JP2012173379A - Film mirror and reflector for solar thermal power generation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film mirror and a solar thermal power generation device manufactured at high productivity, and to provide the film mirror and the solar thermal power generation device having a high regular reflectance in an initial time, even when being subjected to irradiation of ultraviolet light for a long period in the open air, neither lowering the regular reflectance nor deteriorating adhesion between a silver reflection layer and an adjacent layer.SOLUTION: The film mirror is formed by applying coating liquid including an organic silver complex compound onto a resin base material and calcining it, and having at least a single layer of a silver reflection layer. The film mirror includes a hard coat layer containing a UV absorber at a position separated from the silver reflection layer with respect to the resin base material.

Description

  The present invention relates to a film mirror and a solar power generation reflecting device produced by bonding it to a metal support.

  Since the light reflecting device is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, etc., a plate-like glass mirror has been conventionally used. Plate-shaped glass mirrors are highly durable against UV rays, temperature, and humidity, but they are damaged by external pressure during transportation and after installation, and are heavy in mass. There was a problem that the construction cost was expensive.

  On the other hand, the resin-made reflective sheet has been put into practical use as a reflective sheet for a backlight unit of a liquid crystal display. The problem can be solved.

  Such a resin mirror has high suitability for continuous production with respect to a plate-like glass mirror, and can increase productivity. In particular, as described in Patent Document 1, a method of providing a silver reflective layer by depositing silver by applying a solution of an organic complex salt of silver and precipitating silver by heat treatment to provide a silver reflective layer Further, productivity can be further increased.

  However, when forming a silver reflective layer by a method of precipitating silver from a complex salt of silver, the decomposition of the organic silver complex and the precipitation of silver proceed by heat treatment, but the heat resistance of the base resin is lower than that of glass, The temperature of the heat treatment cannot be increased, and the organic compound remains in the silver reflective layer. When the solar power generation reflector is exposed to ultraviolet rays for a long time outdoors, the remaining organic compound is decomposed and colored, resulting in a decrease in reflectance. Further, since the organic compound in the silver reflective layer is decomposed, there is a problem that the adhesion between the silver reflective layer and the adjacent layer is deteriorated, and the silver reflective layer is further deteriorated.

  On the other hand, a film mirror provided with an ultraviolet reflecting film, a plastic film layer, a metal reflecting layer, and a protective layer in order from the side on which sunlight enters is described in Patent Document 2, and the ultraviolet reflecting film is a plastic film layer formed by exposure to ultraviolet rays. By preventing the coloring and deterioration of the film, the decrease in the reflectance is prevented. However, the formation of such an ultraviolet reflection film has the disadvantages that the number of processes is low, the productivity is low, and the blocking of ultraviolet rays is not sufficient. is there. Patent Document 2 describes an example in which a silver reflective complex solution is applied to form a silver reflective layer by forming a silver reflective layer as a method of forming a silver reflective layer, but reduction using ammoniacal silver nitrate as the silver inorganic complex salt. Glucose is used as an agent, and when such an inorganic complex salt is used, the reaction speed is fast, so that there is a problem that minute irregularities are easily generated in the silver reflection layer, and a silver reflection layer having a high regular reflectance cannot be formed. It was.

Special table 2009-535661 gazette JP 2010-237415 A

  The present inventor examined the deposition of silver from an organic silver complex compound in order to produce a film mirror having a high regular reflectance. However, the organic silver complex remaining after baking or the decomposed organic compound was not exposed to sunlight. It is known that coloring and decomposition by irradiation reduce regular reflectance and adhesion between the silver reflective layer and the adjacent layer, and prevent decline in regular reflectance and adhesion in outdoor exposure. Became an issue.

  It is an object of the present invention to provide a film mirror and a solar thermal power generation apparatus that can be manufactured with high productivity. Furthermore, the initial regular reflectance is high, and regular reflectance is maintained even when exposed to ultraviolet rays for a long time outdoors. It is an object to provide a film mirror and a solar power generation device that do not have a decrease in the thickness and do not have a decrease in the adhesion between the silver reflection layer and the adjacent layer.

  The above object has been achieved by the following means.

