing an ultraviolet absorber having corrosion resistance on the silver reflective layer.

The content of the UV absorber contained in the UV absorber layer containing the UV absorber having corrosion prevention ability varies depending on the compound used, but is generally 0.1 to 1.0 g / preferably in the range of m ^2.

It is preferable that the ultraviolet absorber having a corrosion preventing ability has an adsorptive group for silver and has an ultraviolet absorbing ability.

<Ultraviolet absorber with an adsorptive group for silver and anti-corrosion ability>
As an ultraviolet absorber having an adsorptive group for silver and having a corrosion inhibiting ability, amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, Desirably, the compound is selected from a compound having an imidazole ring, a compound having an indazole ring, a compound having a mercapto group, at least one kind of naphthalene, or a mixture thereof.

Examples of amines and their derivatives include O-toluidine, diphenylamine, benzamide, p-ethoxychrysidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropylammonium benzoate, diisopropylammonium nitrite, cyclohexyl Amine carbamate, nitronaphthalene ammonium nitrate, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexanecarboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate, etc., or a mixture thereof Thing, and the like.

As compounds having a mercapto group, thiophenol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, -Mercaptobenzothiazole, 2-mercaptobenzimidazole, etc., or a mixture thereof.

Examples of naphthalene-based compounds include thionalide.

(Gas barrier layer)
The film mirror of the present invention preferably has a gas barrier layer.

The gas barrier layer according to the present invention is intended to prevent deterioration of the humidity, particularly deterioration of the resin base material and various functional elements protected by the resin base material due to high humidity. As long as the above characteristics are maintained, various types of gas barrier layers can be provided. In the present invention, it is preferable to provide a gas barrier layer above the reflective layer made of the metal.

As the moisture barrier property of the gas barrier layer, the water vapor permeability at 40 ° C. and 90% RH is 100 g / m ² · day / μm or less, preferably 50 g / m ² · day / μm or less, more preferably 20 g / m ^2. -It is preferable to adjust the moisture-proof property of the gas barrier layer so as to be not more than day / μm. Also. The oxygen permeability is preferably 0.6 ml / m ² / day / atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.

The gas barrier layer according to the present invention is not particularly limited in its formation method, but after applying the ceramic precursor of the inorganic oxide film, the inorganic oxide film is formed by heating and / or ultraviolet irradiation of the coating film. The method is preferably used.

<Ceramic precursor>
The gas barrier layer according to the present invention can be formed by applying a general heating method after applying a ceramic precursor that forms an inorganic oxide film by heating, but is preferably formed by local heating. The ceramic precursor is preferably a sol-like organometallic compound or polysilazane.

<Organic metal compound>
The organometallic compound according to the present invention includes silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), and indium. It is preferable to contain at least one element of (In), tin (Sn), lanthanum (La), yttrium (Y), and niobium (Nb). In particular, the organometallic compound is at least one element of silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), zinc (Zn), and barium (Ba). It is preferable to contain. Furthermore, it is preferable to contain at least one element of silicon (Si), aluminum (Al), and lithium (Li).

The organometallic compound is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include metal alkoxides.

The metal alkoxide is represented by the following general formula (I).

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

Examples of the metal alkoxide represented by the general formula (I) include lithium ethoxide LiOEt, niobium ethoxide Nb (OEt) ₅ , magnesium isopropoxide Mg (OPr-i) ₂ , aluminum isopropoxide Al (OPr -I) ₃ , zinc propoxide Zn (OPr) ₂ , tetraethoxysilane Si (OEt) ₄ , titanium isopropoxide Ti (OPr-i) ₄ , barium ethoxide Ba (OEt) ₂ , barium isopropoxide Ba ( OPr-i) ₂ , triethoxyborane B (OEt) ₃ , zirconium propoxide Zn (OPr) ₄ , lanthanum propoxide La (OPr) ₃ , yttrium propoxide Y (OPr) ₃ , lead isopropoxide Pb (OPr- i) ₂ etc. are mentioned suitably. All of these metal alkoxides are commercially available and can be easily obtained. Moreover, the metal alkoxide is also commercially available as a low condensate obtained by partial hydrolysis, and it can be used as a raw material.

