JP2014199297A - Film mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film mirror having excellent light resistance.SOLUTION: A film mirror sequentially comprises a supporting body, an intermediate layer which contains an ultraviolet absorbent that has the maximum absorption in the UV-B region, a metal reflective layer and a protective layer in this order.

Description

  The present invention relates to a film mirror.

  In recent years, research on alternative energy alternatives to fossil fuels typified by oil, coal, natural gas, etc. has been conducted extensively. In particular, natural energy such as solar light, wind power, and geothermal heat has attracted attention as clean energy without concern about resource depletion and global warming. Among these, solar energy using sunlight is expected to be further developed as energy that can be stably supplied.

  On the other hand, solar energy has a problem of low energy density. In order to solve this problem, in recent years, attempts have been made to collect sunlight using a huge reflector.

  Until now, a reflector for condensing sunlight has been used outdoors because it is installed outdoors and exposed to ultraviolet rays, heat, wind and rain, sand dust and the like caused by sunlight. However, although a glass reflector is excellent in weather resistance, it is heavy, easily damaged, and lacks flexibility, so it is difficult to handle. Therefore, recently, it has been considered to replace the glass reflector with a light and flexible resin reflector sheet.

However, when a resin-made reflective sheet is used as a solar light collecting film mirror, there is a problem that the resin deteriorates due to exposure to sunlight for a long period of time, and the reflectivity of the film mirror decreases.
For this problem, an ultraviolet absorber that absorbs ultraviolet rays in the UV-A region and an ultraviolet absorber that absorbs ultraviolet rays in the UV-B region are contained on the light incident side of the resin base material and the silver reflective layer. Attempts have been made to provide layers (see, for example, Patent Document 1). According to the film mirror described in Patent Document 1, light having a wavelength that passes through the silver reflective layer can be efficiently shielded by the layer containing the ultraviolet absorber, and the decrease in regular reflectance can be suppressed. Is supposed to be possible.

International Publication No. 2011/0777816 Pamphlet

However, the film mirror described in Patent Document 1 contains an ultraviolet absorber that absorbs ultraviolet rays in the UV-A region and an ultraviolet absorber that absorbs ultraviolet rays in the UV-B region on the light incident side of the silver reflecting layer. Therefore, the light in the wavelength region that can be reflected is absorbed by the ultraviolet absorber, and the utilization efficiency of sunlight is reduced. Moreover, since the film mirror described in patent document 1 does not take any protective means against sunlight on the resin base material side of the silver reflection layer, the light reflected from the ground is long from the resin base material side. If it receives for a period, a resin base material will deteriorate. The deterioration of the resin base material becomes a factor that leads to corrosion of the silver reflection layer, and causes a reduction in the reflection performance of the film mirror.
Therefore, realization of a film mirror in which deterioration of the resin due to both sunlight from the light incident side and sunlight from the resin base material due to reflection is suppressed without reducing the utilization efficiency of sunlight is required. It was.

  This invention is made | formed in view of the said situation, and the subject of this invention is providing the film mirror excellent in light resistance.

Specific means for achieving the above object are as follows.
<1> A film mirror having a support, an intermediate layer containing an ultraviolet absorber having maximum absorption in the UV-B region, a metal reflective layer, and a protective layer in this order.

The film mirror as described in <1> whose content of the ultraviolet absorber in a <2> intermediate | middle layer is 1 mass%-20 mass% with respect to the total solid of an intermediate | middle layer.

<3> intermediate layer further comprises a photopolymerization initiator, the content per unit area of the ultraviolet absorber in the intermediate layer ^{is 0.02g / m 2 ~0.7g / m 2} <1> or <2>.

<4> The film mirror according to any one of <1> to <3>, further including a back surface protective layer containing an ultraviolet absorber on the side opposite to the intermediate layer side of the support.

<5> The film mirror according to any one of <1> to <4>, wherein the metal reflective layer is formed by a plating method.

<6> The film mirror according to any one of <1> to <5>, which is used for collecting sunlight.

<7> A solar reflective plate in which the film mirror according to any one of <1> to <6> is bonded to a substrate made of resin, metal, or ceramic via an adhesive layer. .

  In this specification, “UV-B region” means a wavelength region of 260 nm to 320 nm, and “UV-A region” means a wavelength region of 321 nm to 400 nm.

  In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  In this specification, the “light incident side” means a side on which light reflected by the metal reflection layer is incident.

  ADVANTAGE OF THE INVENTION According to this invention, the film mirror excellent in light resistance can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

[Film mirror]
The film mirror of the present invention is characterized by having a support, an intermediate layer containing an ultraviolet absorber having a maximum absorption in the UV-B region, a metal reflective layer, and a protective layer in this order. Moreover, the film mirror of this invention may have further the back surface protective layer containing a ultraviolet absorber on the opposite side to the intermediate | middle layer side of a support body.
The film mirror of this invention becomes the thing excellent in light resistance by having the intermediate | middle layer containing the ultraviolet absorber which has maximum absorption in a UV-B area | region between a support body and a metal reflective layer.
The reason is presumed as follows.
The light in the UV-B region is transmitted through the metal reflection layer, and when the intermediate layer including the ultraviolet absorber having the maximum absorption in the UV-B region is provided between the support and the metal reflection layer, the metal reflection layer The light in the UV-B region that has passed through is absorbed by the ultraviolet absorber contained in the intermediate layer, and as a result of suppressing the deterioration of the intermediate layer, a film mirror excellent in light resistance can be realized.
In addition, when the reflected light from the ground is received from the support side, since the intermediate layer contains the ultraviolet absorber having the maximum absorption in the UV-B region, the deterioration of the intermediate layer adjacent to the metal reflective layer is suppressed. As a result, a film mirror excellent in light resistance can be realized.
In the film mirror of the present invention, it is possible to avoid absorption of light in the wavelength region that can be reflected by the metal reflective layer by having a layer containing an ultraviolet absorber on the side opposite to the light incident side of the metal reflective layer. It can be reflected without reducing the light utilization efficiency.
Hereinafter, each material which can comprise the film mirror of this invention is demonstrated in detail.

<Support>
In the present invention, as the material for the film substrate used as the support, a resin film obtained by molding a resin into a film shape is preferably used from the viewpoint of flexibility and weight reduction.
The resin is not particularly limited as long as it can be formed into a film shape. For example, phenol resin, epoxy resin, polyimide resin, bismaleimide triazine (BT) resin, polyphenylene ether (PPE) resin, tetra Fluoroethylene resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyamide resin (including aramid resin), polyethersulfone, triacetylcellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene Polypropylene, polystyrene, polybutadiene, polyacetylene and the like are preferable. Of these, polyester resins and polyimide resins are particularly suitable.
In the present invention, these resins may be used alone, or a plurality of resins may be used in combination.
In addition, a resin film obtained by molding glass epoxy, liquid crystal polymer, or the like into a film shape can also be used.

In the present invention, the support may be subjected to a surface treatment in order to facilitate the formation of an intermediate layer provided thereon.
Examples of the surface treatment include treatment for decomposing and activating the surface of the support by UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment, and the like. Examples of other surface treatments include treatment with an alkaline solution such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution, and potassium hydroxide solution, treatment with an acidic solution such as sulfuric acid, hydrochloric acid, and nitric acid. Further, the support may be subjected to a cleaning treatment with water or an organic solvent such as methanol, ethanol, toluene, ethyl acetate, or acetone in order to remove dirt on the surface thereof.

  In the present invention, from the viewpoint of improving the reflection performance of the film mirror, it is preferable to use a support having a surface roughness (Ra) of 50 nm or less, more preferably a support of 20 nm or less, and a support of 5 nm or less. More preferably, the body is used.

The support may contain either a polymer type ultraviolet absorber such as benzotriazole, benzophenone, triazine, or cyanoacrylate, or an inorganic particle type ultraviolet absorber such as titanium oxide.
Furthermore, the support may contain a plasticizer from the viewpoint of maintaining flexibility, and may contain an antioxidant, a radical scavenger, and the like from the viewpoint of preventing deterioration of the film itself.

  The thickness of the support in the present invention is preferably 10 μm to 500 μm, more preferably 50 μm to 400 μm, and more preferably 75 μm to 300 μm from the viewpoint of handling during production, mechanical strength, cost, and the like. Further preferred.

