JP2015161826A - Film mirror and reflection device for solar thermal power generation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film mirror having excellent scratch resistance.SOLUTION: A film mirror is provided with a resin base material, and a silver reflection layer and a corrosion prevention layer on at least one face of the resin base material, wherein the film mirror comprises (i) a hard coat layer comprising a material having a metaloxane skeleton on an outermost surface layer; and (ii) an organic-inorganic hybrid layer between the hard coat layer and silver reflection layer.

Description

  The present invention relates to a film mirror and a solar power generation reflector. Specifically, the present invention relates to a high-hardness solar thermal power generation film mirror and a solar thermal power generation reflector.

  In recent years, utilization of natural energy has been studied as an alternative energy to fossil fuel energy such as oil and natural gas. Among them, solar energy, which is the most stable alternative energy for fossil fuels and has a large amount of energy, is attracting attention.

  As another method for converting sunlight into energy, solar thermal power generation, which generates electricity using heat obtained by collecting sunlight using a mirror as a medium, has attracted attention. If this method is used, it is possible to generate power regardless of day and night, and from a long-term perspective, it is considered that the power generation efficiency is higher than that of a solar cell, so that sunlight can be used effectively.

  Although a thick glass mirror is currently used as a mirror for solar thermal power generation, it is heavy and easily broken, so there are problems of poor installation workability and high maintenance cost. Therefore, in recent years, a film mirror obtained by turning a mirror into a film has attracted attention. If it is a film, it is light and does not break, so it can be easily mounted and has a high reflectivity. A disadvantage is that scratch resistance (particularly, scratch resistance) is lower than that of a glass mirror.

  Solar thermal power plants are constructed in areas with a large amount of solar radiation, such as desert areas, but the problem is that dust falls on the mirror surface and the reflectivity decreases over time. In addition, due to the large temperature difference between day and night, a large amount of dew condensation water is generated on the mirror surface in the morning in some areas, sand and soil are mixed in the dew condensation water, and the dirt is strongly attached to the mirror surface by drying. Reflectivity decreases. In particular, in the case of a film mirror, since the resin layer is provided on the outermost surface layer, the surface is strongly charged and dirt is easily adsorbed. Therefore, once every two weeks to two months, ion-exchanged water is sprayed onto the film mirror and rubbed with a brush to periodically remove dirt. However, a large amount of water is used for washing and washing. A large amount of cleaning costs are required because human labor is also required. Further, since ion-exchanged water is periodically sprayed on the mirror and rubbed with a brush, a very high mirror surface hardness is required (see Non-Patent Document 1). In addition, since it is exposed to the outdoors for a long time, a very high UV resistance is also required.

  In consideration of the above problems, for example, Patent Document 1 reports a film mirror having a specific surface hardness.

International Publication No. 2011/096320

Final report on the operation and maintenance improvement program for concentrating solar power plants. Printed June 1999, Gilbert E. et al. Cohen, David W. Kearney, Gregory J .; Kolb

  The film mirror described in Patent Document 1 defines the outermost layer, but since the layer structure is formed mainly of organic materials, a certain degree of durability is ensured, but it is difficult to use for more than 20 years. Also, scratch resistance (particularly scratch resistance) is not sufficient.

  Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film mirror and a solar power generation reflector that are excellent in scratch resistance (particularly, scratch resistance).

  Another object of the present invention is to provide a film mirror and a solar power generation reflecting device having excellent durability.

  As a result of intensive studies to solve the above problems, the present inventor has paid attention to high scratch resistance and weather resistance (surface protection) of inorganic components and high flexibility (flexibility) of organic components, and the outermost layer. By providing a metalloxane-based hard coat layer with high scratch resistance and weather resistance (surface protection), and providing an organic-inorganic hybrid layer with high flexibility (flexibility) between the hard coat layer and the silver reflective layer, The present inventors have found that the above problems can be solved and have completed the present invention.

  That is, the object is a film mirror in which a silver base layer and a corrosion prevention layer are provided on at least one surface of the resin base material, and (i) a material having a metalloxane skeleton in the outermost layer. And (ii) a film mirror having an organic-inorganic hybrid layer between the hard coat layer and the silver reflective layer.

  ADVANTAGE OF THE INVENTION According to this invention, the film mirror excellent in the balance of scratch resistance (especially abrasion resistance) and flexibility can be provided.

It is a schematic sectional drawing which shows one Embodiment of the structure of the film mirror of this invention. It is a schematic sectional drawing which shows one Embodiment of the structure of the solar power generation reflective apparatus which concerns on this invention.

  The present invention is a film mirror in which a silver base layer and a corrosion prevention layer are provided on at least one surface of the resin base material, and (i) a hard containing a material having a metalloxane skeleton in the outermost layer A film mirror having a coating layer (hereinafter also referred to as “metalloxane-based hard coating layer” or “hard coating layer”); and (ii) an organic-inorganic hybrid layer between the hard coating layer and the silver reflective layer About. The film mirror of the present invention is characterized in that a metalloxane-based hard coat layer is provided on the outermost layer, and an organic-inorganic hybrid layer is provided between the hard coat layer and the silver reflective layer.

  As described above, sunlight is reflected / condensed, and power is generated using the heat. In solar thermal power generation, a glass mirror has been used as a sunlight reflecting member. Film mirrors that are difficult, light and flexible are drawing attention. However, the film mirror has a problem that even when a hard coat layer is provided on the surface, the surface hardness is inferior to that of the glass mirror, and scratches are likely to occur during cleaning with a brush. In addition, since solar power generation is installed in a very severe environment such as a desert, high ultraviolet resistance (light resistance, weather resistance, durability) is required. Therefore, the development of film mirrors that use both UV absorbers and inorganic materials to achieve both scratch resistance and weather resistance has been carried out. However, if scratch resistance and weather resistance, particularly scratch resistance, are given priority, the flexibility decreases. No one has sufficient scratch resistance and flexibility. However, the film mirror usually has a concave shape in order to obtain an efficient light collecting property. In addition, as described above, solar power generation plants are often installed in desert regions having a large temperature difference, so that they need flexibility to withstand the temperature difference. For this reason, the film mirror preferably has a good balance between scratch resistance and flexibility.

  In the film mirror described in Patent Document 1, the outermost layer is formed of inorganic (double) oxide fine particles and acrylate or urethane resin. As described above, the outermost layer formed mainly with the organic material is excellent in flexibility, but has insufficient scratch resistance. For this reason, when water is sprayed on the film mirror and rubbed with a brush to remove dust, the dust will damage the mirror surface, and the reflectance will deteriorate with time (poor scratch resistance). On the other hand, although the outermost layer formed of an inorganic material is excellent in scratch resistance, the outermost layer has high hardness, and therefore is inferior in flexibility. As described above, conventionally, scratch resistance and flexibility are in a trade-off relationship, and there has been no demand for a film mirror having an outermost layer satisfying both in a well-balanced manner.

  On the other hand, the film mirror of the present invention is excellent in both scratch resistance and flexibility. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following mechanism.

  That is, the film mirror of the present invention has a hard coat layer containing a material having a metalloxane skeleton in the outermost layer. Here, the metalloxane-based hard coat layer is mainly composed of a material having a metalloxane skeleton which is an inorganic material (preferably composed of a material having a metalloxane skeleton). Since the inorganic material (inorganic component) has strong binding energy, the outermost layer is hard and is not cut by ultraviolet rays contained in sunlight. For this reason, the outermost layer made of such an inorganic material is excellent in scratch resistance (scratch resistance), and has an advantage that the film function hardly changes even when left outdoors for a long period of time. However, on the other hand, such a layer has the disadvantages that it is brittle and has poor flexibility (flexibility) due to its strong binding energy. On the other hand, the organic-inorganic hybrid layer includes both an inorganic material (inorganic component) and an organic material (organic component) (for example, resin). Here, the inorganic material (inorganic component) is excellent in scratch resistance as described above, but is inferior in flexibility. On the other hand, an organic material (organic component) is relatively easily deteriorated by ultraviolet rays, but has excellent flexibility and flexibility. For this reason, the organic-inorganic hybrid resin as a material combining these functions is inferior in scratch resistance and weather resistance than inorganic alone, but is excellent in flexibility and flexibility. For this reason, a metalloxane-based hard coat layer having excellent scratch resistance is disposed on the outermost surface layer that is most easily damaged by ultraviolet rays, and an organic-inorganic hybrid layer having excellent flexibility (flexibility) is disposed underneath (light reflecting layer side). As a result, the film mirror can maintain the flexibility unique to the film while effectively suppressing scratches during surface cleaning.