<Inorganic oxide>
The inorganic oxide according to the present invention is formed by local heating from a sol using the organometallic compound as a raw material. Therefore, silicon (Si), aluminum (Al), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), indium (In) contained in the organometallic compound, It is an oxide of an element such as tin (Sn) or niobium (Nb).

For example, silicon oxide, aluminum oxide, zirconium oxide and the like. Of these, silicon oxide is preferable.

In the present invention, as a method for forming an inorganic oxide from an organometallic compound, it is preferable to use a so-called sol-gel method and a method of applying polysilazane.

<Sol-gel method>
Here, the “sol-gel method” is to obtain a hydroxide sol by hydrolyzing an organometallic compound, etc., dehydrate it into a gel, and further heat-treat the gel. It refers to a method for preparing a metal oxide glass having a certain shape (film, particle, fiber, etc.). A multi-component metal oxide glass can be obtained by a method of mixing a plurality of different sol solutions, a method of adding other metal ions, or the like.

Specifically, it is preferable to produce an inorganic oxide by a sol-gel method having the following steps.

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

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

In the sol-gel method, the organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction. The solvent for dilution is not particularly limited as long as it can dissolve the organometallic compound and can be uniformly mixed with water. Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof. Further, a mixed solvent of butanol, cellosolve, and butyl cellosolve, or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.

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

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

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

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

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

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

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

The pH of the reaction solution is selected depending on the purpose, and for the purpose of forming a film (film) made of an inorganic composition having an inorganic matrix (metal oxide glass), for example, the pH is adjusted using an acid such as hydrochloric acid. It is preferable to ripen the mixture by adjusting it to the range of 4.5 to 5. In this case, for example, it is convenient to use a mixture of methyl red and bromocresol green as an indicator.

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

Next, the reaction product (reaction solution after aging) obtained in the previous step is heated to a temperature of 200 ° C. or lower, dried and vitrified. In heating, it is preferable that the temperature is raised gradually while paying particular attention to a temperature range of 50 to 70 ° C., followed by a preliminary drying (solvent volatilization) step and further raising the temperature. This drying is important for forming a non-porous film in the case of film formation. The temperature for heating and drying after the preliminary drying step is preferably 70 to 150 ° C, more preferably 80 to 130 ° C.

<Method of applying polysilazane>
It is also preferable that the gas barrier layer according to the present invention contains an inorganic oxide formed by local heating of a coating film after applying a ceramic precursor that forms an inorganic oxide film by heating.

When the ceramic precursor contains polysilazane, the resin substrate is coated with a solution containing a catalyst in the polysilazane represented by the following general formula (II) and an organic solvent as necessary, and the solvent is added to the ceramic precursor. Evaporate and remove, thereby leaving a polysilazane layer having a layer thickness of 0.05-3.0 μm on the resin substrate, and oxygen, active oxygen, in some cases, and nitrogen in an atmosphere containing water vapor It is preferable to employ a method of forming a glass-like transparent film on the resin substrate by locally heating the polysilazane layer in the presence.

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

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

In one of the preferred embodiments, a solution containing perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is used.

In yet another preferred embodiment, the coating according to the present invention comprises at least one polysilazane of the following general formula (III):

Formula (III): — (SiR ₁ R ₂ —NR ₃ ) _n — (SiR ₄ R ₅ —NR ₆ ) _p —
In the general formula (III), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, optionally substituted alkyl group, aryl group, vinyl group or ( Represents a trialkoxysilyl) alkyl group, wherein n and p are integers, and n is defined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

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

Also preferred are solutions containing at least one polysilazane of the general formula (IV).

Formula (IV): — (SiR ₁ R ₂ —NR ₃ ) _n — (SiR ₄ R ₅ —NR ₆ ) _p — (SiR ₇ R ₈ —NR ₉ ) _q —
In general formula (IV), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently of one another hydrogen or optionally substituted alkyl. A group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group, wherein n, p and q are integers, and n represents a number average molecular weight of 150 to 150,000 g / mol of the polysilazane. It is determined to have.

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

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

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

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

Still other components of the polysilazane formulation include, for example, additives that affect the formulation viscosity, substrate wetting, film formability, lubrication or exhaust properties, or inorganic nanoparticles such as SiO ₂ , TiO ₂ , It can be ZnO, ZrO ₂ or Al ₂ O ₃ .

