WO2015022877A1 - Film mirror and reflective device for solar thermal power generation - Google Patents

Abstract

The objective of the present invention is to provide: a film mirror which is able to be suppressed in deterioration of the reflectance or the like due to corrosion or color change of a silver reflective layer caused by separation between the silver reflective layer and another constituent layer adjacent thereto even if the film mirror is used outdoors for a long period of time or is subjected to a load of cleaning work or the like; and a reflective device for solar thermal power generation, which is provided with this film mirror. This film mirror is characterized by being provided with: a silver reflective layer that is provided on a resin base; and a nitrogen-containing layer that is adjacent to the silver reflective layer and contains a compound having a nitrogen atom that has an unshared electron pair which is not involved in aromaticity. This film mirror is also characterized in that the compound has an effective unshared electron pair content n/M of 2.0 × 10^-3 or more, where n is the number of unshared electron pairs which are not involved in aromaticity and M is the molecular weight.

Description

Film mirror and reflector for solar power generation

The present invention relates to a film mirror and a solar power generation reflector. Reflection caused by corrosion or discoloration of the silver reflective layer due to peeling between the silver reflective layer and other adjacent constituent layers, even when subjected to long-term outdoor use or cleaning work. The present invention relates to a film mirror that can suppress a decrease in rate and the like, and a solar power generation reflection device including the same.

In recent years, solar energy has been considered to be the most stable and abundant amount of natural energy that can be used as an alternative to fossil fuels. By collecting solar energy with a huge reflector, power is generated using that thermal energy as a medium. Solar power generation has been proposed.

Since this reflector is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, etc., glass mirrors have been used in the past, but recently it is light and flexible, and solar heat is low in production and transportation costs. A film mirror is being studied as a power generation mirror.

A film mirror for solar power generation is accompanied by a discoloration of a resin coating layer that suppresses corrosion of the silver reflection layer on a metal reflection layer provided on the film substrate, for example, a silver reflection layer, and a resin-made structural layer due to exposure to ultraviolet rays. Durability is improved by laminating an ultraviolet absorbing layer that suppresses a decrease in reflectance, a hard coat layer that suppresses scratches on the surface, and the like.
For example, in the technique described in Patent Document 1, an acrylic resin layer containing an ultraviolet absorber is provided on the outermost layer of the film, and a decrease in reflectance due to discoloration of the resin layer due to ultraviolet exposure is suppressed. .

Here, since such a film mirror is installed in an outdoor environment, it is regularly cleaned by high-pressure water discharge or brushing in order to suppress a decrease in reflectance caused by dust and the like adhering to the film mirror surface. Work is done.
In the technique described in Patent Document 1, a polyethylene terephthalate (PET) layer and an adhesive layer are sandwiched between a silver reflective layer and an acrylic resin layer, and after washing outdoors for more than half a year, washing by brushing is performed. There is a possibility that peeling occurs between the silver reflecting layer and the PET layer due to the stress generated during the cleaning.

As described above, in the film mirror that easily peels between the silver reflective layer and other adjacent constituent layers, the silver reflective layer and the adjacent layer are peeled off to be provided on the adjacent layer. Functions such as a corrosion prevention layer and an ultraviolet absorption layer may be hindered, and corrosion resistance and light resistance may be reduced.
Furthermore, when a hard coat layer is provided on the surface of such a film mirror, stress is generated on the surface of the film mirror due to peeling between the silver reflective layer and other adjacent constituent layers, and the hard mirror layer is hard. It has also been found that cracks may occur in the coat layer.

Special table 2009-520174

The present invention has been made in view of the above problems, and the problem to be solved is that, even when subjected to a load due to outdoor use or cleaning work for a long period of time, other constituent layers adjacent to the silver reflective layer It is providing the film mirror which can suppress the fall of the reflectance etc. accompanying corrosion or discoloration of a silver reflective layer resulting from peeling between, and a solar power generation reflective apparatus provided with the same.

As a result of investigating the cause of the above-mentioned problems in order to solve the above-mentioned problems relating to the present invention, a silver reflecting layer is provided on a resin substrate, and the nitrogen is made of a compound containing a nitrogen atom adjacent to the silver reflecting layer. And the compound has an effective unshared electron pair content n / M of 2.0 × 10 ⁻³ or more, where n is the number of unshared electron pairs not involved in aromaticity and M is the molecular weight. It is found that a film mirror capable of suppressing a decrease in reflectance caused by corrosion or discoloration of the silver reflective layer caused by peeling between the silver reflective layer and other adjacent constituent layers can be provided. It was.
That is, the said subject which concerns on this invention is solved by the following means.

1. A film mirror provided with a silver reflective layer on a resin substrate,
A nitrogen-containing layer containing a compound having a nitrogen atom adjacent to the silver reflective layer and having an unshared electron pair not involved in aromaticity;
The compound is a compound having an effective unshared electron pair content ratio n / M of 2.0 × 10 ⁻³ or more, where n is the number of unshared electron pairs not involved in aromaticity and M is the molecular weight. A film mirror characterized by

2. 2. The film mirror according to item 1, wherein the effective unshared electron pair content ratio n / M is 3.9 × 10 ⁻³ or more.

3. 3. The film mirror according to item 1 or 2, wherein a hard coat layer containing a polymer having a metalloxane skeleton is provided on the surface.

4). The film mirror according to any one of items 1 to 3,
And a support base material for supporting the film mirror.

According to the present invention, it is possible to suppress the peeling between the silver reflective layer and other constituent layers adjacent to each other even when subjected to a load due to outdoor use or cleaning work for a long period of time. The film mirror which can suppress the fall of the reflectance accompanying corrosion, discoloration, etc. of the silver reflection layer which originates, and a solar power generation reflective apparatus provided with the same can be provided.
In addition, since peeling between the silver reflective layer and other adjacent constituent layers can be suppressed, when a hard coat layer is provided on the surface of the film mirror, the occurrence of cracks in the hard coat layer is suppressed. You can also.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
That is, since the layer adjacent to the silver reflective layer is a nitrogen-containing layer containing a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, the compound contained in the nitrogen-containing layer is not shared. When the electron pair interacts with the silver atom, the adhesion between the silver reflective layer and the nitrogen-containing layer adjacent to the silver reflective layer is improved. Further, when the effective unshared electron pair content ratio n / M of the compound contained in the nitrogen-containing layer is 2.0 × 10 ⁻³ or more, nitrogen atoms capable of interacting with silver atoms in the silver reflecting layer Are contained in the nitrogen-containing layer in large numbers, and high adhesion between the silver reflecting layer and the nitrogen-containing layer is obtained. As a result, high adhesion can be maintained between the silver reflective layer and other adjacent constituent layers even when subjected to a long-term outdoor use or a load due to cleaning work, etc. It is possible to suppress a decrease in reflectance caused by corrosion or discoloration of the silver reflecting layer.
Moreover, since the silver reflection layer and the nitrogen-containing layer have high adhesion, peeling does not occur between the layers, and stress is hardly generated on the film mirror surface. Thereby, when the hard-coat layer is provided in the film mirror surface, it can suppress that a crack generate | occur | produces in the said hard-coat layer.