  Therefore, the film mirror of the present invention has high scratch resistance and weather resistance, and can maintain a good regular reflectance for sunlight for a long time even when installed in a harsh environment for a long time. Excellent flexibility (flexibility). Therefore, the film mirror of this invention can be used conveniently for the solar power generation reflective apparatus.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from the actual ratios.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Film mirror]
As shown in FIG. 1, the film mirror of the present invention has a metalloxane-based hard coat layer, an organic-inorganic hybrid layer, a corrosion prevention layer, a light reflection layer, and a resin base material. Specifically, FIG. 1A is a schematic cross-sectional view showing an embodiment of the configuration of the film mirror of the present invention. As shown in FIG. 1A, the film mirror 10 of the present embodiment includes, in order from the light incident (outermost) side, a metalloxane-based hard coat layer (outermost layer) 4, an organic-inorganic hybrid layer 3, and a light reflecting layer (for example, silver It has at least a reflection layer 2, a corrosion prevention layer 5, and a resin base material (for example, resin film) 1. In addition to the above, the film mirror 10 may have an adhesive layer 6 on the side where the light reflecting layer 2 of the resin substrate 1 is not disposed. According to the said form, since the light reflection layer 2 does not contact | connect the adhesion layer 6, a contaminant invades from the interface of the adhesion layer 6 and the light reflection layer 2, the light reflection layer 2 corrodes, and a reflectance falls. Can be suppressed / prevented. Moreover, since the resin base material 1 is provided between the adhesive layer 6 and the light reflecting layer 2, the unevenness of the adhesive layer 6 is not reflected on the light reflecting layer 2, and the light reflecting layer 2 having high planarity. And a higher reflectance can be achieved.

  In addition, another layer may be interposed between each of the above-mentioned layers, and each layer may be adjacent. For example, an ultraviolet absorbing layer, a gas barrier layer, a corrosion prevention layer, an anchor layer (primer layer), an adhesive layer, and the like may be provided between the hard coat layer and the silver reflective layer as necessary. Further, a release layer or the like may be provided on the light incident side of the hard coat layer. In the present invention, the metalloxane-based hard coat layer and the organic-inorganic hybrid layer are preferably adjacent to each other. By taking this structure, both scratch resistance and flexibility can be improved in a more balanced manner. For this reason, the film mirror of this form is used in a solar power generation reflector, and even when exposed to ultraviolet rays, heat, wind and rain, sandstorms, etc. due to sunlight for a long time, the high reflectivity of the film mirror is more effectively demonstrated. Can be maintained.

  The total thickness of the film mirror of the present invention is not particularly limited, but is preferably 75 to 300 μm, more preferably 90 to 250 μm, and still more preferably 100 to 250 μm from the viewpoints of prevention of bending, regular reflectance, and handling properties. . In addition, it is preferable that the center line average roughness (Ra) of the outermost surface layer on the light incident side of the film mirror is 3 nm or more and 20 nm or less from the viewpoint of preventing scattering of reflected light and increasing the light collection efficiency.

  Moreover, the outline | summary of the reflective apparatus for solar power generation is shown to FIG. 1B.

  As described above, the film mirror 10 shown in FIG. 1A is provided by laminating the corrosion prevention layer 5, the light reflection layer 2, the organic-inorganic hybrid layer 3, and the metalloxane-based hard coat layer 4 on the resin base material 1 in this order. It has been. An adhesive layer 6 is provided on the opposite surface of the resin substrate 1 on the light incident side. As shown in FIG. 1B, the solar power generation reflecting device 20 using the film mirror 10 joins the adhesive layer 6 in the film mirror 10 to the support base material 7, and attaches the film mirror 10 and the support base material 7. This is a reflecting mirror.

  Details of each constituent layer will be described below.

(Metaloxane hard coat layer)
The metalloxane-based hard coat layer according to the present invention includes a material having a metalloxane skeleton. Here, the material having a metalloxane skeleton is not particularly limited, and examples thereof include polymethoxane such as silicon, titanium, zirconium, and aluminum, polysilazane, perhydropolysilazane, alkoxysilane, alkylalkoxysilane, and polysiloxane. Of these, the material having a metalloxane skeleton preferably contains a bifunctional, trifunctional, or tetrafunctional polysiloxane or a mixture thereof. That is, the material having a metalloxane skeleton is represented by the following general formula (A):

It is preferable that it is polysiloxane which has a repeating unit shown by these. By using such a hard coat layer containing polysiloxane, scratch resistance (surface protection) and weather resistance can be further improved. In addition, the material which has the said metalloxane skeleton may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

In the general formula (A), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group. Here, X ¹ , X ² and X ³ may be the same or different. In addition, when there are a plurality of each repeating unit (that is, m, n, or o is an integer of 2 or more), each repeating unit may be the same or different.

  In the above general formula (A), m is the following tetrafunctional siloxane repeating unit:

Indicates the number present in polysiloxane (a material having a metalloxane skeleton), and is an integer of 0 to 3000. Considering more excellent scratch resistance (surface protection) and weather resistance, m is preferably an integer of 0 to 2500, more preferably an integer of 0 to 2000.

  n is the following trifunctional siloxane repeating unit:

Indicates the number present in polysiloxane (a material having a metalloxane skeleton), and is an integer of 1 to 3000. In consideration of better scratch resistance (surface protection) and weather resistance, n is preferably an integer of 1 to 2500, and more preferably an integer of 1 to 2000.

  o is the following bifunctional siloxane repeating unit:

Indicates the number present in polysiloxane (a material having a metalloxane skeleton), and is an integer of 0 to 3000. In consideration of better scratch resistance (surface protection) and weather resistance, n is preferably an integer of 1 to 2500, and more preferably an integer of 1 to 2000.

  The polysiloxane is a thermosetting silicone hard coat made of a partially hydrolyzed oligomer of an alkoxysilane compound, and is preferably made of a thermosetting polysiloxane resin. The hard coat layer may contain other components such as an ultraviolet absorber and an antioxidant described later, but preferably does not substantially contain an organic polymer (resin). “Substantially free of organic polymer (resin)” means that the organic polymer (resin) is contained in the metalloxane-based hard coat layer in an amount of 3% by weight or less in terms of solid content. , Preferably 0% by weight or less (lower limit: 0).

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

  A catalyst may be used for the purpose of accelerating the curing of the hard coat layer. Here, the catalyst is not particularly limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, and hydrofluoric acid. Preferably, in addition to inorganic acids such as hydrochloric acid and nitric acid, organic acids having sulfo groups (also referred to as sulfonic acid groups) or carboxyl groups, such as acetic acid, polyacrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, methylsulfonic acid, etc. Is used. As the organic acid, a compound having a hydroxyl group and a carboxyl group in one molecule is preferably used. For example, hydroxydicarboxylic acid such as citric acid or tartaric acid is preferably used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

Alternatively, a commercially available product may be used as the silicone-based hard coat agent. Commercially available products include, but are not limited to, silicone-based thermal polymerization curing hard coat agents (for example, methyltrimethoxysilane (manufactured by Kanto Chemical Co., Ltd., chemical formula is CH ₃ Si (OCH ₃ ) ₃ ), Co., Ltd. Kenken: SARCoat (trademark) series, Doken Co., Ltd .: NP series, Toshiba Silicone: Tosgard 510 (silicone resin), SR2441 (Toray Dow Corning), Shin-Etsu Chemical Co., Ltd .: KP- 86), Perma-New (registered trademark) 6000 (California Hard coating Company), and the like.

  Alternatively, the hard coat layer may be formed by coating polysilazane and heat-curing it. When the precursor of the hard coat layer contains polysilazane, for example, after applying a solution to which a catalyst is added as necessary in an organic solvent containing polysilazane represented by the following general formula (6), the solvent is evaporated. Thereby removing a polysilazane layer having a layer thickness of 0.05 to 3.0 μm on the outermost surface of the film mirror. Then, by locally heating the polysilazane layer in the presence of oxygen, active oxygen, and possibly nitrogen in an atmosphere containing water vapor, a glass-like transparent hard coat film is formed on the outermost surface of the film mirror. It is preferable to employ a method of forming.

In the above general formula (6), Y ¹ , Y ² and Y ³ are the same or different and are independently of each other a hydrogen atom, or an optionally substituted alkyl group, aryl group, vinyl group or (trialkoxy). A silyl) alkyl group, preferably a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl) Represents a group selected from: In this case, n is an integer, and n is determined so that polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

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

In one preferred embodiment, a solution containing perhydropolysilazane in which all of Y ¹ , Y ² and Y ^{3 in} the general formula (6) are hydrogen atoms is used.