By using the method of the present invention, it is possible to produce a dense glass-like layer having excellent barrier action against gas because there are no cracks and holes.

The thickness of the coating film to be formed is preferably in the range of 100 nm to 2 μm.

(Scratch prevention layer)
In the present invention, a scratch preventing layer can be provided as the outermost layer of the film mirror. The scratch prevention layer is provided for preventing scratches.

The scratch prevention layer can be composed of acrylic resin, urethane resin, melamine resin, epoxy resin, organic silicate compound, silicon resin, and the like. In particular, silicon resins and acrylic resins are preferable in terms of hardness and durability. Further, in terms of curability, flexibility, and productivity, those made of an active energy ray-curable acrylic resin or a thermosetting acrylic resin are preferable.

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

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

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

Commercially available polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam (registered trademark)” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol (registered trademark)” series, etc. ), Shin Nakamura Co., Ltd. (trade name “NK Ester” series, etc.), DIC Corporation; (trade name “UNIDIC (registered trademark)” series, etc.), Toagosei 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 .; (trade name "KAYARAD (registered trademark)" series, etc.), Products such as “light ester” series, “light acrylate” series, etc.) can be used.

In the present invention, various additives can be further blended in the scratch-preventing layer as required, as long as the effects of the present invention are not impaired. For example, stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, surfactants, leveling agents, antistatic agents, and the like can be used.

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

(Adhesive layer)
The film mirror according to the present invention may have an adhesive layer. The adhesive layer is used to enhance the adhesion between the reflective layer made of metal and the resin base material (resin film) (adhesiveness), the one that enhances the adhesion between other constituent layers, the reflective layer made of metal It may have heat resistance that can withstand the heat when it is formed by vacuum deposition, etc., and smoothness to bring out the high reflection performance inherent to the reflective layer made of metal, but it must be made of resin Is preferred.

The resin used for the adhesive layer is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness. Polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide resin Resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin or the like can be used alone or a mixed resin thereof. From the viewpoint of weather resistance, a mixed resin of a polyester resin and a melamine resin is preferable. It is more preferable to use a thermosetting resin mixed with an agent. Among polyester resins, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.

The thickness of the adhesive layer is preferably from 0.01 to 3 μm, more preferably from 0.1 to 1 μm, from the viewpoints of adhesion, smoothness, reflectance of the reflecting material, and the like.

As a method for forming the adhesive layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used. When the adhesive layer is a metal oxide, it can be formed by various vacuum film forming methods such as silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, and lanthanum nitride. For example, there are a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, a sputtering method, and the like.

(Metal layer)
In the present invention, a metal layer containing a metal having a higher ionization tendency than silver, such as copper or zinc, is adjacent to the silver reflective layer between the ultraviolet absorber layer having corrosion resistance and the silver reflective layer. It is preferable.

Since the metal layer according to the present invention has a sacrificial anticorrosive function for silver, it is necessary to use a layer adjacent to silver and having a higher ionization tendency than silver. For example, lithium, cesium, rubidium, potassium, barium, strontium, calcium, sodium, magnesium, aluminum, manganese, tantalum, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, etc. Can be mentioned. In particular, aluminum, zinc, iron, tin, and copper are preferable.

The manufacturing method of the metal layer may be formed by a wet method collectively referred to as a plating method, or the above-described vacuum film forming method may be used.

The film thickness of the metal layer is in the range of 10 nm to 500 nm in consideration of the sacrificial anticorrosive function of silver. The thickness is preferably 50 to 300 μm, more preferably 100 to 200 μm.

(Thickness of the entire film mirror)
The total thickness of the film mirror according to the present invention is preferably 75 to 250 μm, more preferably 90 to 230 μm, and still more preferably 100 to 220 μm, from the viewpoints of prevention of deflection of the mirror, regular reflectance, handling properties, and the like.

(Reflector for solar thermal power generation)
The film mirror of the present invention can be preferably used for the purpose of collecting solar heat. Although it can also be used as a solar heat collector mirror with a single film mirror, more preferably, through an adhesive layer coated on the resin substrate surface opposite to the side having the silver reflective layer across the resin substrate, The film mirror is affixed on another base material, particularly on a metal base material, and used as a reflection device for solar thermal power generation.