Explanatory drawing which shows an example of a structure of the mirror for solar power generation of this invention Explanatory drawing which shows an example of a structure of the mirror for solar power generation of this invention Explanatory drawing which shows an example of a structure of the reflective apparatus for solar thermal power generation of this invention

The film mirror of the present invention is a film mirror in which a silver reflective layer is provided on a resin base material, and is a compound having a nitrogen atom adjacent to the silver reflective layer and having an unshared electron pair not involved in aromaticity And when the number of unshared electron pairs not involved in aromaticity is n and the molecular weight is M, the effective unshared electron pair content n / M is 2.0 ×. It is characterized by being a compound of 10 ⁻³ or more. This feature is a technical feature common to claims 1 to 4.
Moreover, it is preferable that this invention equips the surface with the hard-coat layer containing the polymer which has a metalloxane skeleton. Thereby, the scratch resistance of the surface can be improved.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<Outline of Film Mirror and Solar Power Reflecting Device of the Present Invention>
The film mirror of the present invention is a film mirror in which a silver reflective layer is provided on a resin base material, and is a compound having a nitrogen atom adjacent to the silver reflective layer and having an unshared electron pair not involved in aromaticity And when the number of unshared electron pairs not involved in aromaticity is n and the molecular weight is M, the effective unshared electron pair content n / M is 2.0 ×. It is characterized by being a compound of 10 ⁻³ or more.

[1] Outline of configuration of film mirror An outline of the film mirror of the present invention will be described.

The film mirror F is configured, for example, as shown in FIG. 1A, in which a silver reflective layer 5 is formed on a resin base material 3 and a hard coat layer 10 is provided as an outermost layer thereon. Therefore, in the example shown in FIG. 1A, the nitrogen-containing layer adjacent to the silver reflecting layer in the present invention corresponds to the resin base material 3 and the hard coat layer 10, and at least one of the resin base material 3 and the hard coat layer 10. Contain a compound having a nitrogen atom with an unshared electron pair not involved in aromaticity.

Moreover, it is preferable to provide various functional layers in the film mirror F in practice, and for example, it may be configured as shown in FIG. 1B.

In the example shown in FIG. 1B, an anchor layer 4 is provided between the resin base material 3 and the silver reflective layer 5, and a resin coat layer containing a corrosion inhibitor or an antioxidant on the light incident side of the silver reflective layer 5. 6, a gas barrier layer 11 that protects the silver reflection layer 5 and the resin coat layer 6, an adhesive layer 7 provided on the gas barrier layer 11, an acrylic resin layer 8 containing an ultraviolet absorber, and an intermediate provided on the acrylic resin layer 8 The layer 9 and the hard coat layer 10 as the outermost layer are provided in this order.
Further, the adhesive layer 2 may be provided on the surface of the resin base 3 opposite to the light incident side, and further, a release layer 12 for protecting the adhesive layer is provided on the adhesive layer 2. May be.
In addition, the structure of the film mirror F is not restricted to this, As long as the resin base material 3 and the silver reflection layer 5 are provided at least, either layer of each said structure layer may not be provided. .

In the case of the configuration of FIG. 1B, the nitrogen-containing layer adjacent to the silver reflecting layer in the present invention corresponds to the anchor layer 4 and the resin coat layer 6, and at least one of the anchor layer 4 and the resin coat layer 6 is aromatic. It contains a compound having a nitrogen atom having an unshared electron pair that is not involved in the family.
In order to enhance the effect of the present invention, it is preferable that both the anchor layer 4 and the resin coat layer 6 contain a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity.

In addition, the layer adjacent to the silver reflective layer means that the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity acts on the silver atoms of the silver reflective layer in addition to the layer directly in contact with the silver reflective layer. In the case where the effect of the present invention can be exhibited, a thin film layer (for example, a resin layer) that does not contain the compound may be present between the layers.

The total thickness of the film mirror is preferably in the range of 75 to 250 μm, more preferably in the range of 90 to 230 μm, still more preferably in the range of 100 to 220 μm, from the viewpoints of mirror deflection prevention, regular reflectance, handling properties, and the like. Is within.

Hereinafter, each constituent layer constituting the film mirror of the present invention will be described in order. First, a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, which is a feature of the present invention, will be described.

[2] Compound having a nitrogen atom having an unshared electron pair not involved in aromaticity The nitrogen-containing layer is a layer provided adjacent to the silver reflecting layer 5 and is an unshared electron pair not involved in aromaticity It is comprised using the compound which has a nitrogen atom with. In addition, among the nitrogen atoms contained in the compound, the compound particularly refers to an unshared electron pair of a nitrogen atom that stably binds to silver, which is a main material constituting the silver reflective layer 5, as an “effective unshared electron pair”. The content of the effective unshared electron pair is within a predetermined range.

Here, the “effective unshared electron pair” refers to an unshared electron pair that does not participate in aromaticity among the unshared electron pairs of the nitrogen atom contained in the compound. The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel rule”, and includes the electrons contained in the π electron system on the ring. The condition is that the number is “4n + 2” (n = 0 or a natural number).

The “effective unshared electron pair” as described above is an unshared electron pair possessed by a nitrogen atom regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a heteroatom constituting an aromatic ring. Is selected depending on whether or not is involved in aromaticity. For example, even if a nitrogen atom is a heteroatom constituting an aromatic ring, if the nitrogen atom has an unshared electron pair that does not participate in aromaticity, the unshared electron pair is expressed as “effective unshared electron”. It is counted as one of “pair”. In contrast, even if a nitrogen atom is not a heteroatom that constitutes an aromatic ring, if all of the non-shared electron pairs of the nitrogen atom are involved in aromaticity, the nitrogen atom is not shared. An electron pair is not counted as an “effective unshared electron pair”. In each compound, the number n of “effective unshared electron pairs” described above matches the number of nitrogen atoms having “effective unshared electron pairs”.