<Intermediate layer>
The film mirror of this invention has an intermediate | middle layer containing the ultraviolet absorber (henceforth a "ultraviolet absorber B" suitably) which has maximum absorption in a UV-B area | region between a support body and a metal reflective layer. .
In the present invention, the UV absorber B is contained in the intermediate layer provided between the support and the metal reflective layer, thereby suppressing the deterioration of the resin due to the light in the UV-B region transmitted through the metal reflective layer. In addition, deterioration of the resin from the support side due to light such as reflection is suppressed, and consequently corrosion of the metal reflection layer is suppressed.

  The ultraviolet absorber contained in the intermediate layer of the present invention is not particularly limited as long as it has a maximum absorption in the UV-B region. For example, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, Benzoate ultraviolet absorbers and ultraviolet absorbers having a cyanoacrylate skeleton are preferred. Examples of commercially available ultraviolet absorbers having maximum absorption in the UV-B region include, for example, “UVINUL 3000”, “UVINUL 3008”, “UVINUL 3030”, “UVINUL 3035”, “UVINUL 3039” manufactured by BASF Japan Ltd. ”,“ UVINUL 3040 ”,“ UVINUL 3088 ”,“ TINUVIN 400 ”,“ TINUVIN 405 ”,“ TINUVIN 1577 ”,“ TINUVIN 120 ”,“ LA 51 ”manufactured by ADEKA, and the like.

  The content of the ultraviolet absorber B in the intermediate layer is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass with respect to the total solid content of the intermediate layer. More preferably, it is 10 mass%-10 mass%. When the content of the ultraviolet absorber B in the intermediate layer is within the above range, the ultraviolet absorber B does not bleed out and a sufficient light resistance effect is obtained.

Content per unit area of the ultraviolet absorbent B in the intermediate ^layer, it is ^{preferably, 0.05g / m 2 ~0.5g / m} 2 is 0.02g / ^{m 2} ~0.7g / m 2 it is more ^preferable, and further preferably from ^{0.1g / m 2 ~0.3g / m 2} . When the content per unit area of the ultraviolet absorber B in the intermediate layer is within the above range, the adhesion and plating properties between the intermediate layer and the metal reflective layer are good.
By controlling the content per unit area of the ultraviolet absorber B in the intermediate layer, the reason why the adhesion and plating properties between the intermediate layer and the metal reflective layer are not clear, but the present inventor, I guess as follows.
If the intermediate layer is cured too much by UV irradiation, the surface resistance will increase in the pre-plating treatment step, resulting in insufficient plating. On the other hand, when the ultraviolet absorber B is contained in the intermediate layer, the ultraviolet absorber B absorbs UV for curing, and curing is moderately suppressed. As a result, the surface resistance is suitable for the formation of plating, and a sufficient amount of precursor adheres to the intermediate layer, so that the adhesion between the intermediate layer and the metal reflective layer and the adhesion of the plating are good. It is thought that it becomes.

  The thickness of the intermediate layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, from the viewpoint of suppressing the deterioration of the support due to UV-B that passes through the metal reflective layer. More preferably, the thickness is 0.3 μm to 2 μm.

  An intermediate | middle layer is provided in order to improve the adhesiveness of a support body and a metal reflective layer. The intermediate layer is not particularly limited as long as it has a function of improving the adhesion between the support and the metal reflective layer. For example, an intermediate layer, a metal reflective layer for easily adhering metal are provided. Examples thereof include a plating undercoat polymer layer useful in the case of forming by a plating method, and these may be composed of a single layer or may be composed of two or more layers.

[Easily adhesive layer]
In the present invention, an easy-adhesion layer may be provided in order to improve the adhesion between the support and the metal reflective layer. When the plating undercoat polymer layer is provided on the easy adhesion layer, the easy adhesion layer improves the adhesion between the support and the plating undercoat polymer layer, and as a result, the adhesion between the support and the metal reflective layer is improved. More improved.

The easy-adhesion layer preferably contains the same resin as the resin constituting the support or a resin having an affinity for the resin constituting the support from the viewpoint of adhesion to the adjacent support.
Examples of the resin having affinity with the resin constituting the support include resins having similar thermal properties such as glass transition point, elastic modulus, and linear expansion coefficient.

As for resin contained in an easily bonding layer, a thermosetting resin, a thermoplastic resin, or a mixture thereof is mentioned, for example. Examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, unsaturated polyester resins, bismaleimide resins, isocyanate resins, and the like. Examples of the thermoplastic resin include acrylic resin, polyester resin, polyurethane resin, polyolefin resin, ethylene acrylic acid copolymer resin, ethylene acrylic acid ester copolymer resin, phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, Examples thereof include polyphenyl ether and polyether imide. You may use these individually or in mixture of 2 or more types.
Note that the thermoplastic resin and the thermosetting resin may be used alone or in combination. The combined use of two or more kinds of resins is performed for the purpose of exhibiting a more excellent effect by compensating for each defect.

When using a thermoplastic resin, it is preferable to use a crosslinking agent as needed. As a kind of the crosslinking agent, a crosslinking agent having a plurality of reactive groups that react with a functional group such as a carboxylic acid group, a hydroxyl group, an amino group, and a mercaptan group, which the thermoplastic resin has, is preferable. Preferred types of reactive groups include carbodiimide groups, oxazoline groups, isocyanate groups, epoxy groups, melamines and the like. Examples of the compound having a plurality of these reactive groups include cross-linking agents such as carnodilite (manufactured by Nisshinbo Co., Ltd.), Epocross (manufactured by Nippon Shokubai Co., Ltd.), Denacol (manufactured by Nagase ChemteX Corporation), becamine (manufactured by DIC Kita Nippon Polymer Co., Ltd.), etc. Is commercially available.
The addition amount of the crosslinking agent is preferably adjusted so that the functional group of the thermoplastic resin and the reactive group of the crosslinking agent are equivalent, but in order to obtain appropriate film properties, the addition amount of the crosslinking agent is You may increase / decrease suitably.

  As long as the effects of the present invention are not impaired, the easy-adhesion layer may be provided with various additives such as a surfactant, an antistatic agent, and waxes as a coating material, a mat material made of organic or inorganic fine particles. You may add 1 type (s) or 2 or more types.

  When any additive is added, it is preferably added in the range of more than 0% by mass to 50% by mass or less, and more than 0% by mass to 20% by mass with respect to the resin as the main component. It is more preferable to add in the range of% or less. When the additive is used in a range exceeding 50% by mass with respect to the resin, there is a concern that properties such as strength inherent in the resin itself are deteriorated.

[Method of forming easy-adhesion layer]
The easy adhesion layer is obtained by applying a coating solution in which each of the above-described components is dispersed or dissolved in water, or a coating solution in which each component is dissolved in an organic solvent that can be dissolved, to the support by a method such as coating. And / or it can form by hardening by light irradiation.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried, but from the viewpoint of production suitability, the drying temperature is preferably 190 ° C. or lower and the drying time is preferably within 10 minutes. More preferably, the drying temperature is 40 ° C. to 180 ° C. and the drying time is within 5 minutes.

  The solvent used in preparing the coating solution is not particularly limited as long as it can dissolve or disperse the above-described components. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C. to 150 ° C. may be selected. Specifically, cyclohexanone, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, water and the like described in JP-A 2007-154306, paragraph [0045] can be used. Among these, water is particularly preferable from the viewpoint of suppressing VOC (Volatile Organic Compounds, volatile organic compounds). The above exemplified solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 1% by mass to 50% by mass. In addition, when using water as a solvent, it is preferable to make resin contained in the said easily bonding layer into a water dispersion or a water-solubilization thing.

  Generally the thickness of the easily bonding layer in this invention is 0.05 micrometer-5 micrometers, and it is preferable that they are 0.1 micrometer-3 micrometers.

[Plating undercoat polymer layer]
The plating undercoat polymer layer in the present invention includes at least reduced metal particles and a plating undercoat polymer described later.
In the present invention, it is preferable to form a plating undercoat polymer layer containing a metal precursor on a support by a method such as coating using a composition containing a metal precursor and a plating undercoat polymer described later. Further, in the present invention, after forming a layer on a support using a composition containing a plating undercoat polymer described later, the composition containing a metal precursor is brought into contact with the layer by a method such as immersion, It is also preferred to form a plating undercoat polymer layer containing reduced metal particles by forming a polymer layer containing a metal precursor and then reducing the metal precursor contained in the polymer layer.