When used as a reflector for solar power generation, the reflector is shaped like a bowl (semi-cylindrical), and a cylindrical member having fluid inside is provided in the center of the semicircle, and the solar heat is condensed on the cylindrical member. The form which heats an internal fluid and converts the heat energy and generates electric power is mentioned as one form. In addition, heat is obtained by installing flat reflectors at multiple locations, concentrating the solar heat reflected by each reflector on a single reflector (central reflector), and reflecting it by the reflector. A form in which power is generated by converting energy in the power generation unit is also an example. In particular, in the latter form, the film mirror of the present invention is particularly preferably used because a high regular reflectance is required for the reflection device used.

<Adhesive layer>
The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.

For example, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber or the like is used.

The laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity.

The thickness of the pressure-sensitive adhesive layer is usually preferably in the range of about 1 to 50 μm from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.

The other substrate to be bonded to the film mirror of the present invention that is appropriately employed in the present invention may be any substrate that can impart the protective property of the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, Polyarylate film or sheet, polyethylene naphthalate film or sheet, polyethylene terephthalate film or sheet, plastic film or sheet such as fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc. A resin film or sheet that is coated with a resin kneaded with or is subjected to surface processing such as metal deposition is used.

The thickness of the laminated film or sheet is not particularly limited, but is usually preferably in the range of 12 to 250 μm.

In addition, these other base materials may be bonded after providing a concave portion or a convex portion before being bonded to the film mirror of the present invention, or may be formed to have a concave portion or a convex portion after being bonded. In addition, the bonding and the molding so as to have a concave portion or a convex portion may be performed at the same time.

<Metal base material>
As the metal substrate of the solar heat collecting mirror according to the present invention, the steel sheet, copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin plated steel plate, chrome plated steel plate, stainless steel plate, etc. High metal material can be used.

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.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
[Production of film mirror]
(Preparation of film mirror 1)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was used as the resin substrate. On one side of this film, a silver reflective layer having a thickness of 80 nm was formed as a silver reflective layer by vacuum deposition. In a resin in which a polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Co., Ltd.) and a TDI isocyanate (2,4-tolylene diisocyanate) are mixed at a resin solid content ratio of 10: 2 on the silver reflective layer. Furthermore, after adding glycol dimercaptoacetate as a corrosion inhibitor, an amount adjusted to 0.3 g / m ² is added and coated by a gravure coating method to form a silver protective polymer layer having a thickness of 0.1 μm. did. Furthermore, toluene containing 10% by mass of TINUVIN 328 (ultraviolet absorber, manufactured by BASF Japan) in a methyl acrylate: butyl acrylate copolymer (ratio 64:36, ultraviolet curable resin) as a layer containing an ultraviolet absorber thereon. The solution was coated by gravure coating and dried at 105 ° C. for 4 minutes. An acrylic adhesive Sdyne # 7851 (manufactured by Sekisui Chemical Co., Ltd.) is applied in a thickness of 5 μm on the surface of the resin base without the silver reflective layer to form an adhesive layer, and a film mirror 1 of a comparative example is produced. did.

(Preparation of film mirror 2)
In the production of the film mirror 1, TINUVIN 328 (ultraviolet absorber, manufactured by BASF Japan) of the layer containing the ultraviolet absorber is 10% by mass with respect to the ultraviolet curable resin, and TINUVIN 328 (ultraviolet absorber, manufactured by BASF Japan) is ultraviolet cured. A film mirror 2 of a comparative example was produced in the same manner except that 5% by mass with respect to the resin and TINUVIN234 (ultraviolet absorber, manufactured by BASF Japan Ltd.) were changed to 5% by mass with respect to the ultraviolet curable resin.

(Preparation of film mirror 3)
In the production of the film mirror 1, methyl acrylate: butyl acrylate copolymer (ratio 64:36, ultraviolet curable resin) is replaced with isobornyl acrylate (ultraviolet curable resin), and TINUVIN 328 (ultraviolet absorber, manufactured by BASF Japan Ltd.) is used as an ultraviolet ray. A film mirror 3 of a comparative example was produced in the same manner except that 10% by mass with respect to the cured resin and CGL-139 (UV absorber, manufactured by BASF Japan Ltd.) was replaced with 16% by mass with respect to the ultraviolet curable resin.