In the present invention, the number n of “effective unshared electron pairs” with respect to the molecular weight M of the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity is expressed as “effective unshared electron pair content n / M”. It is defined as
The nitrogen-containing layer of the present invention is characterized by containing a compound having an effective unshared electron pair content ratio n / M of 2.0 × 10 ⁻³ or more. In addition, when the effective unshared electron pair content n / M of the compound contained in the nitrogen-containing layer is 3.9 × 10 ⁻³ or more, the adhesion between the silver reflecting layer and the nitrogen-containing layer is further improved. This is preferable. In addition, it is preferable that the effective unshared electron pair content n / M of the compound contained in the nitrogen-containing layer is 1.0 × 10 ⁻² or less because the layer can be easily coated uniformly.

Further, the nitrogen-containing layer only needs to be configured using a compound having an effective unshared electron pair content ratio n / M in the above-described predetermined range, or may be configured only with such a compound. You may be comprised with the mixture of such a compound and another compound. The other compound may or may not contain a nitrogen atom, and even if a nitrogen atom is contained, the effective unshared electron pair content n / M may not be within the above-described range.

When the nitrogen-containing layer is composed of a plurality of compounds, for example, based on the mixing ratio of the compounds, the molecular weight M of the mixed compound obtained by mixing these compounds is obtained, and effective unshared electrons with respect to the molecular weight M are obtained. The total number n of pairs is obtained as an average value of the effective unshared electron pair content n / M, and this value is preferably within the predetermined range described above. That is, it is preferable that the effective unshared electron pair content n / M of the nitrogen-containing layer itself is within a predetermined range.

In addition, if the nitrogen-containing layer is composed of a plurality of compounds and the composition ratio (content ratio) of the compounds is different in the layer thickness direction, the nitrogen on the side in contact with the silver reflective layer 5 The effective unshared electron pair content n / M on the surface of the containing layer may be in the predetermined range described above.

Hereinafter, as specific examples of the compound having an effective unshared electron pair content n / M of 2.0 × 10 ⁻³ or more, Compound No. 1-No. 45 is shown. Table 1 below shows these compound Nos. 1-No. A molecular weight M of 45, a number n of effective unshared electron pairs, and an effective unshared electron pair content n / M are shown. In addition, the following compound No. In 33 copper phthalocyanine, of the unshared electron pairs of the nitrogen atom, the unshared electron pairs that are not coordinated to copper are counted as “effective unshared electron pairs”.
In addition, the following compound No. In 19 and 20, the number n of effective unshared electron pairs and the molecular weight M are values shown in Table 1, respectively, but this is not limited depending on the value of the repeating unit n in each chemical formula. However, regardless of the value of the repeating unit n in each chemical formula, the value of the effective unshared electron pair content n / M is as shown in Table 1.

The compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention is used in an amount sufficient to improve the adhesion with the silver reflective layer, and is usually adjacent to the silver reflective layer. It is preferable that at least one layer to be contained is contained in the range of 0.1 to 5% by mass. More preferably, it is in the range of 1 to 5% by mass. If it is in the said range, adhesiveness can fully be improved and the merit on cost is also high.

The compound having a nitrogen atom having an unshared electron pair not involved in aromaticity is preferably contained in at least one of the anchor layer and the resin coat layer described later, and is contained in both the anchor layer and the resin coat layer. It is more preferable.

Subsequently, each constituent layer constituting the film mirror of the present invention will be described.

[3] Resin base material As the resin base material, various conventionally known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, polycarbonate films, polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable. It is particularly preferable to use a polyester film such as polyethylene terephthalate or an acrylic film. The resin film may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.

In order to make the resin base material contain a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention, for example, if it is a solution casting film, an organic solvent to be prepared is included. It is preferable to add a predetermined amount of the compound to the dope and then cast it on a metal support.
When the compound is contained in the resin base material, it is preferably contained in the range of 0.1 to 5% by mass.

Since the resin base material is located farther from the light incident side than the silver reflecting layer, it is difficult for ultraviolet rays to reach the resin base material. In particular, by making the layer closer to the light incident side than the resin base material contain an ultraviolet absorber or providing an acrylic resin layer containing an ultraviolet absorber, it is even more difficult for ultraviolet rays to reach the resin substrate. Can do. In that case, even a resin that is easily deteriorated by ultraviolet rays can be used as a material for the resin base material. From such a viewpoint, it becomes possible to use a polyester film such as polyethylene terephthalate as the material of the resin base material.

The thickness of the resin base material is preferably set to an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 10 to 300 μm. The range is preferably 20 to 200 μm, more preferably 30 to 100 μm.

In addition, the film mirror of the present invention is preferably manufactured using a long film as a resin base material, and preferably has a length of 1000 m or more, and is a long film of about 5000 m from the viewpoint of productivity and handling. Is preferably used.

[4] Anchor layer The anchor layer is made of a resin, and adheres the resin base material and the silver reflecting layer. The compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention It is preferably contained. Therefore, the anchor layer has a close adhesion between the resin base material and the silver reflective layer, heat resistance that can withstand heat when the silver reflective layer is formed by a vacuum deposition method, and the high reflective performance that the silver reflective layer originally has. Smoothness and the like for drawing out are necessary.

The resin material used as the material of the anchor 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 resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, etc., or a mixture of these resins can be used. From the viewpoint of weather resistance, a polyester resin and a melamine resin mixed resin are preferable. It is more preferable to use a thermosetting resin mixed with a curing agent such as.

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

The thickness of the anchor layer is preferably in the range of 0.01 to 3 μm, more preferably in the range of 0.1 to 1 μm. When the thickness is greater than 0.01 μm, the adhesion is improved, the unevenness on the surface of the resin substrate is covered and smoothness is improved, and as a result, the effect of increasing the reflectance of the silver reflective layer is exhibited. . Moreover, it is preferable that the thickness is 3 μm or less because there is no uneven formation of the anchor layer and the smoothness is high, and the anchor layer is sufficiently cured.

The anchor layer preferably contains a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity within a range of 0.1 to 5% by mass, and more preferably within a range of 1 to 5% by mass. It is. The compound is preferably dissolved in an organic solvent such as methanol, glycols, and ketones and added to the resin material.

[5] Silver reflection layer The silver reflection layer is a layer containing silver having a function of reflecting sunlight.

The surface reflectance of the silver reflective layer is preferably 80% or more, more preferably 90% or more.

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

As a method for forming this reflective layer, either a wet method or a dry method can be used. A typical example of the wet method is a plating method, in which a film is formed by depositing a metal from a solution. Specific examples include silver mirror reaction. On the other hand, as a typical example of the dry method, there is a vacuum film forming method, and concrete examples include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition. Method and sputtering method. In particular, a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. For example, in a film mirror manufacturing method, a method of forming a silver reflective layer by silver vapor deposition is preferably used.