(Plating undercoat polymer)
The plating undercoat polymer used for forming the plating undercoat polymer layer will be described.
The plating undercoat polymer used to form the plating undercoat polymer layer has at least a functional group that interacts with the metal precursor (hereinafter, referred to as “interactive group” as appropriate), and has water resistance and chemical resistance. From the viewpoint, it is preferable to have a polymerizable group as necessary.
As the main skeleton of the plating undercoat polymer, an acrylic polymer, polyether, polyacrylamide, polyamide, polyimide, methacrylic polymer, polyester, polyurethane, ethylene acrylic acid copolymer, and the like are preferable, and an acrylic polymer is more preferable.

The plating undercoat polymer preferably has the polymerizable group and the interactive group in the molecule, and when the polymerizable group has the polymerizable group, the polymerizable group is added to at least the main chain terminal and the side chain of the polymer. It only has to have in either. Examples of the plating undercoat polymer include a polymer composed of the structural unit having the polymerizable group and the structural unit having the interactive group, and the like. It may be a polymer comprising a functional group. Moreover, the plating undercoat polymer may contain 2 or more types of polymeric groups, and may contain 2 or more types of interactive groups. The polymerizable group may be introduced by a polymer reaction after the production of the polymer.
Moreover, the plating undercoat polymer may contain structural units other than the structural unit containing a polymeric group and the structural unit containing an interactive group according to the objective. By including a structural unit other than the structural unit containing a polymerizable group and a structural unit containing an interactive group, when it is used as a plating undercoat composition, it becomes excellent in solubility in water or an organic solvent, and is uniform. Various layers can be formed.

A preferable embodiment of the plating undercoat polymer includes an acrylic polymer having an acidic group and a polymerizable group as an interactive group in the side chain.
Hereinafter, a polymerizable group, an interactive group and the like contained in the plating undercoat polymer will be described in detail.

-Polymerizable group-
The polymerizable group of the plating undercoat polymer is a functional group that can form a chemical bond between polymers or between the polymer and the base layer (support or an undercoat layer provided on the support) by applying energy. I just need it. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Among these, a radical polymerizable group is preferable from the viewpoint of reactivity.
Examples of the radical polymerizable group include methacryloyl group, acryloyl group, itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group, maleic acid ester group, styryl group, vinyl group, acrylamide group and methacrylamide group. It is done. Among these, methacryloyl group, acryloyl group, vinyl group, styryl group, acrylamide group, and methacrylamide group are preferable, and methacryloyl group, acryloyl group, acrylamide group, and methacrylamide are preferable from the viewpoint of radical polymerization reactivity and synthetic versatility. A group is more preferable, and from the viewpoint of alkali resistance, an acrylamide group and a methacrylamide group are more preferable.
Examples of the polymerizable group introduced into the acrylic polymer include various polymerizations such as (meth) acrylic groups such as (meth) acrylate groups and (meth) acrylamide groups, vinyl ester groups of carboxylic acids, vinyl ether groups, and allyl ether groups. Sexual groups are preferred.

-Interactive group-
The interaction group possessed by the plating undercoat polymer is a functional group that interacts with the metal precursor (for example, a coordination group, a metal ion-adsorptive group, etc.), and a functional group that can interact electrostatically with the metal precursor. A nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination group with a metal precursor can be used.
Specific examples of the interactive group include amino group, amide group, imide group, urea group, triazole ring, imidazole group, pyridine group, pyrimidine group, pyrazine group, triazine group, piperidine group, piperazine group, pyrrolidine group and pyrazole. Groups, groups containing alkylamine structures, nitrogen-containing functional groups such as cyano groups, cyanate groups (R—O—CN); ether groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, carbonate groups, carbonyl groups, ester groups, N -Oxygen-containing functional groups such as a group containing an oxide structure, a group containing an S-oxide structure, a group containing an N-hydroxy structure; a thiophene group, a thiol group, a thiourea group, a sulfoxide group, a sulfonic acid group, a sulfonic acid ester structure Sulfur-containing functional groups such as containing groups; Phosphate groups, phosphoroamide groups, phosphine groups, phosphates Phosphorus-containing functional group and a group containing Le structure; chlorine, such as group containing a halogen atom such as bromine and the like, in a functional group capable of having a salt structure can also be used salts thereof.
The interactive group may be a non-dissociable functional group or an ionic polar group. The plating undercoat polymer may have these at the same time, but preferably has an ionic polar group as an interactive group and does not have a non-dissociable functional group.

As the ionic polar group, a carboxylic acid group, a sulfonic acid group, from the viewpoint of adhesion to a support of a plating undercoat polymer (in the case where the easy-adhesion layer is formed on the support), Phosphoric acid groups and boronic acid groups are preferably mentioned. Among these, there are moderate acidity (not decomposing other functional groups), less concern of affecting other functional groups, Carboxylic acid groups are particularly preferred from the standpoint of excellent affinity for and the availability of raw materials.
An ionic polar group such as a carboxylic acid group can be introduced into the plating undercoat polymer by copolymerizing a radical polymerizable compound having an acidic group.

As the polymer having a radical polymerizable group and an interactive group composed of a non-dissociable functional group, the polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540 are preferably used. it can.
As the polymer having a radically polymerizable group and an interactive group composed of an ionic polar group, the polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 are preferably used. Can do.
Further, as a polymer having a radical polymerizable group, an interactive group composed of a non-dissociative functional group, and an interactive group composed of an ionic polar group, paragraph [0010] of JP 2010-248464 A is disclosed. To [0128], JP 2010-84196 A, and US Patent Application Publication No. 2010-080964, paragraphs [0030] to [0108] can be suitably used.

The plating undercoat polymer layer preferably contains a radical polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator in order to increase sensitivity to energy application. The radical polymerization initiator is not particularly limited, and generally known ones are used.
However, when energy is applied, the plating undercoat polymer can generate an active site that interacts with the support or the easy-adhesion layer, that is, a polymer having a polymerization initiation site in the polymer skeleton is used as the plating undercoat polymer. In some cases, it is not necessary to add these radical polymerization initiators.

  The amount of the radical polymerization initiator contained in the composition for forming the plating undercoat polymer layer (hereinafter, appropriately referred to as “a composition for forming a plating undercoat polymer layer”) is the amount of the composition for forming the plating undercoat polymer layer. Although it is selected according to the configuration, it is generally preferably about 0.05% by mass to 30% by mass in the composition for forming a plating undercoat polymer layer, and 0.1% by mass to 10.0%. More preferably, it is about mass%.

[Method of forming plating undercoat polymer layer]
-Application of a composition for forming a plating undercoat polymer layer-
The plating undercoat polymer layer is formed, for example, by applying a composition for forming a plating undercoat polymer layer on the surface of the support or the easy-adhesion layer provided on the support and applying energy thereto. be able to.
When the plating undercoat polymer layer is directly provided on the support, it is preferable to carry out an easy adhesion treatment (for example, corona treatment, plasma treatment, etc.) such as applying energy to the surface of the support in advance.
The method of providing the polymer layer containing the plating undercoat polymer on the support is not particularly limited. For example, the method of immersing the support in the composition for forming the plating undercoat polymer layer or the formation of the plating undercoat polymer layer And a method of applying the composition for use on a support. From the viewpoint of easily controlling the thickness of the layer to be obtained, a method of coating the plating undercoat polymer layer forming composition on the support is preferred.

The coating amount of the plating undercoat polymer layer forming composition is preferably from the viewpoint of a sufficient interaction with the later-described metal precursor is 0.05g ^/ m ² ~10g / m 2 in terms of solid content , and particularly preferably ^{0.3g / m 2 ~5g / m 2} .
The plating undercoat polymer layer forming composition applied to a support or the like is preferably dried at 20 ° C. to 60 ° C. for 1 second to 2 hours, and then dried at a temperature exceeding 60 ° C. for 1 second to 2 hours, It is more preferable to dry at a temperature of 60 ° C. to 60 ° C. for 1 second to 20 minutes and then to dry at a temperature exceeding 60 ° C. for 1 second to 20 minutes.

  When energy is applied after coating the composition for forming a plating undercoat polymer layer on the surface of the support or the easy-adhesion layer provided on the support, the polymer has a polymerizability in the energy application region. An interaction is formed between the groups or the polymerizable group of the polymer and the support or the easy-adhesion layer provided on the support, and the support (or the easy-adhesion layer) is formed on the support. A plated undercoat polymer layer is formed which is immobilized on the support via the substrate. In this way, the support and the plating undercoat polymer layer are firmly adhered.