  In another preferred embodiment, the hard coat layer contains at least one polysilazane represented by the following general formula (7).

In the general formula (7), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y 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 of 150 to 150,000 g / mol.

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

  Furthermore, in another preferable embodiment, the transparent hard coat layer contains at least one polysilazane represented by the following general formula (8).

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

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

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

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

  As an additional component of this polysilazane solution, further binders such as those conventionally used in the production of ordinary paints (hard coat agents) can be used. For example, cellulose ethers and cellulose esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose acetobutyrate, natural resins such as rubber or rosin resins, or synthetic resins such as polymerized resins or condensed resins such as aminoplasts, in particular Urea resins and melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, or polysiloxanes.

Further, as another component to be further added to the polysilazane formulation, for example, an additive which affects the viscosity of the formulation, the wettability of the base or the film formability, or inorganic nanoparticles such as SiO ₂ , TiO ₂ , ZnO, ZrO ₂ or Al ₂ O ₃ can be used.

  The hard coat layer preferably contains an ultraviolet absorber. Thereby, the lower layer (for example, organic-inorganic hybrid layer) can be more effectively protected than the hard coat layer itself and the hard coat layer. For this reason, durability of a film mirror can be improved more. Here, the ultraviolet absorber is not particularly limited, for example, an organic ultraviolet absorber such as thiazolidone, benzotriazole, acrylonitrile, benzophenone, aminobutadiene, triazine, phenyl salicylate, benzoate, Alternatively, there are fine powder type ultraviolet blocking agents such as cerium oxide and magnesium oxide and inorganic ultraviolet absorbing agents such as titanium oxide, zinc oxide and iron oxide. Of these, organic ultraviolet absorbers and inorganic ultraviolet absorbers are preferred, and triazine ultraviolet absorbers and inorganic ultraviolet absorbers are more preferred. That is, the ultraviolet absorber is preferably a triazine ultraviolet absorber or an inorganic ultraviolet absorber.

  Examples of organic ultraviolet absorbers include JP-A Nos. 46-3335, 55-15276, JP-A Nos. 5-197774, Nos. 5-232630, Nos. 5-307232, Nos. 6-211813, and Nos. 8-8. -53427, 8-234364, 8-239368, 9-310667, 10-115898, 10-147777, 10-182621, German Patent No. 19739797A, Europe Japanese Patent No. 711804A and Japanese Patent Publication No. 8-501291, U.S. Pat. No. 1,023,859, No. 2,685,512, No. 2,739,888, No. 2,784, No. 087, No. 2,748,021, No. 3,004,896, No. 3,052,636, No. 3,215,530, No. 3,253,9 No. 1, No. 3,533,794, No. 3,692,525, No. 3,705,805, No. 3,707,375, No. 3,738,837, No. The compounds described in 3,754,919, British Patent 1,321,355 and the like can be used.

  Specifically, as the benzophenone-based ultraviolet absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy -Benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4 , 4′-tetrahydroxy-benzophenone and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1, 3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercially available products are LA31 from ADEKA Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl- 1-phenylethyl) phenol (molecular weight 447.6; examples of commercially available products are TINUVIN234 manufactured by BASF), 2- (2H-benzotriazole- - yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN928, trade name, manufactured by BASF), and the like.

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

  Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine, [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol] (TINUVIN1577FF, trade name, manufactured by BASF), TINUVIN477 ( Hydroxyphenyl triazines such as trade name, manufactured by BASF), TINUVIN479 (trade name, manufactured by BASF), [2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2 -Yl] -5- (octyloxy) phenol] (CYASORB UV-1164, trade name, manufactured by Cytec Industries) I can get lost.

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

  Among these UV absorbers, UV absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high temperature molding, so that the weather resistance can be effectively improved with a relatively small amount of addition. it can.

  In addition, UV absorbers with a molecular weight of 400 or more have low transferability from thin hard coat layers to other constituent layers and are not easily deposited on the surface of the laminate, so the amount of UV absorber contained is maintained for a long time. It is preferable from the viewpoint of excellent durability of the weather resistance improvement effect.

  Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl)- Benzotriazoles such as 4- (1,1,3,3-tetramethylbutyl) phenol, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate and other hindered amines, as well as 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1, 2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, etc., which have both hindered phenol and hindered amine structures in the molecule These may be used alone or in combination of two or more. Among these, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2- (2H-benzotriazol-2-yl) -6- (1 -Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2-methylenebis [4- (1,1,3,3-tetrabutyl) -6- (2H -Benzotriazol-2-yl) phenol] is particularly preferred.

  In addition to the above, as the ultraviolet absorber, a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy can also be used. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers acting as a light energy conversion agent, called quenchers, can be used in combination. However, when using the above-mentioned ultraviolet absorber, it is necessary to select one in which the light absorption wavelength of the ultraviolet absorber does not overlap with the effective wavelength of the photopolymerization initiator. When a normal ultraviolet absorber is used, it is effective to use a photopolymerization initiator that generates radicals with visible light.

  In addition, the said ultraviolet absorber can also respectively use those 2 or more types as needed. Further, if necessary, an ultraviolet absorber other than the above-described ultraviolet absorber, for example, a salicylic acid derivative, a substituted acrylonitrile, a nickel complex, or the like can be contained.

The content (in terms of solid content) of the ultraviolet absorber in the hard coat layer is not particularly limited, but is preferably 0.1 to 25% by weight, more preferably 0.5 to 0.5% with respect to the hard coat layer. 20% by weight, more preferably 1 to 15% by weight. Further, the content (content per unit area of the film) of the ultraviolet absorber in the hard coat layer is not particularly limited, but is preferably 0.17 to 2.28 g / m ² , more preferably 0.4 to ² . .28 g / m ² . By making the content of the UV absorber in the above range, it is more effective to cause rolls and films to become dirty due to bleeding out of the UV absorber (and hence haze increase) while exhibiting sufficient weather resistance. Can be suppressed / prevented.

  The hard coat layer preferably contains inorganic fine particles. Thereby, hardness and scratch resistance can be further improved. Here, the inorganic fine particles are not particularly limited, and examples thereof include silica, zinc oxide, titanium oxide, and cerium oxide. In addition, inorganic fine particles may act as an ultraviolet absorber. The size of the inorganic fine particles is not particularly limited, but the average particle diameter is preferably 5 to 200 nm, more preferably 5 to 100 nm, from the viewpoint of scratch resistance, weather resistance and the like. Here, as a method for measuring the average particle diameter, a known method can be used. For example, by observing particles with a transmission electron microscope (TEM) and determining the number average particle size of the particle size distribution therefrom, a method for determining an average particle size using an electron force microscope (AFM), dynamic light It can be measured using a particle size measuring apparatus by a scattering method, for example, “ZETASIZER Nano Series Nano-ZS” manufactured by Malvern. In addition, there is a method of deriving the particle size distribution from the spectrum obtained by the X-ray small angle scattering method using the particle size distribution simulation calculation of the particle. In the present invention, an electron force microscope (AFM) is used. A method of obtaining an average particle diameter using a slag is preferred.

  In addition, zinc oxide, titanium oxide, and cerium oxide preferably have low photocatalytic activity from the viewpoint of suppressing / preventing crack generation. Such inorganic fine particles having low photocatalytic activity are not limited to the following, but a method of coating the surface of the inorganic fine particles with an oxide or hydroxide such as silica or surface treatment (surface coating) with hydrolyzable silane. A method of coating the surface of inorganic fine particles with a hydrolyzate of an alkoxide such as aluminum alkoxide, silicon alkoxide, zirconium alkoxide, tin alkoxide, etc. And a method of increasing the crystallinity by heating the deposited oxide or hydroxide.

  Commercially available products may be used as the inorganic fine particles. Specifically, Nissan Chemical Industries, Ltd. Snowtex-O, OS, OL, methanol-dispersed silica sol, methyl ethyl ketone-dispersed silica sol, etc .; CIK Nanotech Co., Ltd. E88; silica particles manufactured by JGC Catalysts & Chemicals Co., Ltd. can be used.

  The content (in terms of solid content) of the inorganic fine particles in the hard coat layer is not particularly limited, but is preferably 10 to 80% by weight, more preferably 20 to 70% by weight with respect to the hard coat layer. Preferably it is 30 to 60% by weight. By setting the content of the inorganic fine particles in the above range, scratch resistance and weather resistance can be more fully exhibited.