As described above, when the thickness of the silver reflective layer is in the range of, for example, 30 to 300 nm, the functional film having the silver reflective layer can be used as a film mirror for solar power generation. More preferably, it is in the range of 80 to 200 nm from the viewpoint of durability. By making the layer thickness of the silver reflective layer in the above range, it is possible to suppress a decrease in reflectance in the visible light region due to light transmission or light scattering due to unevenness on the surface. .

[6] Resin Coat Layer The resin coat layer is provided on the light incident side of the silver reflective layer, and is preferably adjacent to the silver reflective layer.

By incorporating a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention into the resin coat layer, the adhesion between the silver reflective layer and the resin coat layer can be greatly improved. .

The content of the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity in the resin coat layer is in the range of 0.1 to 5% by mass. More preferably, it is in the range of 1 to 5% by mass.

In addition, the resin coat layer contains a corrosion inhibitor or an antioxidant, as long as it does not inhibit the effect of the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention, and reflects silver. It is also preferable that a function for preventing corrosion and deterioration of the layer is provided.

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

As the binder for the resin coating layer, the following resins can be preferably used. For example, cellulose ester, polyester, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyethylene terephthalate, polyethylene naphthalate, polyester, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate propionate , Cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide, polyamide, fluororesin, nylon, polymethyl A methacrylate, an acrylic resin, etc. can be mentioned. Among them, an acrylic resin having high resistance to ultraviolet rays is preferable from the viewpoint of light resistance.

(6-1) Corrosion inhibitor The corrosion inhibitor preferably has an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which a metal (silver) is chemically or electrochemically eroded or deteriorated by an environmental material surrounding it (see JIS Z0103-2004).

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

Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, and having an imidazole ring It is desirable to be selected from a compound, a compound having an indazole ring, a copper chelate compound, a compound having a thiol group, a thiourea, a naphthalene-based compound, or a mixture thereof.

In compounds such as benzotriazole, an ultraviolet absorber may also serve as a corrosion inhibitor. It is also possible to use a silicone-modified resin. The silicone-modified resin used for the resin coat layer is not particularly limited.

As these compounds, compounds described in paragraphs 0061 to 0073 of JP2012-232538A can be preferably used.

Examples of commercially available products include LA31 from ADEKA Corporation and Tinuvin 234 from BASF Japan Corporation.

(6-2) Antioxidant It is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, or a phosphite-based antioxidant as the antioxidant that is a corrosion inhibitor having antioxidant ability. Moreover, a hindered amine light stabilizer and a nickel ultraviolet stabilizer can be preferably used as the light stabilizer.

As these compounds, compounds described in paragraphs 0046 to 0053 of JP2012-232538A can be preferably used.

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

[7] Adhesive layer The adhesive layer is not particularly limited as long as it has a function of enhancing the adhesion between the layers. In the example shown to FIG. 1B, it forms in order to improve the adhesiveness of a resin coat layer and an acrylic resin layer. Therefore, the adhesive layer needs to have close contact between the layers and smoothness to bring out the high reflection performance inherent in the silver reflective layer.

The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.1 to 10 μm, from the viewpoints of adhesion, smoothness, reflectance of the reflective material, and the like.

When the adhesive layer is a resin, the resin is not particularly limited as long as it satisfies the above adhesiveness and smoothness conditions, polyester resin, urethane resin, acrylic resin, melamine resin, epoxy resin Resin, polyamide 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 a curing agent such as isocyanate. 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.

Further, when the adhesive layer is a metal oxide, the adhesive layer can be formed by depositing, for example, silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like by various vacuum film forming methods. For example, a film can be formed by resistance heating vacuum deposition, electron beam heating vacuum deposition, ion plating, ion beam assisted vacuum deposition, sputtering, or the like.

[8] Acrylic resin layer The acrylic resin layer is preferably a layer containing an ultraviolet absorber for the purpose of preventing deterioration of the film mirror by ultraviolet rays. The acrylic resin layer is preferably provided on the light incident side with respect to the resin base material, and is preferably provided on the light incident side with respect to the silver reflecting layer.

The acrylic resin layer is a layer using an acrylic resin as a binder, and the thickness of the acrylic resin layer is preferably in the range of 1 to 200 μm.

As the acrylic resin layer, Sumipex Technoloy S001G 75 μm (manufactured by Sumitomo Chemical Co., Ltd.), which is an acrylic film containing a commercially available ultraviolet absorber, can be preferably used.

Moreover, in addition to providing the acrylic resin layer on the film mirror, an ultraviolet absorber is added to any one of the constituent layers provided on the light incident side of the resin substrate so that it also serves as the acrylic resin layer. Also good. For example, it is preferable to add an ultraviolet absorber to the hard coat layer.

The ultraviolet absorber is roughly classified into an organic type and an inorganic type.
Examples of organic ultraviolet absorbers include benzophenone, benzotriazole, phenyl salicylate, and triazine, and inorganic ultraviolet absorbers include, for example, titanium oxide, zinc oxide, cerium oxide, and oxide. Iron etc. are mentioned. Among these, benzophenone compounds, benzotriazole compounds with little coloring, and triazine compounds are preferable. Further, ultraviolet absorbers described in JP-A Nos. 10-182621 and 8-337574, and polymer ultraviolet absorbers described in JP-A Nos. 6-148430 and 2003-113317 may be used. Examples of the ultraviolet absorber preferably used include compounds described in JP-A-2012-232528, paragraphs 0036 to 0045.

The content of the ultraviolet absorber is in the range of 0.1 to 20% by mass, preferably in the range of 1 to 15% by mass, and more preferably in the range of 3 to 10% by mass. By making it within these ranges, it becomes possible to improve the weather resistance while maintaining good adhesion of the other constituent layers.

[9] Intermediate layer The intermediate layer is a constituent layer that improves the adhesion between the acrylic resin layer and a hard coat layer described later.

This intermediate layer contains at least one of polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass. Polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass have a hydroxy group as a reactive group.

Examples of the method for forming the intermediate layer include a method by coating. When coating a coating film to be an intermediate layer by a coating method, various conventionally used coating methods such as spray coating, spin coating, bar coating, etc. can be used, such as polyvinyl alcohol resin, vinyl acetate. The intermediate layer can be formed by applying and applying a solution containing at least one of resin, water-soluble cellulose, and water glass on, for example, an acrylic resin layer.

The layer thickness of the intermediate layer is preferably from 0.1 to 5 μm, particularly preferably from 0.1 to 1 μm.