(Preparation of film mirror 4)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was used as the resin substrate. On one side of this film, a silver reflective layer having a thickness of 80 nm was formed as a silver reflective layer by vacuum deposition. In a resin in which a polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Co., Ltd.) and a TDI isocyanate (2,4-tolylene diisocyanate) are mixed at a resin solid content ratio of 10: 2 on the silver reflective layer. Furthermore, after adding glycol dimercaptoacetate as a corrosion inhibitor, an amount adjusted to 0.3 g / m ² is added and coated by a gravure coating method to form a silver protective polymer layer having a thickness of 0.1 μm. did. Furthermore, as a layer containing an ultraviolet absorber, a water-dispersed emulsion type benzotriazole polymer ultraviolet absorbing coating solution UVA-1383MG (manufactured by BASF) is coated by a gravure coating method and dried at 55 ° C. for 4 minutes. did. An adhesive layer is formed by applying an acrylic adhesive Sdyne # 7851 (manufactured by Sekisui Chemical Co., Ltd.) to a thickness of 5 μm as an adhesive on the surface of the resin base without the silver reflecting layer, and the film mirror 4 of the present invention is formed. Produced.

(Preparation of film mirror 5)
In the production of the film mirror 4, as a layer containing an ultraviolet absorber, a benzophenone polymer type ultraviolet absorbing coating solution UVA-933LP (manufactured by BASF) and a methyl acrylate: butyl acrylate copolymer (ratio 64:36) are 6: A film mirror 5 of the present invention was produced in the same manner except that the methyl ethyl ketone solution adjusted to 4 was coated by gravure coating and dried at 105 ° C. for 4 minutes.

(Preparation of film mirror 6)
In the production of the film mirror 4, a benzophenone polymer type UV absorbing coating solution UVA-933LP (made by BASF) of a layer containing a UV absorber is changed to a benzotriazole polymer type UV absorbing coating solution UVA-1933LP (made by BASF). A film mirror 6 according to the present invention was produced in the same manner except that was replaced with.

[Evaluation of film mirror]
[Preparation of solar power generation reflector]
An actual solar power generation reflector has a length of at least 1 m on a side and cannot be evaluated with an evaluation measurement device with the size as it is. Therefore, a solar power generation reflector with a small size as shown below was produced. Using this, the film mirror of the solar power generation reflecting device was evaluated.

The prepared film mirrors 1 to 6 are pasted on a slide glass having a thickness of 1 mm and a length of 25.4 mm × width of 76.2 mm through an adhesive layer having a thickness of 5 μm. 6 was produced.

[Evaluation of reflector for solar thermal power generation]
About the solar power generation reflective apparatus obtained above, regular reflectance, adhesion, weather resistance, and thermal shock resistance were evaluated by the following methods.

(Regular reflectance)
Cut out the reflector for solar power generation into 2.5cm square of measurement size, select the reflectance measurement mode of spectrophotometer U4000 (manufactured by Hitachi High-Technologies), and set the incident angle of incident light with respect to the normal of the reflecting surface The angle was adjusted to 5 °, and the reflected light of the incident light was guided to an integrating sphere to measure the regular reflectance. The regular reflection average value was calculated by averaging the reflectance in the visible light region (400 to 800 nm) and evaluated according to the following criteria.
◯: Regular reflectance average value is 90% or more Δ: Regular reflectance average value is 80% or more and less than 90% ×: Regular reflectance average value is less than 80% (Adhesion)
According to the procedure of JISK5600-5-6, 100 grids were made by cutting at intervals of 2 mm using a cutter from the light incident side of the solar power generation reflector. Adhesive tape (manufactured by Nichiban) was firmly attached to the film surface, the tape was peeled off vigorously, and the number of squares remaining without peeling was measured and evaluated according to the following criteria.
5: 90-100 squares left 4: 70-89 left squares 3: 50-69 squares left 2: 30-49 squares left 1: left squares left 29 or less (weather resistance)
The reflectance of the solar power generation reflecting device after being left for 30 days under the conditions of 85 ° C. and 85% RH was measured by the same method as the regular reflectance measurement. The reduction rate of the regular reflectance of the film mirror before and after the forced deterioration test was calculated and evaluated according to the following criteria.
5: Reflectivity decrease rate is less than 5% 4: Reflectance decrease rate is 5% or more and less than 10% 3: Reflectance decrease rate is 10% or more and less than 15% 2: Reflectivity decrease rate is 15% or more Less than 20% 1: Decrease rate of reflectivity is 20% or more (cold thermal shock resistance)
An atmosphere of −40 ° C. to + 80 ° C. was put into a thermal shock tester that repeats in a cycle of 6 hours for 10 days, and the bleed-out on the film mirror surface was visually observed and evaluated according to the following criteria.
○: 10 or less powders visually visible within an area of 1 cm square △ 11 to 20 powders visually visible within an area of 1 cm square x 21 or more powders visually visible within an area of 1 cm square Evaluation The results are shown in Table 1.