  The hard coat layer may contain an antioxidant in order to prevent deterioration. Thereby, the lower layer (for example, organic-inorganic hybrid layer) can be more effectively protected than the hard coat layer itself and the hard coat layer. Here, the antioxidant is not particularly limited, but it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, or a phosphite-based antioxidant. Here, as the phenol-based antioxidant, the thiol-based antioxidant, and the phosphite-based antioxidant, known antioxidants described in WO 2012/165460, respectively, can be used.

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

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

  Examples of the method for producing the hard coat layer include conventionally known coating methods such as gravure coating, reverse coating, die coating, and bar coating. In addition to applying and coating a predetermined material, various surface treatments and the like may be combined.

  In addition, it is preferable that the thickness of a hard-coat layer is 0.05 micrometer or more and 10 micrometers or less. The thickness of the hard coat layer is more preferably 1 μm or more and 7 μm or less, and particularly preferably 2 μm or more and 5 μm or less. With such a thickness, both hardness and flexibility can be achieved to some extent, and warpage can be prevented from occurring in the film mirror while obtaining sufficient scratch resistance.

(Organic / inorganic hybrid layer)
The organic-inorganic hybrid layer according to the present invention includes an inorganic material (inorganic component) and an organic material (organic component), but has an inorganic material (inorganic component) and a curable resin (organic material, organic component) having a reactive functional group. It is preferable that it is comprised. Since the organic-inorganic hybrid layer contains an organic material (organic component), it is excellent in flexibility (flexibility). Therefore, by providing an organic-inorganic hybrid layer under the hybrid layer having a high hardness (on the light reflection layer side) adjacent to the hard coat layer having a particularly high hardness, the film mirror has a scratch resistance (particularly, a scratch resistance). Excellent balance between abrasion and flexibility.

  An organic / inorganic hybrid coating agent composed of an inorganic component having a reactive functional group and a curable resin is obtained by copolymerizing and crosslinking an inorganic component having a reactive functional group with a radical polymerizable monomer. An organic-inorganic hybrid layer is formed. For this reason, the organic-inorganic hybrid layer according to the present invention is less susceptible to curing shrinkage than the organic / inorganic composite coating agent containing an inorganic component in an organic binder, and exhibits high scratch resistance. it can.

  The inorganic component having a reactive functional group is not particularly limited, but from the viewpoint of curing shrinkage, it preferably contains ultraviolet-reactive silica, and more preferably contains ultraviolet-reactive colloidal silica. Or a commercial item may be used for the inorganic component which has a reactive functional group. Specifically, Dynasylan (registered trademark) (manufactured by EVONIC, silicate), Colcoat (manufactured by Colcoat) and the like can be used.

  Moreover, polyfunctional (meth) acrylate is mentioned as a radically polymerizable monomer. For example, as the bifunctional (meth) acrylate, ethylene oxide-modified diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, bisphenol A ethylene oxide modified diacrylate, dimethylol-tricyclodecane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, epoxy (meth) diacrylate, urethane ( And (meth) diacrylate.

  Also, trifunctional or higher polyfunctional (meth) acrylates include pentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane triethoxy (meth). Examples include acrylate, urethane tri (meth) acrylate, urethane tetra (meth) acrylate, urethane hexa (meth) acrylate, polyester tetra (meth) acrylate, and polyester hexa (meth) acrylate.

  Alternatively, a commercially available product may be used as the curable resin (organic material, organic component). Specifically, SSG (registered trademark) coat (manufactured by Nitto Bo Medical Co., Ltd., organic-inorganic hybrid resin), composeran (produced by Arakawa Chemical Industry Co., Ltd., organic-inorganic hybrid resin), HUV-CMA series (manufactured by Atomics Co., Ltd., organic inorganic) Hybrid resin) can be used.

  Moreover, you may add monofunctional (meth) acrylate suitably in order to adjust the cure shrinkage rate and viscosity in an organic-inorganic hybrid layer, and to improve the solubility of a small amount of additives. Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, methoxypolyethylene (Meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are mentioned.

  The content of the inorganic component having a reactive functional group in the organic / inorganic hybrid coating agent (organic / inorganic hybrid layer) is not particularly limited, but is 5% by weight from the viewpoint of surface hardness, transparency, punching workability, and the like. It is preferably at least 70% by weight, more preferably at least 10% by weight and less than 65% by weight, most preferably at least 15% by weight and less than 60% by weight.

  Alternatively, the organic-inorganic hybrid layer according to the present invention may be formed from a weather resistant hard coat composition described in JP2012-219159A. JP 2012-219159 A aims at a composition that can achieve a long life and scratch resistance as a structural member instead of glass. However, in the examples of the above publication, a thick organic-inorganic hybrid layer is formed on a polycarbonate plate, and even with this description, it is not easily conceived to be applied as it is to the film mirror of the present invention.

  The organic-inorganic hybrid layer preferably contains an ultraviolet absorber. Thereby, lower layers can be more effectively protected than the organic / inorganic hybrid layer itself and the organic / inorganic hybrid layer. For this reason, durability of a film mirror can be improved more. That is, it is preferable that at least one of the hard coat layer and the organic-inorganic hybrid layer further includes an ultraviolet absorber. Here, the ultraviolet absorber is not particularly limited and has the same definition as that described for the hard coat layer, and thus the description thereof is omitted here.

  The organic-inorganic hybrid layer preferably contains inorganic fine particles. Thereby, the hardness and scratch resistance of the organic-inorganic hybrid layer can be further improved. That is, it is preferable that at least one of the hard coat layer and the organic-inorganic hybrid layer further includes inorganic fine particles. Here, the inorganic fine particles are not particularly limited and have the same definitions as those described for the hard coat layer, and thus the description thereof is omitted here.

  Moreover, the organic-inorganic hybrid layer may contain an antioxidant. Here, the antioxidant is not particularly limited and has the same definition as that described for the hard coat layer, and thus the description thereof is omitted here.

  Examples of a method for producing the organic / inorganic hybrid layer include conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method. In addition to applying and coating a predetermined material, various surface treatments and the like may be combined.

  In addition, it is preferable that the thickness of an organic inorganic hybrid layer is 15 micrometers or more and less than 100 micrometers. The thickness of the organic-inorganic hybrid layer is more preferably 20 μm or more and 60 μm or less, and particularly preferably 25 μm or more and 50 μm or less. With such a thickness, both hardness and flexibility can be achieved to some extent, and warpage can be prevented from occurring in the film mirror while obtaining sufficient scratch resistance.

  In the film mirror according to the present invention, a hard coat layer having high hardness (excellent in scratch resistance) but inferior in flexibility and an organic / inorganic hybrid layer inferior in scratch resistance but excellent in flexibility are combined in a balanced manner. A film mirror excellent in both scratch resistance and flexibility is provided. As a result of further intensive studies on the above combination, the present inventor appropriately adjusted the amount of inorganic material (ratio of inorganic components) between the corrosion prevention layer and the hard coat layer to thereby improve scratch resistance (surface protection). It has been found that a good balance between resistance and flexibility and flexibility (flexibility) can be achieved more effectively.

  That is, the ratio of the inorganic component between the corrosion prevention layer and the hard coat layer (hereinafter also simply referred to as “inorganic component ratio”) is preferably 15 to 85% by weight, and preferably 20 to 80% by weight. Is more preferable. By setting the inorganic component ratio in such a range, the balance between scratch resistance (surface protection) and weather resistance and flexibility (flexibility) can be further improved.

  In this specification, the “inorganic component” refers to a substance (material) having a structure in which three or more elements other than carbon such as silicon (Si) and titanium (Ti) are connected. In addition, even if a methyl group or an ethyl group is modified with an element other than carbon such as silicon (Si) or titanium (Ti), the inorganic component is used. On the other hand, the “organic component” refers to a structure in which three or more carbon elements are connected, and is regarded as a carbon component even if Si or N is incorporated in the carbon element. In the present invention, the hard coat layer contains an inorganic component as a main component. On the other hand, since the organic-inorganic hybrid includes both an organic component and an inorganic component, the ratio of the organic component and the inorganic component varies depending on the composition. "Ratio of inorganic components between corrosion prevention layer and hard coat layer (inorganic component ratio) (%)" is the content of inorganic and organic components in each layer existing between the corrosion prevention layer and the hard coat layer. The amount (weight) is measured, the total weight of the inorganic component and the total weight of the organic component are calculated, and the amount is determined according to the following formula (a). In addition, when a light reflection layer is included between the corrosion prevention layer and the hard coat layer, the light reflection layer is not included in the calculation of the inorganic component ratio. Further, in the following formula (a), in calculating the inorganic component ratio, the total weight of the organic component and the inorganic component is determined in consideration of the volume (thickness) of each layer (for example, the organic-inorganic hybrid layer and the hard coat layer). Also good.