The intermediate layer contains at least one of polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass, so that they and reactive groups on the surface of the acrylic resin layer (hydroxy group, carboxy group, etc.) And when the hard coat layer and the hard coat layer contain a polysiloxane compound, the intermediate bond between the intermediate layer and the acrylic resin layer and the interlayer between the intermediate layer and the hard coat layer are obtained by chemically bonding with the compound. The bond becomes a stronger bond. As a result, the adhesion between the acrylic resin layer and the hard coat layer via the intermediate layer is improved.

It is also preferable that the intermediate layer contains polyisocyanate. In particular, when a polyvinyl alcohol resin and water-soluble cellulose are used as the material for the intermediate layer, it is preferable that a water-dispersed polyisocyanate is contained.

When the intermediate layer contains polyisocyanate, the interlayer bond between the intermediate layer and the acrylic resin layer and the interlayer bond between the intermediate layer and the hard coat layer are further strengthened.

It is also preferable that the intermediate layer contains conductive fine particles. When the intermediate layer contains conductive fine particles, the intermediate layer can also function as an antistatic layer.

[10] Hard coat layer The hard coat layer is a constituent layer (protective layer) provided on the outermost layer of the film mirror. When the film mirror is configured as shown in FIG. 1A, a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention is present in the hard coat layer in an amount of 0.1 to It is preferably contained in the range of 5% by mass.

If the thickness of the hard coat layer is too thick, there is a risk of cracking due to stress, and if the thickness of the hard coat layer is too thin, the hardness cannot be maintained. Therefore, the layer thickness is preferably in the range of 0.5 to 10 μm, more preferably in the range of 1 to 5 μm.

In particular, the hard coat layer used in the present invention preferably has weather resistance, scratch resistance, and antifouling properties. Regarding scratch resistance, it is preferable that the pencil hardness of the hard coat layer surface is H or more and less than 6H and 30 or less scratches in a steel wool test with a load of 500 g / cm ² . Regarding the antifouling property, it is preferable that the falling angle of the hard coat layer is larger than 0 ° and not more than 30 ° because water droplets are easily dropped and the antifouling property is excellent.

The pencil hardness is evaluated based on the pencil hardness test JIS-K5400. In the steel wool test, steel wool (# 0000) was attached as a wear material to a reciprocating abrasion tester (HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.), and each water repellent / antifouling article was tested under a load of 500 g / cm ² . In this test, the surface is reciprocated 10 times at a speed of 10 mm / sec to evaluate the number of scratches. The sliding angle was measured by attaching a sliding method kit DM-SA01 to a contact angle meter DM501 (Kyowa Interface Chemistry), dropping 50 μl of water, tilting the support from a horizontal state at a speed of 0.5 ° / second, The angle at which the rolls down is measured as the fall angle. A smaller rolling angle is preferable because water droplets can be easily dropped and have excellent antifouling properties.

(10-1) Polymer having a metalloxane skeleton This hard coat layer is preferably a layer containing an inorganic oxide or inorganic nitride derived from a polymer having a metalloxane skeleton.

The metalloxane skeleton as used in the present invention is a skeleton having a bond between a metal atom and an oxygen atom, that is, a MO bond, and a polymer having a metalloxane skeleton has a repeating main chain skeleton of this MO bond. A sol-gel method is preferable as a method for polymerizing the polymer compound. Examples of the polymetalloxane include polysiloxane, polytitanoxane, polyaluminoxane, polyzircoxane and the like.

Examples of the polymer material having a metalloxane skeleton include polymethoxane such as silicon, titanium, zirconium, and aluminum, or polysilazane, perhydropolysilazane, alkoxysilane, alkylalkoxysilane, and polysiloxane. Preferably, it is a polymer having a metalloxane skeleton containing at least one element selected from silicon, aluminum, zirconium and titanium.

The binder having a metalloxane skeleton according to the present invention is preferably a polysiloxane, a polytitanoxane, a polyaluminoxane, or a polyzirconoxane composed of a polymetalloxane formed from a metal alkoxide. Metal alkoxides include Si (OC ₂ H ₅ ) ₄ , Al (OC ₂ H ₅ ) ₄ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (iso-OC ₃ H ₇ ) ₄ , Ti Examples thereof include single metal alkoxides such as (OC ₄ H ₉ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (iso-OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ .

Among the above, polysiloxane is preferable, and polysiloxane represented by the following general formula (1) is particularly preferable. It is preferable to form the outermost layer by applying and drying a material containing these metalloxane skeletons. The outermost layer is preferably formed by a thermosetting reaction using a sol-gel method.

In the general formula (1), R ¹¹ and R ¹² may be the same as or different from each other, and represent a hydrogen atom or an organic group such as an alkyl group or an aryl group. p represents a repeating unit.

Also, as the polysiloxane, for example, any of the following may be used. Tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycyl Sidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl Partial hydrolysates of silane compounds having hydrolyzable silyl groups such as methyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane , It can be used such as those obtained by adding the silane compound having a radical polymerizable organo silica sol, or organosilica sol fine particles of silicic anhydride was stably dispersed in an organic solvent. However, the present invention is not limited to this.

The binder is preferably applied by a method in which an inorganic oxide is formed by a thermosetting reaction using a sol-gel method.

The sol-gel method is a method of forming an inorganic oxide from an organometallic compound that is a precursor of an inorganic oxide. That is, using a metal alkoxide, which is a kind of organometallic compound, as a starting material, the solution is hydrolyzed and subjected to polycondensation to form a sol. An inorganic oxide is obtained. For example, in the process of forming a silica glass film, when tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), which is a metal alkoxide of silicon, is used, tetraethoxysilane is dissolved in a solvent such as alcohol, and a catalyst such as an acid is used. By adding a small amount of water and mixing well, a liquid polysiloxane sol is formed according to the following reaction formula.

Hydrolysis reaction Si (OC ₂ H ₅ ) ₄ + 4H ₂ O → Si (OH) ₄ + 4C ₂ H ₅ OH
Dehydration condensation reaction nSi (OH) ₄ → [SiO ₂ ] n + 2nH ₂ O

When a polysiloxane sol is applied to a resin substrate and dried, the volume of the sol shrinks with the evaporation of water and ethyl alcohol (C ₂ H ₅ OH) generated by the solvent and reaction. Residual OH groups at the ends of the polymer undergo a dehydration condensation reaction and are bonded, and the coating film becomes a gel (solidified body). Furthermore, when the obtained gel film is baked to strengthen the bond between the polysiloxane particles, a strong gel film can be obtained.