  1. In a film mirror having at least one silver reflection layer formed by applying and baking a coating solution containing an organic silver complex compound on a resin substrate, the resin substrate is separated from the silver reflection layer. A film mirror comprising a UV-absorbent-containing hard coat layer at a position.

  2. 2. The film mirror according to 1 above, comprising the resin substrate, the silver reflection layer, the corrosion inhibitor-containing layer, the UV absorber-containing layer, and the UV absorber-containing hard coat layer in this order.

  3. 3. The film mirror according to 1 or 2 above, wherein a molecular weight of the corrosion inhibitor contained in the corrosion inhibitor-containing layer is 800 or less.

  4). 4. The film mirror as described in any one of 1 to 3, wherein the UV absorber-containing hard coat layer contains a triazine-based UV absorber or an inorganic UV absorber.

  5). The UV absorber-containing hard coat layer contains an antioxidant and a resin, and the antioxidant is contained in an amount of 0.1 to 5% by mass based on the resin solid content. 2. A film mirror according to claim 1.

  6). The film mirror according to any one of 1 to 5, wherein the UV absorber-containing hard coat layer contains a triazine UV absorber in an amount of 0.1 to 10% by mass based on the resin solid content. .

  7). The UV absorber-containing hard coat layer contains 1 to 50% by mass of an inorganic UV absorber based on the resin solid content, and the inorganic UV absorber is titanium oxide, zinc oxide, cerium oxide or iron oxide. The film mirror according to any one of 1 to 6, which is characterized in that

  8). 8. The film mirror according to any one of 4 to 7, wherein the inorganic UV absorber is a fine particle having a number average particle diameter of 10 nm to 100 nm.

  9. 9. The film mirror according to any one of 4 to 8, wherein fine particles of the inorganic UV absorber are surface-coated with a substance other than the UV absorber.

  10. 10. The film mirror according to any one of 1 to 9, wherein the UV absorber-containing hard coat layer contains a resin obtained by curing an acrylic UV curable resin.

  11. The film mirror according to any one of 5 to 10, wherein the antioxidant is a hindered amine compound.

  12 The film mirror according to any one of 1 to 11, wherein the silver reflective layer contains silver and an organic silver complex compound.

  13. The solar power generation reflective apparatus formed by bonding the film mirror of any one of said 1-12, and a metal support body through an adhesive layer.

  According to the present invention, the productivity is high, the initial regular reflectance is high, the regular reflectance does not decrease even when exposed to ultraviolet rays for a long time outdoors, and the adhesiveness between the silver reflective layer and the adjacent layer decreases. A film mirror and an apparatus for solar thermal power generation can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The film mirror of the present invention is a film mirror having a silver reflective layer on a resin substrate, and the silver reflective layer is formed by heating and baking a coating film containing an organic silver complex compound, and further UV absorbing. It has an agent-containing hard coat layer.

(Solar thermal power reflector)
The film mirror of the present invention can be preferably used for the purpose of collecting sunlight. Although it can also be used as a mirror for reflecting sunlight with a single film mirror, from the viewpoint of durability, the other side through an adhesive layer coated on the surface opposite to the side having the silver reflecting layer of the resin substrate It is preferable to attach the film mirror on a base material, particularly on a metal base material, and use it as a solar power generation reflection device.

  When used as a solar power generation reflecting device, the reflecting device is shaped like a bowl (semi-cylindrical), and a cylindrical member having fluid inside is provided at the center of the semicircle, and sunlight is condensed on the cylindrical member. The form which heats an internal fluid by this, converts the heat energy, and generates electric power is mentioned as one form. 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, the film mirror of the present invention is particularly preferably used because a high regular reflectance is required for the reflection device used.

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

  For example, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber, etc. are used.

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

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

(Silver reflection layer)
The silver reflective layer is formed by applying and baking a solution containing an organic silver complex compound.

  The ligand that forms the organic silver complex compound is preferably capable of being decomposed, desorbed, or vaporized by firing the organic silver complex compound, and as a result of firing, metallic silver is precipitated.

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

(Organic silver complex compound)
Examples of such organic silver complex compounds are described in, for example, each of publicly known special table 2009-535661, special table 2010-500475, and the like, and a silver compound represented by the following general formula (1): An organic silver complex compound obtained by reacting an ammonium carbamate compound or an ammonium carbonate compound represented by the general formulas (2) to (4) is preferable.