(Resin base material)
Various conventionally known resin films can be used as the resin base material. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate (PET), polyester film such as polyethylene naphthalate, polyethylene film, polypropylene film Cellophane, cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene Resin film, polymethyl Down Ten films, polyether ketone films, 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. Of these, a polyester film such as polyethylene terephthalate or an acrylic film is preferably used, and a polyester film such as polyethylene terephthalate is particularly preferable. Here, the resin base material may be manufactured by any method, and may be, for example, a film manufactured by melt casting film formation or a film manufactured by solution casting film formation. .

  Since the resin base material is located farther from the light incident side than the light reflecting layer, it is difficult for ultraviolet rays to reach the resin base material. In particular, when an ultraviolet absorber is contained in a translucent resin layer or the like that is closer to the light incident side than the resin base material, the ultraviolet rays are more difficult to reach the resin base material. Therefore, the resin base material can be used even if it is a resin that easily deteriorates with respect to ultraviolet rays. From such a viewpoint, a polyester film such as polyethylene terephthalate can be used as the resin base material.

  The thickness of the resin base material is not particularly limited, but is preferably an appropriate thickness according to the type and purpose of the resin. The thickness of the resin base material is preferably in the range of 10 to 300 μm, for example, and more preferably 20 to 200 μm.

(Light reflecting layer)
The light reflecting layer is a layer made of metal or the like having a function of reflecting sunlight.

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

  The thickness of the light reflection layer is preferably 10 to 200 nm, more preferably 30 to 150 nm, from the viewpoint of reflectance and the like.

Moreover, a layer made of a metal oxide such as SiO ₂ or TiO ₂ may be provided on the light reflecting layer to further improve the reflectance.

  As a method for forming the light reflecting layer, either a wet method or a dry method can be used. The wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction. On the other hand, the dry method is a general term for a vacuum film-forming method. Specific examples include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, and an ion beam assisted vacuum deposition method. And sputtering method. In particular, a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. For example, in the manufacturing method of the film mirror for solar power generation, it is preferable that it is a manufacturing method which forms a light reflection layer by silver vapor deposition (especially vacuum vapor deposition).

(Anchor layer (primer layer))
The anchor layer can be disposed between the resin substrate and the light reflecting layer. An anchor layer consists of resin and makes a resin base material and a light reflection layer closely_contact | adhere. Therefore, the anchor layer has an adhesion property that allows the resin base material and the light reflection layer to adhere to each other, heat resistance that can withstand heat when the light reflection layer is formed by a vacuum deposition method, and the high reflection that the light reflection layer originally has. Smoothness is required to bring out performance.

  The material (resin material) used for the anchor layer and the method for forming the anchor layer are not particularly limited. For example, in the known literature such as WO 2012/165460 pamphlet (particularly, paragraphs “0209” to “0212”). Similar materials and methods as described can be used.

(Corrosion prevention layer)
The corrosion prevention layer is a resin layer containing a corrosion inhibitor and is preferably adjacent to the light reflection layer. Thereby, corrosion of a light reflection layer, especially silver can be effectively prevented. In order to more effectively suppress and prevent corrosion of the light reflecting layer, the corrosion preventing layer is adjacent to the light incident side of the silver reflecting layer. Alternatively, the corrosion prevention layer is preferably adjacent to both sides of the light reflection layer.

  The corrosion prevention layer may consist of only one layer or may consist of a plurality of layers. The thickness of the corrosion prevention layer is preferably 30 nm to 10 μm, more preferably 50 nm to 5 μm.

  The resin and corrosion inhibitor used in the corrosion prevention layer are not particularly limited, but are known, for example, WO 2012/165460 pamphlet (particularly, paragraphs “0079” to “0095”) such as polyester resin and acrylic resin. The same materials as described in the literature can be used.

  The corrosion prevention layer can be formed by applying and coating these resin materials (binders) on the light reflection layer or the like.

  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 corrosion inhibitor is not particularly limited, and a known corrosion inhibitor can be used. Specifically, amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, compounds having an indazole ring, copper chelate compounds , Thioureas, compounds having a mercapto group, naphthalene compounds, and the like. It is also possible to use a silicon-modified resin. It does not specifically limit as a silicone modified resin. The said corrosion inhibitor may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

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

  As a substance having a pyrrole ring, N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, N-phenyl-3, 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

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

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

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

  Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl. Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5 dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4-phenyl Rumyl imidazole, 4-methyl-5-formyl imidazole, 2-ethyl-4-methyl-5-formyl imidazole, 2-phenyl-4-methyl-4-formyl imidazole, 2-mercaptobenzimidazole, etc., or these Of the mixture.

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

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

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

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

  Examples of the naphthalene type include thionalide.

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 .

(UV absorbing layer)
The ultraviolet absorbing layer is a layer containing an ultraviolet absorber for the purpose of preventing deterioration of the film mirror caused by sunlight or ultraviolet rays. The arrangement of the ultraviolet absorbing layer is not particularly limited, but is preferably provided on the light incident side of the resin base material. Moreover, when a film mirror further has a corrosion prevention layer, it is preferable to provide in the light-incidence side rather than a corrosion prevention layer.

  The ultraviolet absorbing layer may contain a resin as a binder. In this case, the resin is not particularly limited as long as it functions as a binder. 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, polyether ketone, polyether ketone imide, polyamide, fluororesin, Nylon, polymethylmethacrylate, acrylic resin, etc. are mentioned. Of these, polyester and acrylic resins are preferred. In addition, the said resin may be used independently or may be used with the form of a 2 or more types of mixture.

  Further, the ultraviolet absorber is not particularly limited and has the same definition as that described for the hard coat layer, and thus the description thereof is omitted here.

  The thickness of the ultraviolet absorbing layer is not particularly limited, but may be composed of only one layer or a plurality of layers. The thickness of the ultraviolet absorbing layer is preferably 30 nm to 10 μm, and more preferably 50 nm to 5 μm.

(Adhesive layer)
The adhesive layer is not particularly limited as long as it has a function of improving the adhesion between the layers. The adhesive layer may be disposed at any position. Therefore, the adhesive layer is an adhesive layer that adheres to each other, heat resistance that can withstand heat when the silver reflective layer is formed by a vacuum deposition method, etc., and a smooth surface that brings out the high reflective performance that the silver reflective layer originally has. It is preferable to have properties.

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

  When the adhesive layer is a resin, the resin is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness, polyester resin, urethane resin, acrylic resin, melamine Resin, epoxy resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, etc. can be used singly or as a mixed resin. From the point of weather resistance, polyester resin and melamine resin mixed resin 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.

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

(Gas barrier layer)
The gas barrier layer is preferably provided on the light incident side with respect to the light reflecting layer. In particular, it is preferable to provide a gas barrier layer between the resin substrate and the light reflecting layer.

The gas barrier layer is intended to prevent the deterioration of the humidity, particularly the deterioration of the resin base material and each component layer supported by the resin base material due to high humidity, but it has special functions and applications. As long as it has a deterioration preventing function, 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, and still more preferably 0. .2 g / m ² · day or less. In addition, the oxygen permeability of the gas barrier layer is preferably 0.6 ml / m ² / day / atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.

  The material used for the gas barrier layer and the method for forming the gas barrier layer are not particularly limited, but are described in known documents such as WO 2012/165460 pamphlet (particularly, paragraphs “0188” to “0209”). The same materials and methods can be used.

(Adhesive layer)
The adhesive layer has adhesiveness that enables the film mirror to be attached to the support substrate, and the adhesive layer is used to join the film mirror to the support substrate to form a solar power generation reflection device. It is a constituent layer.

  The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used. As the adhesive, for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used. The laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity. Moreover, it is preferable that the thickness of an adhesion layer is the range of about 1-100 micrometers normally from viewpoints, such as an adhesion effect and a drying rate.

  In addition, the film mirror may be provided with the peeling sheet (illustration omitted) which covers the surface on the opposite side to the resin base material in an adhesion layer. When a film mirror has a peeling sheet, after peeling a peeling sheet from an adhesion layer, a film mirror can be affixed on a support base material through an adhesion layer.

  A peeling sheet is a member which covers the surface on the opposite side to the light-incidence side of the adhesion layer in a film mirror.

  For example, when the film mirror is shipped, the release sheet is attached to the adhesive layer, and then the release sheet is released from the adhesive layer of the film mirror, and the film mirror is attached to the support substrate to reflect the solar power generation reflection device. Can be formed.