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

In addition, as a preferable method for forming a hard coat layer, there is a method in which polysilazane is coated and formed, and is cured by heating at a temperature of about 50 to 200 ° C. to obtain a cured film. When the precursor of the hard coat layer contains polysilazane, for example, after applying a solution to which a catalyst is added if necessary in an organic solvent containing polysilazane represented by the following general formula (2), the solvent is evaporated. The polysilazane layer having a layer thickness in the range of 0.05 to 3.0 μm is left on the film mirror F. Then, a glass-like transparent hard coat film is formed on the film mirror F by locally heating the polysilazane layer in the presence of oxygen, active oxygen, and in some cases nitrogen in an atmosphere containing water vapor. Can be formed.

General formula (2)
-(SiR ¹ R ² -NR ³ ) _n-

In the general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and are independently of each other a hydrogen atom, or an optionally substituted alkyl group, aryl group, Vinyl group or (trialkoxysilyl) alkyl group, preferably hydrogen atom, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, tert-butyl group, phenyl group, vinyl group, It represents a group selected from the group consisting of a 3- (triethoxysilyl) propyl group and a 3- (trimethoxysilylpropyl) group. In this case, n is an integer, and n is determined so that the polysilazane has a number average molecular weight in the range 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 in the range of 0.5 to 7 mol%, based on polysilazane.

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

In another preferred embodiment, the hard coat layer in the present invention contains at least one polysilazane represented by the following general formula (3).

General formula (3)
-(SiR ¹ R ² -NR ³ ) _n- (SiR ⁴ R ⁵ -NR ⁶ ) _p-

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

Particularly preferred are compounds in which R ¹ , R ³ and R ⁶ represent a hydrogen atom, and R ² , R ⁴ and R ⁵ represent a methyl group. Particularly preferred are compounds in which R ¹ , R ³ and R ⁶ represent a hydrogen atom, R ² and R ⁴ represent a methyl group, and R ⁵ represents a vinyl group. Particularly preferred are compounds in which R ¹ , R ³ , R ⁴ and R ⁶ represent a hydrogen atom and R ² and R ⁵ represent a methyl group.

Furthermore, in another preferred embodiment, the hard coat layer in the present invention contains at least one polysilazane represented by the following general formula (4).

General formula (4)
-(SiR ¹ R ² -NR ³ ) _n- (SiR ⁴ R ⁵ -NR ⁶ ) _p- (SiR ⁷ R ⁸ -NR ⁹ ) _q-

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

Particularly preferred are R ¹ , R ³ and R ⁶ represent a hydrogen atom, R ² , R ⁴ , R ⁵ and R ⁸ represent a methyl group, R ⁹ represents a (triethoxysilyl) propyl group, and R ⁷ is a compound representing an alkyl group or a hydrogen atom.

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

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

The contact angle of water on the surface of the hard coat layer is preferably in the range of 80 to 170 °. The range is preferably 90 to 150 °. Further, the dynamic friction coefficient of the hard coat layer surface is preferably in the range of 0.10 to 0.35.

For example, the hard coat layer may contain a fluorine compound, a silicon compound, fluorine or silicon so that the contact angle of water on the surface of the hard coat layer is in the range of 80 to 170 °. More specifically, the surface energy is lowered by vapor deposition using a mixed gas of a fluorine compound and a silicon compound, or a compound having fluorine and silicon, and the water contact angle of the hard coat layer is in the range of 80 to 170 °. can do.

Also, the hard coat layer preferably has a dynamic friction coefficient in the range of 0.10 to 0.35, more preferably in the range of 0.15 to 0.30, in order to improve the scratch resistance.

By using a material having a metalloxane skeleton for the hard coat layer, the coefficient of dynamic friction between the film surfaces can be in the range of 0.10 to 0.35.

(10-2) Ultraviolet Absorber The hard coat layer preferably contains an ultraviolet absorber.

Examples of organic ultraviolet absorbers include benzophenone-based, benzotriazole-based, phenyl salicylate-based, and triazine-based materials used in the above-described acrylic resin layer.

In addition, examples of the inorganic ultraviolet absorber include metal oxide particles such as titanium oxide, zinc oxide, cerium oxide, and iron oxide.

Particularly, the hard coat layer preferably contains an ultraviolet absorber having an absorption maximum wavelength in the range of 250 to 300 nm. The hard coat layer containing such an ultraviolet absorber suppresses the deterioration of the interface with the intermediate layer, and can maintain the adhesion between the hard coat layer and the intermediate layer over a long period of time. Can be improved.

(10-3) Inorganic fine particles contained in hard coat layer The hard coat layer according to the present invention preferably contains fine particles from the viewpoint of improving scratch resistance and slipperiness. The fine particles are not particularly limited, but are preferably inorganic fine particles composed of an inorganic oxide. As the inorganic oxide fine particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si. , K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba La, Ta, Hf, W, Ir, Tl, Pb, Bi, etc., specifically, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, oxidation Examples include tantalum, magnesium oxide, calcium oxide, strontium oxide, barium oxide, indium oxide, tin oxide, and lead oxide. In the present invention, inorganic oxide fine particles are , Alumina, titanium oxide, is preferably at least one of the transparent inorganic oxide fine particles selected from zinc oxide and zirconium oxide. The fine particles used in the present invention preferably have high transparency.

The average particle diameter of the fine particles is preferably in the range of 10 to 180 nm, from the viewpoint that the root mean square roughness Rq of the surface can be controlled in the range of 5 to 50 nm, and more preferably 10 to 100 nm. Range.

If the average particle diameter is 10 nm or more, the root mean square roughness Rq can be 5 nm or more, and a sufficient surface roughness can be ensured. Moreover, if an average particle diameter is 180 nm or less, the root mean square roughness Rq can be 50 nm or less, and the transparency of a film is not impaired.

In the hard coat layer according to the present invention, the proportion of fine particles when the binder having the metalloxane skeleton is 100% by mass is preferably in the range of 30 to 90% by mass.

(10-4) Formation of hard coat layer The above-mentioned resin material is applied on an intermediate layer provided on a resin base material and cured by heating, whereby the dehydration condensation reaction is promoted and cured / crosslinked. A hard coat layer is formed.

As a method for forming a coating film to be the hard coat layer, it can be formed by a coating method using a wire bar coating, spin coating, dip coating, or the like. The film can also be formed by a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

[11] Gas Barrier Layer In the film mirror of the present invention, it is preferable to form a gas barrier layer if necessary, and it is preferable that a film mirror is formed as the gas barrier layer 11 as shown in FIG. 1B.

The gas barrier layer is preferably provided on the light incident side with respect to the silver reflective layer.

The gas barrier layer is intended to prevent the deterioration of humidity, especially the deterioration of the resin base material and each component layer supported by the resin base material due to high humidity, but with special functions and applications. As long as it has a function of preventing deterioration, various types of gas barrier layers can be provided.