As is apparent from Table 1, it can be seen that the various characteristics of the solar power generation reflecting device of the present invention are superior to the various characteristics of the solar power generation reflecting device of the comparative example. That is, by the above means of the present invention, it is possible to prevent a decrease in the regular reflectance of the silver reflecting layer due to the deterioration of the constituent layers, and to be lightweight and flexible, to suppress the manufacturing cost, and to increase the area and mass production. It can be seen that a solar power generation reflecting device using a film mirror having excellent adhesion, weather resistance and cold shock durability and having good regular reflectance to solar heat can be obtained.

Example 2
[Production of film mirror]
(Preparation of film mirror 1)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was used as the resin substrate. On one side of the polyethylene terephthalate film, a mixture of lanthanum oxide and aluminum oxide mixed at a ratio of 8: 2 was deposited to a thickness of 60 nm by a vacuum deposition method, and then a copper reflective layer having a thickness of 100 nm was deposited by a vacuum deposition method. In the same manner, a silver reflective layer was deposited to a thickness of 150 nm. Next, a resin in which a polyester resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 is coated on the silver reflective layer by a gravure coating method to have a thickness of 0.1 μm. An inhibitor layer was formed to produce a comparative film mirror 1.

(Preparation of film mirror 2)
In the production of the film mirror 1, dicyclohexylammonium cyclohexanecarboxylate (corrosion inhibitor A, corrosion inhibitor having ultraviolet absorbing ability) as a corrosion inhibitor was contained in the corrosion inhibitor layer so as to be 0.3 g / m ² . A film mirror 2 of a comparative example was produced in the same manner except that.

(Preparation of film mirror 3)
In the production of the film mirror 1, the corrosion inhibitor layer contains glycol dimercaptoacetate (corrosion inhibitor B, corrosion inhibitor having no UV absorbing ability) as a corrosion inhibitor so as to have a concentration of 0.3 g / m ^2. A film mirror 3 of a comparative example was produced in the same manner except that an ultraviolet absorber layer was formed by depositing cerium oxide with a thickness of 100 nm on the inhibitor layer by an electron beam heating vacuum deposition method.

(Preparation of film mirror 4)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was used as the resin substrate. On one side of the polyethylene terephthalate film, a mixture of lanthanum oxide and aluminum oxide mixed at a ratio of 8: 2 was deposited to a thickness of 60 nm by a vacuum deposition method, and then a copper reflective layer having a thickness of 100 nm was deposited by a vacuum deposition method. In the same manner, a silver reflective layer was deposited to a thickness of 150 nm. On a silver reflective layer, in a resin in which polyester resin and TDI isocyanate are mixed at a resin solid content ratio of 10: 2, dicyclohexylammonium cyclohexanecarboxylate is adjusted to 0.3 g / m ² as a corrosion inhibitor. The obtained amount was added and coated by a gravure coating method to form a corrosion inhibitor layer having a thickness of 100 nm. In addition, an amount of benzotriazole adjusted to 0.3 g / m ² is added as an ultraviolet absorber to the polyester resin used as the binder for the corrosion inhibitor layer, and coating is performed by a gravure coating method. Then, an ultraviolet absorber layer having a thickness of 100 nm was formed to produce the film mirror 4 of the present invention.

(Preparation of film mirror 5)
In the production of the film mirror 4, the film mirror 5 of the present invention was produced in the same manner except that the ultraviolet absorber layer was formed by cesium oxide by a 100 nm vacuum vapor deposition method.

(Preparation of film mirror 6)
On the ultraviolet absorber layer of the film mirror 5, using a 3% by mass perhydropolysilazane solution in dibutyl ether (Clariant, NL120), bar coating was performed so that the thickness of the dried film was 100 nm. After naturally drying for 3 minutes, the film was annealed in an oven at 90 ° C. for 30 minutes to provide a gas barrier layer to produce the film mirror 6 of the present invention.