-Granting energy-
Examples of the energy application method include heating and exposure.
As an energy application method by exposure, specifically, light irradiation by a UV lamp, visible light, or the like is possible. Examples of the light source used for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Exposure power, to the polymerization readily proceed, for inhibiting the degradation of the polymer, and preferably the polymer is in the range from the viewpoint to the formation of 10mJ ^/ cm ² ~8000mJ / cm 2 good interaction , and more preferably in the range of ^{100mJ / cm 2 ~3000mJ / cm 2} .
Note that exposure may be performed in an atmosphere in which substitution with an inert gas such as nitrogen, helium, or carbon dioxide is performed, and the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less.

Energy application by heating can be performed by, for example, a general heat heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like.
In addition, when energy is applied by heating, the temperature is preferably 20 ° C. to 200 ° C., in order to facilitate the polymerization, and to suppress thermal denaturation of the support, and 40 ° C. to 120 ° C. It is more preferable that

-Removal of unreacted undercoating polymer-
After energy application, a step of removing unreacted polymer may be provided as appropriate. As a method for removing unreacted polymer, for example, a solvent for dissolving the polymer, or in the case of an alkali-soluble polymer, an alkaline developer (sodium carbonate, sodium hydrogen carbonate, ammonia water, sodium hydroxide aqueous solution) or the like is plated. The method of making it contact the support body in which the undercoat polymer layer was formed is mentioned.

The thickness of the plating undercoat polymer layer is not particularly limited, but is preferably 0.05 μm to 10 μm, more preferably 0.3 μm to 5 μm, from the viewpoint of adhesion to the support and the like. preferable.
The surface roughness (Ra) of the plating undercoat polymer layer is preferably 20 nm or less, and more preferably 10 nm or less, from the viewpoint of reflection performance. The surface roughness (Ra) here is an arithmetic average roughness obtained in accordance with JIS B0601 (1994).

-Reduced metal particles-
The plating undercoat polymer layer in the present invention contains reduced metal particles. Reduced metal particles contained in the plating undercoat polymer layer are obtained by applying a metal precursor to the plating undercoat polymer layer and reducing the metal precursor to form reduced metal particles. It is done. When the metal precursor is applied to the plating undercoat polymer layer, the metal precursor adheres to the interactive group due to the interaction.

-Metal precursor-
The metal precursor used in the present invention is not particularly limited as long as it functions as an electrode by changing to a metal by a reduction reaction, but preferably functions as an electrode for plating in the formation of a metal reflective layer. It is done.
Specifically, metal ions such as Au, Pt, Pd, Ag, Cu, Ni, Al, Fe, and Co are used. These metal ions become zero-valent metal particles by a reduction reaction.

It is preferable that the metal ion which is a metal precursor is contained in the composition for forming a plating undercoat polymer layer as a metal salt.
The metal salt to be used is not particularly limited as long as it is dissolved in an appropriate solvent and dissociated into a metal ion and a base (anion). M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. For example, Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, Pd ion and the like can be mentioned. Among them, those capable of multidentate coordination are preferable, in particular, the types of functional groups capable of coordination, In terms of number and catalytic ability, Ag ions, Cu ions, and Pd ions are preferred.

As the Ag ions, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples include silver diethyldithiocarbamate and silver p-toluenesulfonate. Among these, silver nitrate is preferable from the viewpoint of water solubility.
As the Cu ions, those obtained by dissociating copper compounds as shown below can be suitably used. Specific examples of copper compounds include copper nitrate, copper acetate, copper sulfate, copper cyanide, copper thiocyanate, copper chloride, copper bromide, copper chromate, copper chloranilate, copper salicylate, copper diethyldithiocarbamate, diethyldithio Examples include copper carbamate and copper p-toluenesulfonate. Among these, copper sulfate is preferable from the viewpoint of water solubility.

The metal precursor is preferably applied to the formed plating undercoat polymer layer as a dispersion or solution (metal precursor liquid).
As a method of providing, for example, after forming a plating undercoat polymer layer on a support using a composition for forming a plating undercoat polymer layer, a composition containing a metal precursor on the surface of the plating undercoat polymer layer (dispersion) And a method of applying a liquid or a solution. Moreover, the method of immersing the support body in which the plating undercoat polymer layer was formed in the composition (dispersion liquid or solution) containing a metal precursor is mentioned.
The metal precursor is brought into contact with the plating undercoat polymer layer by a dispersion or solution containing the metal precursor, and interaction by intermolecular force such as van der Waals force, or interaction by coordination bond by lone pair of electrons. Can be adsorbed on the interaction group in the plating undercoat polymer.

From the viewpoint of sufficiently adsorbing the metal precursor, the concentration of the metal precursor in the dispersion or solution containing the metal precursor is preferably 0.001% by mass to 50% by mass, It is more preferable that it is mass%-30 mass%.
Water or an organic solvent is used as a solvent for the metal precursor dispersion and solution. By containing water or an organic solvent, the permeability of the metal precursor to the polymer layer is improved, and the metal precursor can be efficiently adsorbed to the interactive group.

When the dispersion is used for applying the metal precursor to the plating undercoat polymer layer, the particle diameter of the metal precursor is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and more preferably 1 nm to 60 nm. More preferably it is. By setting the particle diameter of the metal precursor within the above range, the particle diameter of the reduced metal particles can be controlled to a desired size.
In addition, the particle diameter here is an average primary particle diameter (volume conversion), and is read from an image of SEM (S-5200, manufactured by Hitachi High-Tech Manufacturing & Service Co., Ltd.).

  The metal precursor may be previously contained in the composition for plating undercoat polymer layer. In that case, the content of the metal precursor in the composition for plating undercoat polymer layer is 0 with respect to the total amount of the composition. It is preferably 5% by mass to 100% by mass, and more preferably 1% by mass to 50% by mass.

Metal ions, which are metal precursors applied to the plating undercoat polymer layer, are reduced by a metal activation liquid (reducing liquid). The metal activation liquid includes a reducing agent capable of reducing a metal precursor (mainly metal ions) to a zero-valent metal, and a pH adjuster for activating the reducing agent.
The concentration of the reducing agent with respect to the entire metal activation liquid is preferably 0.05% by mass to 50% by mass, and more preferably 0.1% by mass to 30% by mass.
As the reducing agent, boron-based reducing agents such as sodium borohydride and dimethylamine borane, and reducing agents such as formaldehyde and hypophosphorous acid can be used. In particular, reduction with an aqueous alkaline solution containing formaldehyde is preferred.

The concentration of the pH adjusting agent with respect to the entire metal activation liquid is preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass.
As the pH adjuster, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen carbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and the like can be used.
The temperature during the reduction is preferably 10 ° C to 100 ° C, more preferably 20 ° C to 70 ° C.
These concentrations and temperatures are within the above ranges in view of the particle diameter of the metal precursor, the surface roughness (Ra) of the polymer layer, the conductivity (surface resistance value), and the deterioration of the reducing solution during reduction. It is preferable.

The particle diameter of the reduced metal particles contained in the plating undercoat polymer layer is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and further preferably 1 nm to 60 nm, from the viewpoint of reflection performance. preferable. By being in this range, the reflectance after plating becomes good.
In addition, the particle diameter here is read from an SEM (S-5200, manufactured by Hitachi High-Tech Manufacturing & Service) image.

The surface resistance value of the plating undercoat polymer layer containing the reduced metal particles is preferably 0.001Ω / □ or more and 100Ω / □ or less, and more preferably 0.03Ω / □ or more and 50Ω / □ or less. Within this range, the plated surface is formed uniformly and smoothly, and the reflectance is good.
Moreover, the surface roughness (Ra) of the plating undercoat polymer layer containing the reduced metal particles is preferably 20 nm or less, more preferably 10 nm or less, from the viewpoint of reflection performance. The surface roughness (Ra) here is an arithmetic average roughness obtained in accordance with JIS B0601 (1994).

  The plating undercoat polymer layer containing the metal particles thus obtained is suitably used when a metal reflective layer described in detail below is formed by a plating method that is a wet method, and plating is performed using the plating undercoat polymer layer. The metal reflective layer formed by the method is excellent in adhesion to the support and surface smoothness.

<Metal reflective layer>
A metal reflective layer is a reflective layer comprised with the metal film containing a metal. The metal that forms the metal reflection layer is not particularly limited as long as it reflects light, but a metal that reflects both visible light and infrared light is preferable. Examples of the metal that reflects both visible light and infrared light include silver, aluminum, copper, and nickel.
The metal forming the metal reflection layer in the present invention is preferably silver or an alloy containing silver from the viewpoint of light reflection performance. According to silver or an alloy containing silver, the reflectance in the visible light region of the film mirror can be increased, and the dependency of the reflectance on the incident angle can be reduced. The visible light region here means a wavelength region of 400 nm to 700 nm. The incident angle means an angle with respect to a line perpendicular to the film surface.