  The release sheet may be any sheet that can protect the adhesiveness of the adhesive 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 a plastic film or sheet such as a sheet, a fluorine film, a resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., or a metal such as aluminum is applied to the resin kneaded with these. A resin film or sheet subjected to surface processing such as vapor deposition is used.

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

(Film mirror manufacturing method)
A film mirror for solar power generation can be manufactured by appropriately laminating the above-described constituent layers.

  First, a resin base material (for example, a polyethylene terephthalate film produced by melt film formation) is prepared. If necessary, an anchor layer is formed by applying a predetermined resin material on the resin substrate (after application, drying if necessary). Next, a light reflecting layer (for example, a silver reflecting layer) is formed on the resin substrate (or an anchor layer when an anchor layer is provided on the resin substrate) by a method such as vacuum deposition. A corrosion prevention layer is formed on the light reflecting layer by coating. Next, a predetermined organic-inorganic hybrid resin is applied to form an organic-inorganic hybrid layer.

  Next, a hard coat layer forming liquid containing a hard coat material (including an ultraviolet absorber and / or inorganic fine particles if necessary) is applied on the organic-inorganic hybrid layer thus formed (after application). If necessary, it is dried and further cured if necessary) to form a hard coat layer. Here, the solvent that can be used for the preparation of the hard coat layer forming liquid is not particularly limited as long as it can dissolve the hard coat material, and is appropriately selected depending on the type of the hard coat material to be used. Specifically, for example, methyl ethyl ketone (MEK), toluene, xylene, methylene chloride, 1,2-dichloroethane, cyclohexane, ethyl acetate, t-butyl acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl Examples include alcohol, t-butyl alcohol, sec-butyl alcohol butanol, methyl cellosolve, 4-methoxy-4-methyl-2-pentanone, ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, and diethylamine. However, it is not limited to these. These solvents can be used alone or in combination of two or more. The concentration of the hard coat material in the hard coat layer forming liquid is not particularly limited, but is preferably 20 to 40% by weight, more preferably 25 in consideration of ease of application, ease of adjusting a desired thickness, and the like. -35% by weight. The coating method is not particularly limited, and conventionally known coating methods such as a gravure coating method, a reverse coating method, a die coating method, and a bar coating method can be applied. The drying conditions for the coating film of the hard coat layer forming liquid are not particularly limited as long as a sufficient amount of solvent can be evaporated from the coating film (a hard coat layer can be formed). Specifically, the drying temperature is preferably 70 to 100 ° C, more preferably 80 to 90 ° C. The drying time is preferably 0.5 to 3.0 minutes, more preferably 0.5 to 1.5 minutes. In the case where a thermosetting hard coat material is used, the drying and curing can be performed simultaneously.

  Furthermore, a film is formed by coating an adhesive material on the back side of the resin base (the side on which the resin base and the light reflection layer are not formed, respectively) to form an adhesive layer, and covering the adhesive layer with a release sheet. A mirror is manufactured.

  When manufacturing film mirrors having layers other than those described above, the desired film mirrors are manufactured by laminating the constituent layers necessary for each film mirror in a predetermined order on the resin base material or light reflecting layer. Can do. For example, when the anchor coat layer is formed between the resin base material and the light reflecting layer, a predetermined resin material (an anchor coat layer forming liquid containing a predetermined resin material if necessary) is formed on the resin base material. ) Is applied (after application, it is dried if necessary) to form an anchor coat layer. Here, the solvent, drying conditions, and the like that can be used for the preparation of the anchor coat layer forming liquid are not limited. For example, the same description as above can be applied, and thus the description thereof is omitted here. Similarly, when the corrosion prevention layer is formed on the light reflection layer (for example, between the light reflection layer and the organic-inorganic hybrid layer), a resin material containing a corrosion inhibitor on the light reflection layer (necessary) Then, it is possible to form a corrosion prevention layer by applying a corrosion prevention layer forming liquid containing a predetermined resin material and a corrosion inhibitor (after application, drying if necessary). Here, the solvent, drying conditions, and the like that can be used for the preparation of the corrosion-preventing layer forming liquid are not limited. For example, the same description as above can be applied, and thus the description thereof is omitted here. When the film mirror has a gas barrier layer, the gas barrier layer can be formed by subjecting a predetermined layer to a sol-gel method and heating / UV treatment.

  And in the film mirror of the present invention, only the resin base material is a resin film produced by melt film formation, etc., the resin film is not used for the other constituent layers, and sequentially with respect to the resin base material, It is preferable to manufacture a film mirror by repeating film formation by application, coating, vapor deposition, or the like of each constituent layer and laminating predetermined constituent layers. That is, the film mirror manufacturing method of the present invention separately manufactures a resin film having at least a light reflecting layer and a layer (for example, a hard coat layer, an organic-inorganic hybrid layer) disposed on the light incident side, and bonds them. It is preferable not to include a step of bonding with an agent (adhesive layer).

  The film mirror of the present invention has an excellent balance between scratch resistance (particularly, scratch resistance) and flexibility. Specifically, the film mirror of the present invention preferably has a pencil hardness of H to 6H, and more preferably 2H to 4H. In the evaluation of the following examples, the pencil hardness before and after the weather resistance test is preferably in the above range, but the pencil hardness after the weather resistance test is more preferably in the above range.

(Reflector for solar thermal power generation)
The film mirror of the present invention has an excellent balance between scratch resistance (particularly, scratch resistance) and flexibility. For this reason, the film mirror of this invention is used suitably for the solar power generation reflective apparatus. Therefore, this invention also provides the solar power generation reflective apparatus which has the film mirror of this invention.

  The solar power generation reflecting device is a reflecting mirror that includes a film mirror and a self-supporting support base material, and the film mirror is bonded to the support base material via an adhesive layer.

  In addition, the "self-supporting property" as used herein means that the supporting substrate supports the edge portion of the film mirror in a state where the supporting substrate is cut to a size used as a supporting substrate of the solar power generation reflecting 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.

(Supporting substrate)
As a self-supporting support base material, there are one having a pair of metal flat plates and an intermediate layer interposed between the metal flat plates (type A), or one made of a resin material having a hollow structure (type B). It is preferable. As for a specific configuration, self-supporting substrates A and B described in International Publication No. 11/162154 or US Patent Application Publication No. 2013/0114155 can be employed.

(Holding member)
The solar power generation reflection device may have a holding member that holds the reflection device itself.

  The holding member preferably holds the reflecting surface (film mirror) of the solar power generation reflecting device in a state where the sun can be tracked. The form of the holding member is not particularly limited, but for example, a plurality of places on the support base on the back side of the solar power generation reflecting device are formed in a bar shape so that the solar power generating reflection device can hold a desired shape and posture. The form held by a columnar member or a beam-like member is preferable.

  The holding member has a configuration for holding the solar power generation reflecting device in a state in which the sun can be tracked. However, in the case of solar tracking, the holding member may be driven manually, or a separate driving device may be provided to automatically track the sun. It is good also as composition to do.

  The solar power generation reflecting device having such a configuration can be preferably used for the purpose of collecting sunlight.

  When this solar power generation reflector is used, the reflector is shaped like a bowl (semi-cylindrical), and a cylindrical member having fluid inside is provided in the center of the semicircle, and sunlight is collected on the cylindrical member. One mode is a mode in which the internal fluid is heated by light and the heat energy is converted to generate electricity.

  In addition, flat reflectors were installed at multiple locations, and the sunlight reflected by each reflector was collected on one reflector (central reflector) and reflected by the reflector. The form which generate | occur | produces electricity by converting a thermal energy in a power generation part is also mentioned as one form. In particular, in the latter form, since a high regular reflectance is required for the reflection device used, the film mirror for solar power generation of the present invention is particularly preferably used.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by weight” and “part by weight”, respectively.

[Production of reflective film]
A biaxially stretched polyester film (polyethylene terephthalate film, thickness: 150 μm) was used as the resin substrate. On one side of the resin substrate, a polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Co., Ltd.) and a TDI (tolylene diisocyanate) isocyanate (2,4-tolylene diisocyanate) in a resin solid content ratio of 10: 2 (mass ratio) is added, methyl ethyl ketone is added as a solvent, and glycol dimercaptoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) as a corrosion inhibitor is added in an amount of 10% by mass, and coating is performed by gravure coating. Then, a corrosion prevention layer having a thickness (dry film thickness) of 60 nm was formed.