(Preparation of film mirror 7)
On the gas barrier layer of the film mirror 6, a commercially available hard coat agent (manufactured by JSR, Opstar (registered trademark) Z7534) is diluted with methyl ethyl ketone so that the solid content concentration becomes 50 mass%, and the average particle size is 1 A coating material for a scratch-preventing layer was prepared by adding 1% by mass of 5 μm acrylic fine particles (manufactured by Soken Chemical Co., Ltd., Chemisnow (registered trademark) MX series) to the solid content of the hard coat agent. After coating the above-mentioned paint, it was dried at 80 ° C. and further irradiated with ultraviolet rays 1.0 J / cm ² to be cured, and a 6 μm-thick scratch preventing layer was provided to produce the film mirror 7 of the present invention.

(Preparation of film mirror 8)
The film mirror of the present invention was similarly prepared except that the biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was replaced with the biaxially stretched polyester film (polyethylene terephthalate film, thickness 175 μm) in the production of the film mirror 7. 8 was produced.

[Preparation of solar power generation reflector]
The produced film mirrors 1 to 8 are attached on a stainless steel (SUS304) plate having a thickness of 0.1 mm and a length of 4 cm and a width of 5 cm through an adhesive layer having a thickness of 3 μm. 8 were produced.

[Evaluation of reflector for solar thermal power generation]
About the reflective apparatus for solar thermal power generation obtained above, the regular reflectance, weather resistance, light resistance, pencil hardness, and yellowing change were evaluated by the following method.

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

(Weatherability)
The specular reflectance after standing for 30 days under the conditions of 85 ° C. and 85% RH is measured by the same method as described above, and the weather resistance test is performed from the ratio of the regular reflectance before forced degradation and the regular reflectance after forced degradation. The decrease rate of the regular reflectance before and after was calculated. The evaluation criteria for the weather resistance test are shown below.
5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Regular reflectance decrease rate is 20% or more (light resistance)
After irradiating with UV light for 7 days in an environment of 65 ° C using an I-superior eye super UV tester, the regular reflectance is measured by the above method, and the regular reflectance before forced degradation and regular reflectance after forced degradation. From the ratio of the ratio, the decrease rate of the regular reflectance before and after the light resistance test was calculated. The evaluation criteria for the light resistance test are shown below.
5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Decrease rate of regular reflectance is 20% or more (pencil hardness)
Based on JIS-K5400, the pencil hardness of each sample at 45 ° inclination and 1 kg load was measured.

(Yellow change)
Using an I-superior UV tester manufactured by Iwasaki Electric Co., Ltd., ultraviolet irradiation was performed for 7 days in an environment of 65 ° C., and then yellow change was visually observed. The evaluation criteria for yellowing are shown below.
○: No difference in color is visually observed Δ: A slight difference in color is visually observed x: A difference in color is clearly visible visually Table 2 shows the evaluation results.

As is apparent from Table 2, it can be seen that the various characteristics of the solar power generation reflector using the film mirror of the present invention are superior to the solar power generator reflector using the film mirror of the comparative example. That is, the above-described means of the present invention prevents the decrease in regular reflectance due to the deterioration of the silver reflection layer, and is light and flexible, lightweight and flexible, and can be manufactured with a large area and mass production while suppressing manufacturing costs. It can be seen that a solar power generation reflecting device using a film mirror having excellent specularity and good regular reflectance with respect to solar heat can be obtained.