  The silver alloy is one or more metals selected from the group consisting of silver and gold, palladium, tin, gallium, indium, copper, titanium, and bismuth in that the durability of the silver-containing metal layer is improved. An alloy consisting of As the silver alloy, an alloy of silver and gold is particularly preferable from the viewpoints of heat and humidity resistance, reflectance, and the like.

  For example, when the metal reflective layer is a film made of a silver alloy, the silver content is 90 atomic% to 99.8 atomic% in the total (100 atomic%) of silver and other metals in the metallic reflective layer. Preferably there is. Moreover, it is preferable that content of another metal is 0.2 atomic%-10 atomic% from a durable point.

  The surface roughness (Ra) of the metal reflective layer is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. When the surface roughness (Ra) of the metal reflective layer is within the above range, the reflectance of the obtained film mirror is improved, so that sunlight can be efficiently collected.

[Method of forming metal reflective layer]
The metal reflective layer in the present invention can be formed by either a wet method or a dry method. Examples of the wet method include an electroplating method, an electroless plating method, a silver complex coating firing method, and the like. Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method.

  In the present invention, it is preferable to form a metal reflective layer by wet plating in which a surface treatment is performed on an undercoat polymer layer containing reduced metal particles in an aqueous solution in which a metal to be plated is dissolved. According to such a method, since the surface of the intermediate layer is covered with metal, a metal reflective layer that has better adhesion to the intermediate layer than ordinary vapor deposition and is strong against heat is formed. be able to.

Hereinafter, a case where the metal reflective layer is formed by electroplating will be described.
A conventionally known method can be used as the electroplating method.
In the present invention, when the intermediate layer has a function as an electrode, the metal reflective layer can be formed by electroplating the intermediate layer.
Examples of metal compounds used for plating include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver methanesulfonate, silver ammonia, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, and chloranil. Examples thereof include silver compounds such as silver oxide, silver salicylate, silver diethyldithiocarbamate, silver diethyldithiocarbamate, and silver p-toluenesulfonate. Among these, silver methanesulfonate is preferable from the viewpoint of environmental impact and smoothness.

In the present invention, after electroplating, in order to improve the reflection performance and durability of the metal reflective layer, the surface of the metal reflective layer is treated with strong acid, strong alkali, etc. A metal oxide film may be formed. Moreover, you may further provide the discoloration prevention agent layer containing a discoloration prevention agent on the surface of a metal reflective layer.
Anti-discoloring agents are roughly classified into those having an adsorbing group that adsorbs metals and those that prevent oxidation. Examples of the discoloration inhibitor include thioether-based, thiol-based, Ni-based organic compound-based, benzotriazole-based, imidazole-based, oxazole-based, tetrazaindene-based, pyrimidine-based, and thiadiazole-based discoloration inhibitors.

Moreover, in this invention, you may provide the metal layer containing other metals, such as copper, nickel, chromium, iron, as a base metal layer between an intermediate | middle layer and a metal reflective layer, for example. By adding a base metal layer having an appropriate thickness, the reflectance can be improved by smoothing the surface, and pinholes can be reduced.
The thickness of the metal reflective layer is preferably 0.05 μm to 2.0 μm, and preferably 0.08 μm to 2.0 μm, from the viewpoint of not forming irregularities that scatter pinholes or light on the surface of the metal reflective layer. More preferably, it is 5 μm.
In addition, when forming a metal reflective layer by an electroplating method, the thickness of a metal reflective layer can be controlled by adjusting the metal concentration contained in a plating bath, or a current density.

<Protective layer>
The film mirror of the present invention has a protective layer on the light incident side of the metal reflective layer in order to prevent deterioration and breakage of the metal reflective layer due to sunlight, rainwater, dust, etc., and to stabilize the specularity. .
The protective layer in the present invention contains a resin as a binder. The resin used for forming the protective layer is transparent, in particular, in addition to strength, durability against heat and light, air and moisture barrier properties, and adhesion between the protective layer and the adjacent layer (for example, a metal reflective layer). What can form the film or layer excellent in the transmittance | permeability with respect to the light of the wavelength which a film mirror requires is preferable.

Examples of the resin used for forming the protective layer include cellulose ester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyethersulfone) resins, polyester resins (for example, polyethylene terephthalate (PET), Polyethylene naphthalate (PEN), etc.), olefinic resins (eg, polyethylene, polypropylene, etc.), cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol, polyvinyl butyral, ethylene Vinyl alcohol resin, ethylene vinyl acetate resin, ethylene acrylic acid ester copolymer, ethylene acrylic acid copolymer, norbornene resin, polymethylpente Resins, polyamide resins, fluorine resins, polymethyl methacrylate, acrylic resin, polyurethane resin or the like.
Among these, polycarbonate-based resins, polyester-based resins, norbornene-based resins, acrylic resins, fluorine-based resins, olefin-based resins, polyurethane-based resins, and the like are preferable, and acrylic resins are more preferable from the viewpoint of light transmittance.

The protective layer in the present invention may contain a crosslinking agent. When a crosslinking agent is contained, a crosslinked structure is formed in the protective layer, so that the strength is further improved and the adhesion to an adjacent layer, for example, a metal reflective layer is further improved. It is.
The crosslinking agent can be selected depending on the correlation with the resin constituting the protective layer, and examples thereof include a carbodiimide compound, an isocyanate compound, an epoxy compound, an oxetane compound, a melamine compound, and a bisvinylsulfone compound. Are preferably selected from the group consisting of carbodiimide compounds, isocyanate compounds, and epoxy compounds, and at least one crosslinking agent is preferred.

  In addition to the above components, the protective layer contains additives such as an ultraviolet absorber, a photopolymerization initiator, an antistatic agent, a coating aid (leveling agent), an antioxidant, and an antifoaming agent. May be.

  The ultraviolet absorber in the protective layer is not particularly limited, and examples thereof include benzophenone series, benzotriazole series, phenyl salicylate series, hindered amine series, triazine series, and benzoate series.

  When the protective layer contains an ultraviolet absorber, it is possible to reduce deterioration of the metal reflective layer and the intermediate layer due to light, but in some cases, light in the wavelength region to be reflected is absorbed by the ultraviolet absorber, and the film The light utilization efficiency of the mirror is reduced. From the viewpoint of increasing the utilization efficiency of light in the wavelength region desired to be reflected, it is preferable to select an ultraviolet absorber that does not have maximum absorption in the wavelength region of light desired to be reflected as the protective layer. Examples of such commercially available products include “TINUVIN 1577” having a maximum absorption wavelength at 274 nm and “TINUVIN 120” having a maximum absorption wavelength at 265 nm manufactured by BASF Japan.

  When the ultraviolet absorber is contained in the protective layer, the content thereof is preferably 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass with respect to the total solid content of the protective layer. More preferably, it is more preferably 10% by mass to 20% by mass. When the content of the ultraviolet absorber in the protective layer is within the above range, deterioration of the metal reflection layer or the like due to light can be reduced, and adhesion with an adjacent layer (for example, a metal reflection layer) can be reduced. It becomes a good protective layer.

(Method for forming protective layer)
Examples of the method for forming the protective layer on the surface of the metal reflective layer include the following methods. However, the present invention is not limited to these methods.
(1) By dissolving the resin and components used in combination as required in a solvent to prepare a coating solution for forming a protective layer, applying this coating solution for forming a protective layer on the surface of the metal reflective layer, and drying. A method of forming a protective layer.
(2) The protective layer forming coating solution of (1) above is applied on the surface of the metal reflective layer and dried to form a film on the surface of the metal reflective layer. A method of forming a protective layer by applying UV irradiation or the like.
(3) After heating the mixture of the resin and components used together as required to a temperature at which the resin melts, the resulting melt is cast on the surface of the metal reflective layer to form a protective layer. Method.
(4) A mixture of the above resin and each component used in combination is formed into a film in advance, and this film is bonded to the metal reflective layer using an adhesive, or is applied to the metal reflective layer by thermal lamination or the like. A method of forming a protective layer by fusing.

  In the methods (1) and (2), the solvent used for dissolving the resin and optionally used components is not particularly limited. For example, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone (MEK) ), N, N-dimethylformamide (DMF), cyclohexane, cyclohexanol, cyclohexanone, ethylbenzene and the like. A solvent can be used 1 type or in combination of 2 or more types.