  A silver reflective layer having a thickness of 80 nm was formed by vacuum deposition on the corrosion prevention layer formed as described above. Next, in the formation of the corrosion prevention layer on the silver reflection layer, a corrosion prevention layer was used except that a benzotriazole-based ultraviolet absorber (manufactured by Ciba Japan, Tinuvin 234) was used instead of glycol dimercaptoacetate. In the same manner as in the above, an ultraviolet absorbing layer was formed to obtain a reflective film.

Comparative Example 1
Beam set 577 (Arakawa Chemical Co., Ltd., urethane acrylate) is dissolved in methyl ethyl ketone so that the concentration (solid content concentration) is 20% by weight, and further triazine ultraviolet absorber (BASF, TINUVIN477) is 5% by weight. And coating solution (1) was prepared so that the total solid content was 25% by weight.

  The coating solution (1) thus prepared is applied on the reflective film using an applicator, dried at 100 ° C. for 30 seconds, and output 65 using a UV irradiation device (electrodeless lamp manufactured by Heraeus). %, Conveyance speed: 10 m / min, and an acrylic resin layer having a thickness (dry film thickness; the same applies hereinafter) of 25 μm was formed on the reflective film.

  15 parts by weight of UV-7600B (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, UV curable urethane acrylate resin), 3 parts by weight of IRGACURE 184 (manufactured by BASF, photopolymerization initiator), triazine UV absorber (BASF) 5 parts by weight (manufactured by TINUVIN 477) was added to methyl ethyl ketone so that the total solid content was 30% to prepare a coating solution (2).

  On the acrylic resin layer formed as described above, the coating liquid (2) is applied with a wire bar, dried at 90 ° C. for 50 seconds, and then using a UV irradiation device with an output of 65% and a conveyance speed of 10 m / min. It hardened | cured and formed the hard-coat layer of thickness 5 micrometers on an acrylic resin layer, and produced the sample (1).

  In addition, in this comparative example, it is the content shown by Formula (A), and as can be seen from the structure of this hard coat, the inorganic ratio is 0% by weight.

Comparative Example 2
In Comparative Example 1, SSG (registered trademark) coat HB31BN (manufactured by Nitto Bo Medical Co., Ltd., organic-inorganic hybrid resin) in a ratio of 1 part by weight to 20 parts by weight of beam set 577 (manufactured by Arakawa Chemical Co., Ltd., urethane acrylate) Furthermore, it added so that it might become, and the coating liquid (2) was prepared. In Comparative Example 1, the coating solution (2) was used instead of the coating solution (1).
Next, as a hard coat layer, NP720 (trifunctional polymethylsiloxane hard coat manufactured by Kinken Co., Ltd.) was applied with a wire bar, dried at 90 ° C. for 50 seconds, and the hard coat layer having a thickness of 3 μm was acrylic resin. A sample (2) was produced by forming on the layer.

  In this comparative example, since the inorganic content of HB31BN is 50% by weight, the organic ratio of the organic-inorganic hybrid layer is 98.1%. When the film thickness of the layer is converted, the inorganic content of sample (2) The ratio is 12.4% by weight.

Comparative Example 3
2 parts by weight of SSG (registered trademark) coat HB31BN is added to 40 parts by weight of Dynasylan (registered trademark) 40 (Evolic Corp., ethyl polysilicate), 5 parts by weight of TINUVIN 477 is added, and methyl ethyl ketone is added. The coating solution (3) was prepared so that the total solid content was 40% by weight.

  The coating liquid (3) thus prepared is applied onto the reflective film using a wire bar and dried at 110 ° C. for 2 minutes to form an organic / inorganic hybrid layer having a thickness of 25 μm on the reflective film. did.

  On this organic / inorganic hybrid layer, NP720 was applied with a wire bar, dried at 90 ° C. for 50 seconds, and a hard coat layer having a thickness of 3 μm was formed on the organic / inorganic hybrid layer. Produced.

  In addition, in this comparative example, the inorganic content rate of a hard-coat layer is 100 weight%, the inorganic content rate of an organic-inorganic hybrid layer is 88%, and if it converts it with a film thickness, the inorganic ratio of a sample (3) will be 90% by weight.

Comparative Example 4
In the same manner as in Comparative Example 3, an organic / inorganic hybrid layer having a thickness of 25 μm was formed on the reflective film.

  On the organic-inorganic hybrid layer formed as described above, the coating liquid (2) is applied with a wire bar, dried at 90 ° C. for 50 seconds, and then using a UV irradiation device, the output is 65%, the conveyance speed is 10 m / min. And a hard coat layer having a thickness of 5 μm was formed on the organic-inorganic hybrid layer to prepare a sample (4).

  In addition, in this comparative example, it calculated similarly to the above and the inorganic ratio of the sample (4) was 72 weight%.

Example 1
10 parts by weight of SSG (registered trademark) coat HB31BN (manufactured by Nitto Bo Medical Co., Ltd., organic-inorganic hybrid resin) is added to 7 parts by weight of Dynasylan (registered trademark) 40 (Evolic Inc., ethyl polysilicate). Was dissolved in methyl ethyl ketone, and 5 parts by weight of a zinc oxide ultraviolet absorber (manufactured by Teika Co., Ltd., ZD019) was added to prepare a coating liquid (5) so that the total solid content was 53% by weight.

  The thus prepared coating solution (5) is applied onto the reflective film using a wire bar and dried at 110 ° C. for 2 minutes to form an organic / inorganic hybrid layer having a thickness of 25 μm on the reflective film. did.

  On this organic / inorganic hybrid layer, NP720 (manufactured by Kinken Co., Ltd., trifunctional polysiloxane hard coat) is applied with a wire bar and dried at 90 ° C. for 50 seconds. A sample (5) was produced by forming on the hybrid layer.

  In this example, the organic ratio of the organic-inorganic hybrid layer is 22.7% by weight. When the film thickness of the layer is converted, the inorganic ratio of sample (5) is 80% by weight.

Example 2
In Example 1, in the formation of the organic-inorganic hybrid layer, Dynasylan (registered trademark) 40 was not added, and 5 parts of triazine ultraviolet absorber (BASF, TINUVIN477) was added to 2 parts by weight of SSG (registered trademark) coat HB31BN. Sample (6) was prepared in the same manner as in Example 1 except that the coating solution was prepared by adding parts by weight.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 85.7% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (6) was 23% by weight.

Example 3
In Example 2, in the formation of the organic-inorganic hybrid layer, 1.5 parts by weight of Dynasylan (registered trademark) 40, 4 parts by weight of SSG (registered trademark) HB31BN, and a triazine ultraviolet absorber (manufactured by BASF, TINUVIN477) ) Was added in the same manner as in Example 2 except that a coating solution was prepared by adding 5 parts by weight of sample (7).

  In this example, the organic ratio of the organic-inorganic hybrid layer was 66.6% by weight, and the inorganic ratio of sample (7) was 40% by weight when the film thickness of the layer was converted.

Example 4
In Example 2, in the formation of the organic-inorganic hybrid layer, the amount of Dynasylan (registered trademark) 40 was 7 parts by weight, the amount of SSG (registered trademark) HB31BN was 7 parts by weight, and a triazine ultraviolet absorber (manufactured by BASF). Sample (8) was prepared in the same manner as in Example 2 except that 5 parts by weight of TINUVIN477) was added to prepare a coating solution.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 44.7% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (8) was 60% by weight.

Example 5
In Example 1, in the formation of the organic-inorganic hybrid layer, dyssylan (registered trademark) 40 is 12 parts by weight, SSG (registered trademark) coat HB31BN is 8.6 parts by weight, and a zinc oxide-based ultraviolet absorber (Taika Co., Ltd.). Sample (9) was prepared in the same manner as in Example 1, except that 5 parts by weight of ZD019) was added to prepare a coating solution.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 16.8% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (9) was 85% by weight.

Example 6
In Example 2, in the formation of the organic-inorganic hybrid layer, Dynasylan (registered trademark) 40 was not added, and 5 parts of triazine UV absorber (manufactured by BASF, TINUVIN477) was added to 1 part by weight of SSG (registered trademark) HB31BN. A sample (10) was produced in the same manner as in Example 2 except that the coating solution was prepared by adding parts by weight.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 91.7% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (10) was 18% by weight.

Example 7
Dynasylan (registered trademark) 40 was not added, 10 parts by weight of SSG (registered trademark) coated HB31BN was added, and this was dissolved in methyl ethyl ketone. Manufactured, solvent-dispersed silica particles) was added to prepare a coating solution (6) so that the total solid content was 45% by weight.