Claims

A film mirror having at least a reflective layer made of a metal and an ultraviolet absorbing layer on a resin substrate, wherein the ultraviolet absorbing layer is made of an ultraviolet absorbing layer containing a polymeric ultraviolet absorber, or made of the metal The reflection layer is a silver reflection layer, and the ultraviolet absorption layer is composed of an ultraviolet absorption layer (1) containing an ultraviolet absorber and an ultraviolet absorption layer (2) containing an ultraviolet absorber having an anticorrosive ability for silver. Characteristic film mirror.
A film mirror having, on a resin substrate, at least a reflective layer made of metal and an ultraviolet absorbing layer, wherein the ultraviolet absorbing layer comprises an ultraviolet absorbing layer containing a polymer type ultraviolet absorber. 1. The film mirror according to 1.
The film mirror according to claim 1 or 2, wherein the resin substrate is a resin film containing polyester, polyethylene naphthalate, acrylic, polycarbonate, polyolefin, cellulose, or polyamide.
4. The film mirror according to claim 2, wherein the reflective layer made of metal includes gold, silver, copper, aluminum, or an alloy thereof.
The film mirror according to any one of claims 2 to 4, wherein the reflective layer made of metal is produced by wet plating.
The film mirror according to any one of claims 2 to 4, wherein the reflective layer made of metal is produced by dry plating.
The film mirror according to any one of claims 2 to 6, wherein the reflective layer made of the metal is provided on the light incident side of the resin base material.
The film mirror according to any one of claims 2 to 7, wherein the layer containing the polymeric ultraviolet absorber is provided closer to the light incident side than the reflective layer made of the metal.
8. The layer containing the polymer type ultraviolet absorber is obtained by applying and drying a polymer type ultraviolet absorber liquid dispersed in an emulsion form. The film mirror according to item.
The layer containing the polymer type ultraviolet absorber is obtained by adding a polymer type ultraviolet absorber to a resin solution dissolved in an organic solvent and evaporating and drying the solvent after coating. The film mirror according to any one of claims 2 to 8.
The layer containing the polymer type ultraviolet absorber is obtained by adding a polymer type ultraviolet absorber to an ultraviolet curable monomer resin solution and curing it after application. 10. The film mirror according to any one of 10 above.
The layer according to any one of claims 2 to 11, wherein the layer containing the polymeric ultraviolet absorber has a thickness of 50 µm or less and an average value of light transmittance of 90% or more. Film mirror.
The film mirror according to any one of claims 2 to 12, wherein a Cu layer is provided in contact with the reflective layer made of the metal.
A thioether-based, thiol-based, Ni-based organic compound-based, benzotriazole-based, imidazole-based, oxazole-based, tetrazaindene-based, pyrimidine-based, or thiadiazole-based corrosion inhibitor layer is provided in contact with the metal reflective layer. The film mirror according to any one of claims 2 to 13, wherein the film mirror is provided.
A film mirror having at least a reflective layer made of a metal and an ultraviolet absorbing layer on a resin base material, the reflective layer made of the metal being a silver reflective layer, and having a silver corrosion preventing ability on the silver reflective layer 2. The film mirror according to claim 1, further comprising an ultraviolet absorbing layer (2) containing the ultraviolet absorber and further having an ultraviolet absorbing layer (1) containing the ultraviolet absorber.
16. The film mirror according to claim 15, wherein the ultraviolet absorber having corrosion inhibiting ability contained in the ultraviolet absorbing layer (2) has an adsorptive group for silver and has ultraviolet absorbing ability.
The film mirror according to claim 15 or 16, wherein the ultraviolet absorber contained in the ultraviolet absorbing layer (1) is an inorganic ultraviolet absorber.
A metal layer containing a metal having a higher ionization tendency than silver is adjacent to the silver reflective layer between the ultraviolet absorbing layer (2) and the silver reflective layer. 2. A film mirror according to claim 1.
The film mirror according to any one of claims 15 to 18, wherein an adhesive layer is provided between the ultraviolet absorbing layer (2) and the silver reflecting layer or between the ultraviolet absorbing layer (2) and the metal layer.
The film mirror according to any one of claims 15 to 19, further comprising a gas barrier layer above a layer adjacent to the silver reflective layer.
The film mirror according to any one of claims 15 to 20, wherein the outermost layer has a scratch-preventing layer.
The film mirror according to any one of claims 15 to 21, wherein the total thickness of the layer including the resin base material is 75 to 250 µm.
A film mirror manufacturing method for manufacturing the film mirror according to any one of claims 1 to 22, wherein the reflective layer made of the metal is formed by silver vapor deposition.
A solar power generation reflecting apparatus using the film mirror according to any one of claims 1 to 22 or the film mirror obtained by the film mirror manufacturing method according to claim 23, wherein the resin base material is used. The film mirror is pasted on a metal substrate through an adhesive layer coated on the side having the reflective layer made of the metal and the opposite side of the resin substrate. Reflector for solar thermal power generation.