The solid content concentration of the protective layer-forming coating solution in the methods (1) and (2) is preferably in the range of 1% by mass to 30% by mass from the viewpoint of adhesion to the metal reflective layer.
The coating method of the coating liquid for forming the protective layer in the above methods (1) and (2) is not particularly limited, and the gravure coating method, reverse coating method, die coating method, blade coater method, roll coater method, air knife Conventionally known coating methods such as a coater method, a screen coater method, a bar coater method, and a curtain coater method can be used.

  The thickness of the protective layer is selected in accordance with the characteristics of the resin as long as a necessary protective function can be realized, but in general, it is preferably in the range of 1 μm to 100 μm.

<Back side protective layer>
The film mirror of the present invention preferably further has a back surface protective layer containing an ultraviolet absorber on the side opposite to the intermediate layer side of the support from the viewpoint of suppressing deterioration of the resin from the support side due to reflected light. .
For example, when the film mirror of the present invention is used as a reflecting mirror for concentrating sunlight installed outdoors, a surface opposite to the side on which the intermediate layer of the support is formed (hereinafter referred to as “support” as appropriate). (Referred to as “the back of the body”) receives light from the ground for a long time. Deterioration of the resin from the support side due to light can lead to deterioration of the intermediate layer and, consequently, corrosion of the metal reflection layer, which can be a factor of reducing the reflection performance of the film mirror.
In the present invention, by providing a back surface protective layer containing an ultraviolet absorber on the back surface of the support,
It is possible to suppress the deterioration of the resin from the support side, which can be a factor for reducing the reflection performance of the film mirror.

  The resin used for forming the back surface protective layer is preferably one that can form a film or a layer excellent in strength and adhesiveness between the back surface protective layer and an adjacent layer (for example, an intermediate layer).

The resin used for forming the back surface protective layer is the same as the resin used for forming the above protective layer, and the preferred embodiment is also the same.
The ultraviolet absorber contained in the back surface protective layer is not particularly limited and has the same meaning as the ultraviolet absorber contained in the above protective layer.
The back surface protective layer may contain additives such as a photopolymerization initiator, an antistatic agent, a coating aid (leveling agent), an antioxidant, and an antifoaming agent.

  The content of the ultraviolet absorber in the back surface protective layer is preferably 1% by mass to 50% by mass and more preferably 5% by mass to 30% by mass with respect to the total solid content of the back surface protective layer. More preferably, it is 10 mass%-20 mass%. When the content of the ultraviolet absorber in the back surface protective layer is within the above range, deterioration of the resin from the support side due to reflected light can be reduced, and with the adjacent layer (for example, an intermediate layer) It becomes a back surface protective layer with good adhesion.

[Method for forming back surface protective layer]
The method for forming the back surface protective layer on the back surface of the support is the same as the method for forming the protective layer on the surface of the metal reflective layer described above except that an ultraviolet absorber is essential as a forming material.

  The thickness of the back surface protective layer is selected in accordance with the characteristics of the resin as long as a necessary protective function can be realized, but is generally preferably in the range of 1 μm to 100 μm.

<Sunlight reflector>
The solar reflective plate of the present invention is produced using the film mirror of the present invention. Specifically, the solar reflective plate of the present invention is a substrate made of any of resin, metal, or ceramic. Further, the film mirror of the present invention is bonded through an adhesive layer.
The film mirror according to the present invention can be used for collecting sunlight, but is preferably used as a sunlight reflecting plate by being stuck on a substrate such as a resin.
Since the film mirror of the present invention has the characteristics of a film mirror that is lightweight and flexible and has excellent light resistance, the solar reflector produced using this film is particularly suitable for solar power generation. Is preferred.

  As a board | substrate which hold | maintains the film mirror of this invention, it is either resin, a metal, or a ceramic, Preferably it is a metal. Examples of the metal substrate include steel plates, copper plates, aluminum plates, copper-plated steel plates, tin-plated steel plates, aluminum-plated steel plates, stainless steel plates, chrome-plated steel plates, and the like having high thermal conductivity. From the viewpoint, a plated steel plate, a stainless steel plate, and an aluminum plate are preferable.

The material for forming the adhesive layer for bonding the film mirror of the present invention and the substrate is not particularly limited, and examples thereof include an adhesive, a laminating agent, a heat sealant, and the like, and an adhesive is preferable from the viewpoint of specularity. .
As the adhesive, for example, an acrylic resin, a urethane resin, a polyester resin, a polyvinyl acetate resin, a nitrile rubber or the like is preferable, and from the viewpoint of light resistance and adhesiveness, an acrylic resin or An adhesive mainly composed of a urethane resin is particularly preferable.
An acrylic adhesive mainly composed of an acrylic resin is particularly excellent in weather resistance and light resistance. Moreover, the urethane adhesive which has urethane resin as a main component can obtain strong adhesive strength by using a two-component mixed adhesive composed of polyisocyanate and polyol.

  The thickness of the adhesive layer is preferably in the range of 1 μm to 20 μm from the viewpoints of adhesiveness, ease of formation, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Production of film mirror]
[Example 1]
-Formation of intermediate layer (plating undercoat polymer layer)-
Acrylic polymer 1 having the following structure (the number of each repeating unit in the following structure represents a composition ratio in terms of mass) (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), and water (20 parts by mass) ), A UV absorber (TINUVIN 405, hydroxyphenyltriazine UV absorber, maximum absorption wavelength: 289 nm, manufactured by BASF Japan Ltd.) (0.05 parts by mass), and a photopolymerization initiator (Esacure KTO-46) (Made by Lamberdee) (5 parts by mass) was added and stirred to prepare a coating solution for forming an intermediate layer containing acrylic polymer 1. In addition, the weight average molecular weight of the acrylic polymer 1 was 40000 (polystyrene conversion value using the above-mentioned GPC), and content of the carboxylic acid group in the acrylic polymer 1 was 4.3 meq / g.

The coating liquid for forming the intermediate layer obtained above is coated on the surface of a polyethylene terephthalate (PET) film (Cosmo Shine A4300, manufactured by TOYOBO) as a support, and the film thickness after drying is 1 μm. After applying by the bar coat method so that the content per unit area of the ultraviolet absorber is 0.015 g / m ² , drying at 25 ° C. for 10 minutes and at 80 ° C. for 5 minutes, a UV irradiation device ( UV exposure (wavelength: 254 nm, UV exposure: 1000 mJ / cm ² ) was performed using a UV lamp: metal halide lamp, manufactured by GS Yuasa. Next, the UV-exposed PET film was immersed in a 1% by mass aqueous sodium hydrogen carbonate solution for 5 minutes. Then, it washed by pouring for 1 minute with pure water, and the unreacted polymer was removed.

(Give metal precursor)
As a solution containing a metal precursor, a 1% by mass silver nitrate aqueous solution was prepared. The PET film on which the intermediate layer obtained above was formed was immersed in the 1% by mass silver nitrate aqueous solution adjusted to 25 ° C. for 5 minutes. Then, it wash | cleaned by pouring for 1 minute with a pure water, and the metal precursor was provided to the intermediate | middle layer obtained above.

(Reduction of metal precursor)
As a reducing solution, a 0.25 mass% formaldehyde aqueous solution containing 0.14 mass% sodium hydroxide was prepared. The PET film on which the intermediate layer provided with the metal precursor was formed was immersed in the reducing solution adjusted to 25 ° C. for 1 minute. Then, the metal precursor was reduced by washing with pure water for 1 minute.
When the surface resistance value after the reduction was measured using a surface resistance meter, it was about 10Ω / □. Moreover, when the surface roughness (Ra) was measured using an atomic force microscope (AFM), it was about 7 nm. Furthermore, when the particle diameter of the metal after reduction was measured using a scanning electron microscope (SEM), it was about 50 nm.