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

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

Examples of the method for forming the gas barrier layer include a method of forming an inorganic oxide or an inorganic nitride by a method such as vacuum deposition, sputtering, ion beam assist, chemical vapor deposition, etc., but inorganic oxidation by a sol-gel method is possible. A method of forming an inorganic oxide film by applying a heat treatment and / or ultraviolet irradiation treatment to the coating film after applying a precursor of the product (polysilazane or the like) is preferably used.

Details of the precursor of the inorganic oxide and the sol-gel method are described in paragraphs 0049 to 0072 of JP2012-047661A, and the polysilazane method is described in paragraphs 0073 to 0085 of the same document. .

[12] Adhesive layer The adhesive layer is a constituent layer for adhering and fixing the film mirror to the metal substrate.

The adhesive layer is not particularly limited as long as it can adhere a film mirror to a metal substrate. For example, a dry laminating agent, a wet laminating agent, an adhesive, a heat sealing agent, a hot melt agent, or the like is used. Can do. Further, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber, or the like may be used.

The laminating method in which the adhesive layer is provided on the back surface of the resin base material is not particularly limited, and for example, a roll-type continuous method is preferable 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.

Specific materials used for the adhesive layer include, for example, “SK Dyne Series” manufactured by Soken Chemical Co., Ltd., “Oribain BPW Series”, “BPS Series” manufactured by Toyo Ink Co., Ltd., “Arcon” “Superester” “High Pale” manufactured by Arakawa Chemical Co., Ltd. The pressure-sensitive adhesive can be suitably used.

In addition, until the film mirror is bonded to the metal substrate, the pressure-sensitive adhesive layer is covered with a release layer, which will be described later, so that the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer is maintained.

In the adhesive layer, the aforementioned corrosion inhibitors, amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring It is also preferable to contain a compound having an indazole ring, a copper chelate compound, a compound having a mercapto group, a thiourea, a naphthalene-based compound, or a mixture thereof.

[13] Release layer The film mirror of the present invention may have a release layer on the side opposite to the light incident side of the adhesive layer. For example, when a film mirror is shipped, the film is shipped with the release layer attached to the adhesive layer, the film mirror having the adhesive layer is peeled from the release layer, and is bonded to another substrate to form a solar power generation reflection device. be able to.

The release layer only needs to protect the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, a polyethylene terephthalate film or sheet, a fluorine film, etc. Plastic film or sheet, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., coating the resin kneaded with these, or surface treatment such as metal deposition of metal such as aluminum A resin film or sheet is used.

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

In addition, it may be bonded after providing a concave portion or a convex portion before bonding these release layers to the film mirror, and may be formed to have a concave portion or a convex portion after bonding. It may be simultaneously performed to have a concave portion or a convex portion.

[14] Reflector for solar thermal power generation The reflective device for solar thermal power generation includes a film mirror and a self-supporting supporting base material, and the reflecting mirror is formed by bonding the film mirror to the supporting base material via an adhesive layer. It is.

In addition, the "self-supporting property" referred to here is a state in which the supporting base material supports the edge portion of the film mirror in a state of being cut to a size used as a supporting base material for the solar power generation reflection device, This means that the film mirror has rigidity enough to support the film mirror. The support base material of the solar power generation reflecting device has self-supporting properties, so that it is easy to handle when installing the solar power generation reflecting device, and the holding member for holding the solar power generation reflecting device has a simple configuration. Therefore, it is possible to reduce the weight of the reflection device itself, and it is possible to suppress power consumption during solar tracking.

The solar power generation reflecting device R includes, for example, a film mirror F and a metal substrate 1 as a support member, as shown in FIG. Specifically, the reflective layer R for solar power generation is formed by bonding the adhesive layer 2 of the film mirror F to the metal substrate 1.

(14-1) Metal Substrate The metal substrate is a support member for supporting the attached film mirror and preferably maintaining the reflecting surface of the film mirror.

As a metal substrate of the solar power generation reflector, for example, a metal material such as a steel plate, a copper plate, an aluminum plate, an aluminum-plated steel plate, an aluminum-based alloy-plated steel plate, a copper-plated steel plate, a tin-plated steel plate, a chrome-plated steel plate, or a stainless steel plate. 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.

The thickness of these metal base materials is preferably about 0.05 mm to 3 mm from the viewpoints of handleability, thermal conductivity, heat capacity, and the like.

(14-2) Holding Member The solar power generation reflection device has a holding member that holds the film mirror. The holding member preferably holds the film mirror in a state where the sun can be tracked. The form of the holding member is not particularly limited. For example, a form in which a plurality of places are held by rod-like holding members so that the film mirror can hold a desired shape is preferable. The holding member has a configuration for holding the film mirror in a state in which the sun can be tracked. However, when the sun is tracked, the holding member may be driven manually, or a separate driving device may be provided to automatically track the sun. good.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.
Here, the structures of the compounds used in the examples described below are shown below.

<< Production of Film Mirror 1 >>
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate 3. The following compound (1) is coated on one side of the polyethylene terephthalate film by a vacuum deposition method to form an anchor layer 4 having a thickness of 0.1 μm, and a silver reflective layer 5 is formed on the anchor layer 4 by a vacuum deposition method. Thus, a silver reflective layer having a thickness of 100 nm was formed. Further, the following compound (1) was coated on the silver reflective layer 5 by a vacuum vapor deposition method to form a resin coat layer 6 having a thickness of 0.3 μm.

Next, on the resin coat layer 6, a transparent acrylic film (Mitsubishi Rayon acrylene HBS010P, thickness 100 μm) as an acrylic resin layer 8 was bonded at a laminating temperature of 60 ° C. by a dry lamination process.

Prior to the dry lamination process of the acrylic resin layer 8, an intermediate layer coating solution in which 5 mass% of PVA-403 (manufactured by Kuraray Co., Ltd.) was dissolved in water was applied on the acrylic resin layer 8. The intermediate layer 9 was formed by partial drying. The dry thickness of the intermediate layer 9 was 0.5 μm.

A hard coat layer coating solution having the following composition was prepared as the coating solution, and the hard coat layer coating solution was applied onto the intermediate layer 9 using a microgravure coater so that the layer thickness after curing was 3 μm. After evaporating and drying the solvent, the hard coat layer 10 was formed by curing with 0.2 J / cm ² ultraviolet irradiation using a high-pressure mercury lamp. The hard coat layer 10 is laminated at a position that becomes the outermost layer after the dry lamination process.