  The thus prepared coating solution (6) is applied onto the reflective film using a wire bar and dried at 110 ° C. for 2 minutes to form an organic / inorganic hybrid layer having a thickness of 25 μm on the reflective film. did.

  On this organic / inorganic hybrid layer, NP720 (manufactured by Kinken Co., Ltd., trifunctional polysiloxane hard coat) is applied with a wire bar and dried at 90 ° C. for 50 seconds. A sample (11) was produced by forming on the hybrid layer.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 55.6% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (11) was 50% by weight.

Example 8
In Example 7, in the formation of the organic-inorganic hybrid layer, 3 parts by weight of Dynasylan (registered trademark) 40, 20 parts by weight of SSG (registered trademark) HB31BN, 5 parts by weight of TINUVIN477, and MEK-AC-2140Z A sample (12) was prepared in the same manner as in Example 7 except that 5 parts by weight of the coating solution was added to prepare a coating solution.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 45.5% by weight, and when the film thickness of the layer was converted, the inorganic ratio of sample (12) was 59% by weight.

Example 9
In Example 1, in the formation of the organic-inorganic hybrid layer, Composeran AC601 (manufactured by Arakawa Chemical Industries, Ltd., acrylic resin-silica (4) with respect to 3 parts by weight of Dynasylan (registered trademark) 40 (EVONIC, ethyl polysilicate). Except that 12 parts by weight of a functional) hybrid) and 5 parts by weight of a zinc oxide UV absorber (manufactured by Teika, ZD019) were added and dissolved in methyl ethyl ketone to prepare a coating solution with a total solid content of 35% by weight. Sample (13) was prepared in the same manner as in Example 1.

  In this example, the organic content of the organic-inorganic hybrid layer is 45% by weight because the inorganic content of Compocellan AC601 is 25% by weight. When the film thickness of the layer is converted, the inorganic content of Sample (13) The ratio was 60% by weight.

Example 10
Sample (14) was produced in the same manner as in Example 3, except that the amount of HB31BN added was changed to 10 parts by weight and the amount of TINUVIN 477 was changed to 2.5 parts by weight.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 53.6% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (14) was 52% by weight.

Example 11
A sample (15) was produced in the same manner as in Example 2, except that the amount of HB31BN added was changed to 15 parts by weight and the amount of TINUVIN 477 added was changed to 0.5 parts by weight.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 57.1% by weight, and the inorganic ratio of sample (15) was 54% by weight when the film thickness of the layer was converted.

Example 12
In Example 3, instead of 5 parts by weight of TINUVIN 477, sample (16) was prepared in the same manner as in Example 3 except that 4 parts by weight of a benzotriazole-based ultraviolet absorbent (manufactured by BASF, TINUVIN 928) was used. Produced.

  In this example, the organic ratio of the organic-inorganic hybrid layer was 63.2% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (16) was 43% by weight.

Example 13
In the same manner as in Example 3, an organic / inorganic hybrid layer having a thickness of 25 μm was formed on the reflective film.

  On this organic-inorganic hybrid layer, a mixture of 6 parts by weight of KM-4 (manufactured by JGC Catalysts & Chemicals, Inc., silica particles) with respect to 15 parts by weight of NP720 was prepared and applied at 90 ° C. with a wire bar. The sample was dried for 50 seconds, and a hard coat layer having a thickness of 3 μm was formed on the organic-inorganic hybrid layer to prepare a sample (17).

  In this example, the organic ratio of the organic-inorganic hybrid layer was 66.6% by weight. When the film thickness of the layer was converted, the inorganic ratio of sample (17) was 56.3% by weight.

[Evaluation of film mirror]
The samples (1) to (17) (film mirrors) prepared in Comparative Examples 1 to 4 and Examples 1 to 13 were evaluated as follows, and the results are shown in Table 1 below.

(Measurement of UV cut rate (UV transmittance))
For each sample, a specular photometer “U-4100” manufactured by Shimadzu Corporation was used to measure the regular reflectance at an incident angle of incident light of 5 ° with respect to the normal of the reflecting surface. Evaluation is measured as an average reflectance from 250 nm to 380 nm.

(Measurement of pencil hardness)
Measured according to the standard of JIS K 5600-5-4: 1999. A scratch test of the outermost surface (hard coat layer side) of each sample is performed with a pencil angle of 45 degrees and a load of 500 g. Ranking was performed with the hardness symbol of the pencil that was not damaged more than 4 times out of 5 times. The measurement was made using a pencil hardness meter (model number: 553-M1) manufactured by Yasuda Seiki Seisakusho.

(Measurement of flexibility)
Based on JIS K5600-5-1: 1999, using a 1506 mandrel bending tester (manufactured by Elcometer), the hard coat layer surface is placed outside and the minimum diameter (mm) at which the hard coat layer does not break when bent is measured. did.

(Weather resistance test)
Each sample was allowed to stand for 10 days under the conditions of UV tester (Iwasaki Electric Co., Ltd.) illuminance 100 mW, temperature 60 ° C., humidity 63% RH. The UV cut rate (UV transmittance), pencil hardness and flexibility of each sample after standing for a predetermined period were measured by the same method as described above.

  In Table 1 below, the results before the weather resistance test are referred to as “initial”, and the results after the weather resistance test are referred to as “after test”, respectively.

  As is clear from the results in Table 1 above, the samples (5) to (17) of the examples are compared with the samples (1) to (4) of the comparative examples, and the pencil hardness and flexibility, particularly the weather resistance test. It turns out that it is excellent in the later pencil hardness and flexibility.

  It can be seen that Samples (5) to (17) of Examples 1 to 13 exhibit high hardness and excellent film performance (flexibility) both before and after the weather resistance test. From this, it is suggested that the film mirror of this invention has favorable softness | flexibility as the whole film, maintaining outermost surface high hardness. That is, according to the present invention, it is possible to prevent a decrease in regular reflectance due to deterioration of the silver reflecting layer, and to be lightweight and flexible, to reduce the manufacturing cost and to increase the area and mass production, and to improve the scratch resistance and prevention. Film mirror for solar power generation and solar power generation reflection with excellent weather resistance that can maintain good regular reflectance for sunlight for a long time even if installed in harsh environment for a long time with excellent soiling It is expected that equipment can be provided.

  In contrast, the samples (1) and (2) of Comparative Examples 1 and 2 are considered to be inferior in the properties (weather resistance) after the weather resistance test because the inorganic ratio is low (there are few inorganic materials). . Moreover, in the sample (3) of the comparative example 3, since the inorganic ratio is high on the contrary, since the flexibility is poor, it is considered that the film is broken even after the weather resistance test. Furthermore, from the result of the sample (4) of Comparative Example 4, it is confirmed that the UV curable hard coat material is not preferable in terms of weather resistance.

  The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

1 ... resin base material,
2 ... light reflection layer,
3 ... Organic-inorganic hybrid layer,
4 ... metalloxane-based hard coat layer,
5 ... corrosion prevention layer,
6 ... Adhesive layer,
7: Support base material,
10 ... Film mirror,
20: Reflector for solar thermal power generation.

Claims (8)

A resin mirror and a film mirror provided with a silver reflection layer and a corrosion prevention layer on at least one surface of the resin substrate,
(I) having a hard coat layer containing a material having a metalloxane skeleton in the outermost layer;
(Ii) having an organic-inorganic hybrid layer between the hard coat layer and the silver reflective layer; and (iii) a ratio of the inorganic component between the corrosion prevention layer and the hard coat layer is 15 to 85% by weight. There is a film mirror.   The film mirror of Claim 1 whose ratio of the inorganic component between the said corrosion prevention layer and a hard-coat layer is 20 to 80 weight%.   The film mirror according to claim 1, wherein at least one of the hard coat layer and the organic-inorganic hybrid layer further includes inorganic fine particles.   4. The film mirror according to claim 1, wherein at least one of the hard coat layer and the organic-inorganic hybrid layer further contains an ultraviolet absorber.   The film mirror according to claim 4, wherein the ultraviolet absorber is a triazine ultraviolet absorber or an inorganic ultraviolet absorber.   The film mirror according to any one of claims 1 to 5, wherein the pencil hardness is 2H to 4H. The material having the metalloxane skeleton is represented by the following general formula (A):
^However, X 1, ^{X 2} and ^{X 3} are each independently a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group; m is an integer from 0 to 3000; n is 1 to An integer of 3000; o is an integer of 0 to 3000,
The film mirror of any one of Claims 1-6 which is polysiloxane which has a repeating unit shown by these.   The solar power generation reflective apparatus which has a film mirror of any one of Claims 1-7.