-Formation of metal reflective layer-
(Electroplating)
10% by mass of Dyne Cleaner AC100 (manufactured by Daiwa Kasei Co., Ltd.) obtained by temperature-controlling the PET film having the intermediate layer containing the reduced metal particles obtained above as a pretreatment for electroplating on the surface. After being immersed in an aqueous solution for 30 seconds, it was washed several times. Subsequently, as an electroplating pretreatment, it was immersed in a 10% by mass aqueous solution of Dyne Silver ACC (main component: methanesulfonic acid, manufactured by Daiwa Kasei Co., Ltd.) for 10 seconds and then washed several times.
Next, Dyne Silver Bright PL50 (main component: silver methanesulfonate, manufactured by Daiwa Kasei Co., Ltd.) adjusted to pH 9.0 with 8M potassium hydroxide was prepared as an electroplating solution. And in this electroplating liquid, the PET film which has the intermediate layer after the said pre-processing on the surface was immersed, and it plated for 20 second at 0.5 A / dm < ² >.
As a post-treatment for electroplating, the plated PET film was immersed in a 10% by weight aqueous solution of Dyne Silver ACC (main component: methanesulfonic acid, manufactured by Daiwa Kasei Co., Ltd.) for 90 seconds, washed several times, A reflective layer was formed.
When the surface roughness (Ra) of the metal reflective layer after the post-plating treatment was measured using an atomic force microscope (AFM), it was about 4 nm.

-Formation of protective layer 1-
On the surface of the metal reflective layer obtained above, the following coating liquid 1 for forming a protective layer is applied by a bar coating method (wire bar, # 26) so that the dry weight is 1.0 g / m ^2. And manufactured by Kobayashi Seisakusho. And after drying this for 2 minutes at 130 degreeC, the high pressure mercury lamp was irradiated so that the irradiation amount might be 750 mJ / cm < ² > in nitrogen atmosphere, and the protective layer 1 was formed.

-Composition of Coating Solution 1 for Protective Layer Formation-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 5.0 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
・ ・ ・ 0.72 parts by mass ・ IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 0.12 parts by mass / ethyl acetate (solvent) ... 5.0 parts by mass

  Thus, the film mirror of Example 1 which has the intermediate | middle layer, the metal reflection layer formed by the plating method, and the protective layer 1 in this order on the PET film which is a support body was produced.

[Example 2]
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (0.2 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), and the intermediate layer-forming coating solution obtained on the surface of the PET film A film mirror of Example 2 was produced in the same manner as in Example 1 except that the UV absorber was applied so that the content per unit area was 0.06 g / m ² .

Example 3
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (0.5 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), and the obtained intermediate layer-forming coating solution on the surface of the PET film A film mirror of Example 3 was produced in the same manner as in Example 1 except that the UV absorber was applied so that the content per unit area was 0.15 g / m ² .

Example 4
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (1 part by mass) and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), and the obtained intermediate layer-forming coating solution on the surface of the PET film A film mirror of Example 4 was produced in the same manner as in Example 1 except that the ultraviolet absorber was applied so that the content per unit area was 0.3 g / m ² .

Example 5
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (2 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), and the obtained intermediate layer-forming coating solution on the surface of the PET film on the intermediate layer A film mirror of Example 5 was produced in the same manner as in Example 1 except that the ultraviolet absorber was applied so that the content per unit area was 0.6 g / m ² .

Example 6
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (0.5 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (1 part by mass), and the obtained intermediate layer forming coating solution was dried on the surface of the PET film. Example 1 was carried out in the same manner as in Example 1 except that the film thickness was 0.05 μm, and that the content per unit area of the UV absorber in the intermediate layer was 0.15 g / m ^2. 6 film mirrors were produced.

Example 7
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 405) (0.5 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (3 parts by mass), and the obtained intermediate layer-forming coating solution on the surface of the PET film after drying Example 1 was carried out in the same manner as in Example 1 except that the film thickness was 0.5 μm, and that the content per unit area of the UV absorber in the intermediate layer was 0.15 g / m ^2. 7 film mirrors were produced.

Example 8
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (30 parts by mass), water (10 parts by mass), ultraviolet absorber ( TINUVIN 405) (0.5 parts by mass) and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), and the obtained intermediate layer-forming coating solution on the surface of the PET film after drying In the same manner as in Example 1 except that the film thickness was 5 μm and that the content per unit area of the UV absorber in the intermediate layer was 0.15 g / m ² . A film mirror was produced.

Example 9
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (30 parts by mass), water (10 parts by mass), ultraviolet absorber ( TINUVIN 405) (0.5 parts by mass) and photopolymerization initiator (Esacure KTO-46) (7 parts by mass), and the obtained intermediate layer forming coating solution was dried on the surface of the PET film. In the same manner as in Example 1, except that the coating was applied so that the content per unit area of the UV absorber in the intermediate layer was 0.15 g / m ² . A film mirror was produced.

[Comparative Example 1]
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to the acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), and photopolymerization start. A film mirror of Comparative Example 1 was produced in the same manner as in Example 1 except that the agent (Esacure KTO-46) (5 parts by mass) was used.

[Comparative Example 2]
In Example 1, the composition of the coating solution for forming the intermediate layer was changed to acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), UV absorber ( TINUVIN 234, benzotriazole-based ultraviolet absorber, maximum absorption wavelength: 343 nm, manufactured by BASF Japan Ltd. (0.5 parts by mass), and photopolymerization initiator (Esacure KTO-46) (5 parts by mass) are obtained. Example 1 except that the obtained intermediate layer forming coating solution was applied to the surface of the PET film so that the content per unit area of the UV absorber in the intermediate layer was 0.15 g / m ^2. Similarly, a film mirror of Comparative Example 2 was produced.

[Evaluation]
The following evaluation was performed using the film mirrors of Examples 1 to 9, Comparative Example 1 and Comparative Example 2 prepared above. The results are shown in Table 1.

1. Plating property The metal reflective layer formed by plating on the intermediate layer was visually observed. And the plating property was evaluated by confirming the formation state of a metal reflective layer. The evaluation criteria are shown below.
Those practically acceptable are classified into “A” and “B”.

(Evaluation criteria)
A: The metal reflective layer is uniformly formed.
B: Slight unevenness is observed in the metal reflection layer, but it does not affect the reflectivity.
C: Large unevenness is observed in the metal reflective layer.

2. Adhesion The adhesion test was performed by a method according to the tape test method of JIS H8504.
The film mirror was cut into a width of 100 mm and a length of 100 mm to prepare a sample for measurement. Using a single-blade razor, eleven scratches were made on the surface of the sample in the vertical and horizontal directions, and a 10 × 10 square cut with a width of 2 mm was made to form 100 squares. Affix the polyester adhesive tape (Mylar tape, manufactured by Nitto Denko) to the cut surface, rub it with poppy rubber, and attach the polyester adhesive tape to the sample completely, then vigorously in the vertical direction I peeled it off. Then, the adhesion was evaluated based on the presence / absence and degree of peeling of the metal reflective layer. The evaluation criteria are shown below. The “peeled mass” in the evaluation criteria refers to a mass from which more than half of the area has been peeled off.
Those practically acceptable are classified into “A” and “B”.

(Evaluation criteria)
A: Peeling is not recognized at all.
B: The peeled square is 10 squares or less out of 100 squares.
C: The peeled square is 11 squares or more out of 100 squares.

3. The reflective film mirror was cut into a width of 30 mm and a length of 30 mm to prepare a measurement sample. The solar spectrum reflectance (TSR: Total Solar Reflectance, reflectance at a wavelength of 280 nm to 2500 nm) (%) of this sample was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) and evaluated as follows. Reflectivity was evaluated according to criteria.
Those practically acceptable are classified into “A” and “B”.

(Evaluation criteria)
A: TSR is 93% or more.
B: TSR is 90% or more and less than 93%.
C: TSR is less than 90%.

4). Light resistance A film mirror was cut into a width of 50 mm and a length of 50 mm to prepare a sample for measurement. This sample was put into a xenon weather meter (SX-75, manufactured by Suga Test Instruments Co., Ltd.), and under conditions of humidity 50% RH and black panel temperature 63 ° C., the protective layer side (layer configuration: protective layer / metal reflective layer / (Intermediate layer / support) was irradiated at 180 W for 1000 hours. And light resistance was evaluated based on the decrease rate of TSR by 1000-hour irradiation computed from the measured value of solar spectrum reflectance (TSR) (%) before and after irradiation. The measurement of TSR was performed by the same method as the measurement in the above evaluation of reflectivity. The evaluation criteria are shown below.
Those practically acceptable are classified into “AA”, “A”, and “B”.

(Evaluation criteria)
AA: The reduction rate of TSR is less than 1%.
A: The reduction rate of TSR is 1% or more and less than 2%.
B: The reduction rate of TSR is 2% or more and less than 3%.
C: The decrease rate of TSR is 3% or more and less than 5%.
D: The reduction rate of TSR is 5% or more.

  As shown in Table 1, the film mirrors of the examples all showed good light resistance. In addition, the film mirrors of the examples all had a good metal reflection layer, had excellent adhesion between the metal reflection layer and the intermediate layer, and had excellent reflection performance as a film mirror. On the other hand, the film mirrors of Comparative Example 1 and Comparative Example 2 were inferior in light resistance.