<Coating liquid for hard coat layer>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoreaction initiator (Irgacure 184 (BASF Japan)) 4 parts by weight Ethyl acetate 150 parts by weight Propylene glycol monomethyl ether 150 parts by weight Silicon compound (BYK- 307 (manufactured by Big Chemie Japan)) 0.4 parts by mass

Next, one side of a 25 μm thick polyester separate film as a release layer 12 was prepared by adding 1 part of a platinum catalyst to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 to form a 35 mass% toluene solution. After coating at 130 ° C. for 5 minutes to form a 25 μm-thick silicone adhesive layer 2 (Si-based), the polyethylene terephthalate film is laminated on the side opposite to the anchor layer 4 and the silver reflective layer 5. And the film mirror 1 of the comparative example was obtained.

<< Production of film mirrors 2 to 11 >>
Film mirrors 2 to 11 were produced in the same manner except that the compounds used in the anchor layer 4 and the resin coat layer 6 were changed to the compounds shown in Table 2 in the production of the film mirror 1.

<< Evaluation of film mirrors 1 to 11 >>
The film mirrors 1 to 11 produced as described above were evaluated for corrosion resistance, light resistance, adhesion between the silver reflective layer and the resin coat layer or between the silver reflective layer and the anchor layer, and generation of cracks according to the following methods. The evaluation results are shown in Table 2 below.

<Corrosion resistance>
The produced film mirror was cut to 5 cm □, immersed in a 5% by mass ammonium sulfide aqueous solution, and left to stand for 3 days. Corrosion resistance was evaluated according to the following criteria.

5: No corrosion is seen at all.
4: A blackened corroded portion can be seen at the cut end, but there is no discoloration on the front.
3: Although the corrosion part blackened from the cut edge part can also be confirmed from the front, the corrosion part exists in the range within 5 mm from the edge part.
2: 50% or more of the reflecting surface is corroded and blackened.
1: All of the reflective surface is corroded and blackened.

<Light resistance>
The reflective surface of the produced film mirror was irradiated with ultraviolet rays at 150 mW for 96 hours using an I-Super UV tester manufactured by Iwasaki Electric under an environment of 65 ° C., and then the regular reflectance was measured.
Here, the regular reflectance was a 5-degree regular reflectance measured by the following method.

Using a spectrophotometer U-4100 (solid sample measurement system) manufactured by Hitachi High-Technologies Corporation, a relative reflectance measurement with respect to a reference sample having an incident angle of 5 degrees was performed. The wavelength range was measured at 250 to 2500 nm, and it was confirmed whether there was any wavelength range in which the reflectance dropped partially. The reflectance in the visible light region (400 to 800 nm) was averaged, and this was defined as a regular reflectance of 5 degrees.

The 5-degree regular reflectance of the film mirror before the ultraviolet irradiation is measured in advance, and the smaller the fluctuation range from the 5-degree regular reflectance after the ultraviolet irradiation is, the better the light resistance is.
Light resistance was evaluated according to the following criteria.

5: The fluctuation range of the reflectance is less than 3%.
4: Reflectance fluctuation range of 3% to less than 5% 3: Reflectance fluctuation range of 5% to less than 8% 2: Reflectance fluctuation range of 8% to less than 10% 1: Reflectance fluctuation range 10% or more

<Adhesion>

The prepared film mirror was irradiated with ultraviolet rays at 150 mW for 96 hours using an I-Super UV tester manufactured by Iwasaki Electric under an environment of 65 ° C., and then when 100 mask loss cut was performed according to JIS K5400 standard. A tape peeling test was performed, and adhesion was evaluated according to the following criteria.

5: Film peeling is 0 square 4: Film peeling is 1 square or more and 5 squares or less 3: Film peeling is 6 square or more and 10 squares or less 2: Film peeling is 11 squares or more 1: Film peeling is 15 squares or more

<crack>
The produced film mirror was irradiated with ultraviolet rays at 150 mW for 30 days in an environment of 65 ° C. using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and then the occurrence of cracks on the surface (hard coat layer 10) was visually observed. confirmed. Cracks were evaluated according to the following criteria.

○: Not generated △: Slightly generated (appropriate with loupe)
×: Appears clearly (appreciable with the naked eye)

From Table 2, the anchor layer 4 and the resin coat layer 6 contain a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, and the effective unshared electron pair content ratio n / M of the compound is 2 It is clear that the film mirrors 3 to 11 of the present invention having a size of 0.0 × 10 ⁻³ or more are excellent in corrosion resistance, light resistance and adhesion as compared with the film mirrors 1 and 2 of the comparative example. .
In addition, it is clear that the occurrence of cracks in the hard coat layer 10 is suppressed in the film mirrors 3 to 11 of the present invention.

Therefore, according to the present invention, even in an environment where the amount of ultraviolet irradiation is very large such as a desert, the reflectance of the silver reflecting layer is reduced due to corrosion or discoloration due to peeling between the silver reflecting layer and other constituent layers. It is possible to provide a film mirror capable of suppressing the above and a solar power generation reflecting device including the same. In addition, since peeling between the silver reflective layer and other constituent layers can be suppressed, deformation and distortion of the film mirror surface can be suppressed, and the occurrence of cracks in the hard coat layer provided on the surface of the film mirror can be suppressed. it can.

As described above, the present invention provides a silver reflective layer caused by peeling between the silver reflective layer and other adjacent constituent layers even when subjected to a load due to outdoor use or cleaning work for a long period of time. It is suitable for providing a film mirror that can suppress a decrease in reflectance caused by corrosion or discoloration of the solar cell, and a solar power generation reflection device including the film mirror.

DESCRIPTION OF SYMBOLS 1 Metal base material 2 Adhesive layer 3 Resin base material 4 Anchor layer 5 Silver reflection layer 6 Resin coat layer 7 Adhesive layer 8 Acrylic resin layer 9 Intermediate layer 10 Hard coat layer 11 Gas barrier layer 12 Release layer F Film mirror R For solar power generation Reflector

Claims (4)

1. A film mirror provided with a silver reflective layer on a resin substrate,
   A nitrogen-containing layer containing a compound having a nitrogen atom adjacent to the silver reflective layer and having an unshared electron pair not involved in aromaticity;
   The compound is a compound having an effective unshared electron pair content ratio n / M of 2.0 × 10 ⁻³ or more, where n is the number of unshared electron pairs not involved in aromaticity and M is the molecular weight. A film mirror characterized by
2. 2. The film mirror according to claim 1, wherein the effective unshared electron pair content ratio n / M is 3.9 × 10 ⁻³ or more.
3. The film mirror according to claim 1 or 2, wherein a hard coat layer containing a polymer having a metalloxane skeleton is provided on the surface.
4. The film mirror according to any one of claims 1 to 3,
   And a support base material for supporting the film mirror.

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