-Formation of back surface protective layer 1-
On the surface opposite to the surface on which the intermediate layer of the PET film (Cosmo Shine A4300, manufactured by TOYOBO) as the support is formed, the following back surface protective layer forming coating solution 1 is dried at a weight of 1.0 g / It was applied by a bar coating method (wire bar, # 26, manufactured by Kobayashi Seisakusho) so as to be m ² . And after drying this at 130 degreeC for 2 minute (s), the PET film in which the back surface protective layer 1 was formed by irradiating a high pressure mercury lamp so that irradiation amount might be set to 750 mJ / cm < ² > in nitrogen atmosphere. It was.

-Composition of coating liquid 1 for forming the back surface protective layer-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 5.0 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
・ ・ ・ 0.72 parts by mass ・ IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 0.12 parts by mass / ethyl acetate (solvent) ... 5.0 parts by mass

-Formation of the back surface protective layer 2-
In the formation of the back surface protective layer 1, the back surface protective layer 2 is formed in the same manner as the back surface protective layer 1 except that the following back surface protective layer forming coating solution 2 is used instead of the back surface protective layer forming coating solution 1. A PET film with a formed was obtained.

-Composition of the back surface protective layer forming coating solution 2-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 47 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
... 1.7 parts by mass TINUVIN 405 [Hydroxyphenyltriazine-based ultraviolet absorber, maximum absorption wavelength: 289 nm, manufactured by BASF Japan Ltd.] (UV absorber)
... 2.6 parts by mass IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 1.2 parts by mass, ethyl acetate (solvent) ... 47.5 parts by mass

-Formation of the back surface protective layer 3-
In the formation of the back surface protective layer 1, the back surface protective layer 3 is formed in the same manner as the back surface protective layer 1 except that the following back surface protective layer forming coating solution 3 is used instead of the back surface protective layer forming coating solution 1. A PET film with a formed was obtained.

-Composition of the back surface protective layer forming coating solution 3-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 47 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
... 1.7 parts by mass TINUVIN 234 [benzotriazole-based ultraviolet absorber, maximum absorption wavelength: 343 nm, manufactured by BASF Japan Ltd.] (ultraviolet absorber)
... 2.6 parts by mass IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 1.2 parts by mass, ethyl acetate (solvent) ... 47.5 parts by mass

Example 10
In Example 2, a PET film in which the back surface protective layer 1 is formed on the surface opposite to the surface on which the intermediate layer is formed is used as the support, and the composition of the coating liquid for forming the intermediate layer is Acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), ultraviolet absorber (TINUVIN 405) (3 parts by mass), and photopolymerization initiator (Esacure) A film mirror of Example 10 was produced in the same manner as in Example 2 except that KTO-46) (3 parts by mass) was used.

Example 11
In Example 10, Example 11 was carried out in the same manner as Example 10 except that a PET film in which the back surface protective layer 2 was formed on the surface opposite to the surface on which the intermediate layer was formed was used as the support. A film mirror was prepared.

Example 12
In Example 10, a PET film having a back surface protective layer 2 formed on the surface opposite to the surface on which the intermediate layer is formed is used as a support, and on the plated surface of the metal reflective layer, the following: A film mirror of Example 12 was produced in the same manner as in Example 10 except that the protective layer 2 was formed using the protective layer forming coating solution 2.

-Composition of coating liquid 2 for forming a protective layer-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 47 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
... 1.7 parts by mass TINUVIN 405 [Hydroxyphenyltriazine-based ultraviolet absorber, maximum absorption wavelength: 289 nm, manufactured by BASF Japan Ltd.] (UV absorber)
... 2.6 parts by mass IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 1.2 parts by mass, ethyl acetate (solvent) ... 47.5 parts by mass

Example 13
In Example 10, the same procedure as in Example 10 was performed except that the protective layer 2 was formed on the plating surface of the metal reflective layer using the protective layer forming coating solution 2 described above. A film mirror was produced.

Example 14
In Example 10, as a support, the composition of the coating solution for forming an intermediate layer was made of acrylic polymer 1 having the above structure (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), Other than using UV absorber (TINUVIN 405) (2.5 parts by mass), UV absorber (TINUVIN 234) (2.5 parts by mass), and photopolymerization initiator (Esacure KTO-46) (5 parts by mass) Produced a film mirror of Example 14 in the same manner as Example 10.

Example 15
In Example 10, Example 15 was carried out in the same manner as Example 10 except that a PET film having the back surface protective layer 3 formed on the surface opposite to the surface on which the intermediate layer was formed was used as the support. A film mirror was prepared.

Example 16
In Example 10, the same procedure as in Example 10 was performed except that the protective layer 3 was formed using the following protective layer forming coating solution 3 on the plated surface of the metal reflective layer. A film mirror was produced.

-Composition of protective layer forming coating solution 3-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 47 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
... 1.7 parts by mass TINUVIN 234 [benzotriazole-based ultraviolet absorber, maximum absorption wavelength: 343 nm, manufactured by BASF Japan Ltd.] (ultraviolet absorber)
... 2.6 parts by mass IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 1.2 parts by mass, ethyl acetate (solvent) ... 47.5 parts by mass

[Comparative Example 3]
In Example 10, a PET film in which the back surface protective layer 1 is formed on the surface opposite to the surface on which the intermediate layer is formed is used as the support, and the composition of the coating liquid for forming the intermediate layer is Acrylic polymer 1 (10 parts by mass), 1-methoxy-2-propanol (60 parts by mass), water (20 parts by mass), and a photopolymerization initiator (Esacure KTO-46) (5 parts by mass), A film mirror of Comparative Example 3 was produced in the same manner as in Example 10 except that the protective layer 4 was formed on the plating surface of the metal reflective layer using the following protective layer forming coating solution 4. .

-Composition of coating liquid 4 for forming the protective layer-
・ Ceranate SSA-3060 (acrylic resin, manufactured by DIC) (binder)
... 5.0 parts by mass / Bernock DN-902S [isocyanate curing agent, manufactured by DIC Corporation] (crosslinking agent)
・ ・ ・ 0.72 parts by mass · TINUVIN 405 [Hydroxyphenyltriazine UV absorber, maximum absorption wavelength: 289 nm, manufactured by BASF Japan Ltd.] (UV absorber)
... 0.25 parts by mass · TINUVIN 234 [benzotriazole ultraviolet absorber, maximum absorption wavelength: 343 nm, manufactured by BASF Japan Ltd.] (ultraviolet absorber)
... 0.25 parts by mass IRGACURE 127 [manufactured by BASF Japan Ltd.] (photopolymerization initiator)
... 0.12 parts by mass / ethyl acetate (solvent) ... 5.0 parts by mass

[Evaluation]
Using the film mirrors of Examples 10 to 16 and Comparative Example 3 prepared above, evaluation of reflectivity and light resistance was performed by the same method as described above. The results are shown in Table 2.

As shown in Table 2, the film mirror (Examples 11 and 12) having the back surface protective layer containing the ultraviolet absorber B (Examples 11 and 12) does not have the back surface protective layer containing the ultraviolet absorber B (Examples 10 and 13). ) And excellent light resistance.
The film mirror (Example 14) containing the ultraviolet absorber A and the ultraviolet absorber B in the intermediate layer is more resistant to light than the film mirror (Comparative Example 3) containing the ultraviolet absorber A and the ultraviolet absorber B in the protective layer. Excellent in reflectivity and reflectivity.

Claims (6)

  The film mirror which has a support body, the intermediate | middle layer containing the ultraviolet absorber which has maximum absorption in UV-B area | region, a metal reflective layer, and a protective layer in this order.   The film mirror according to claim 1, wherein the content of the ultraviolet absorber in the intermediate layer is 1% by mass to 20% by mass with respect to the total solid content of the intermediate layer. Wherein the intermediate layer further comprises a photopolymerization initiator, the content per unit area of the ultraviolet absorber in the intermediate ^layer, according to claim 1 or claim is 0.02g / ^{m 2} ~0.7g / m 2 Item 3. The film mirror according to Item 2.   The film mirror of any one of Claims 1-3 which further has a back surface protective layer containing a ultraviolet absorber on the opposite side to the intermediate layer side of the support.   The film mirror according to any one of claims 1 to 4, wherein the metal reflective layer is formed by a plating method.   The film mirror according to any one of claims 1 to 5, which is used for collecting sunlight.