  The organic silver complex compound according to the present invention is contained in a coating solution (also referred to as a silver coating solution composition), and a coating film containing the complex according to the present invention is formed on a support by coating this. . That is, it is preferable to form a silver reflective layer by forming a coating film on a resin substrate using an organic silver complex compound and then baking the coating film at a temperature in the range of 80 to 250 ° C. More preferably, it exists in the range of 100-220, Most preferably, it exists in the range of 120-200 degreeC. If the firing temperature is 100 ° C. or higher, there is little residue other than silver of the organic silver complex, so the scratch resistance after UV irradiation in a hot and humid environment is strong, and the regular reflectance after UV irradiation in a hot and humid environment Is expensive. Moreover, if it is 220 degrees or less, a low-cost resin base material can be used. The heating and baking means for baking is not particularly limited, and any commonly used heating means can be applied. However, the upper limit of the baking temperature is determined by the heat resistance of the resin base material. When PET is used as the resin base material, it is preferably 100 ° C. or lower, but if a resin having high heat resistance such as polyimide is used, 250 ° C. is also possible. It is.

(Coating solution)
The silver coating liquid composition used for forming the highly reflective and highly glossy reflective surface of the present invention contains the above-mentioned organic silver complex compound, and optionally contains a solvent, a stabilizer, and a leveling agent (Leveling). agent), a thin film auxiliary agent, a reducing agent, and an additive for a thermal decomposition reaction accelerator can be contained in the silver coating composition of the present invention.

(Organic silver complex compound)
As the organic silver complex compound, a complex of silver and an ammonium carbamate compound or an ammonium carbonate compound is preferably used because silver can be precipitated simply by baking.

  As a method for producing the complex, a silver compound represented by the following general formula (1) and an ammonium carbamate compound or an ammonium carbonate compound represented by the general formulas (2) to (4) are mixed and reacted. A method is mentioned.

  Hereinafter, the silver compound represented by the following general formula (1) and the ammonium carbamate compound or the ammonium carbonate compound represented by the general formulas (2) to (4) will be described.

General formula (1): Ag _n X

(In the general formulas (1) to (4), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, It is a substituent selected from carboxylate and derivatives thereof, n is an integer of 1 to 4, and R ^{1 to} R ⁶ are independently of each other hydrogen, C1 to C30 aliphatic or fatty acid. These are substituents selected from cyclic alkyl groups, aryl groups or aralkyl groups, alkyl and aryl groups substituted with functional groups, heterocyclic compound groups, polymer compounds and derivatives thereof.
Specific examples of the general formula (1) include, for example, silver oxide, silver thiocyanate, silver sulfide, silver chloride, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, perchlorine. Examples include, but are not limited to, acid silver, silver tetrafluoroborate, silver acetylacetonate, silver acetate, silver lactate, silver oxalate and derivatives thereof.

In the general formulas (2) to (4), R ^{1 to} R ⁶ are specifically, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl , Nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, aryl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxypropyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxy Ethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenedia , Pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and their derivatives, and polymers such as polyarylamine and polyethyleneamine Examples of the compound and derivatives thereof are not limited thereto.

  Examples of the compounds of the general formulas (2) to (4) include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n- Butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-si Noethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridiumethylhexylcarbamate, triethylenediaminiumisopropyl Bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, isopropylammonium bicarbonate, n-butyl Ammonium n-butyl carbonate, isobutylammonium isobutyl carbonate, t-butylammonium t-butyl carbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium 2- Methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecylcarbonate, dioctade Silammonium bicarbonate, methyldecylammonium methyldecylcarbonate, hexamethyleneimineammonium hexamethyleneiminecarbonate, morpholineammonium morpholinecarbonate, benzylammonium benzylcarbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate, pyridium bicarbonate, triethylenediaminium Examples thereof include, but are not limited to, one or a mixture of two or more selected from isopropyl carbonate, triethylenediaminium bicarbonate, and derivatives thereof.

  On the other hand, the kind and production method of the above-mentioned ammonium carbamate or ammonium carbonate compound need not be particularly limited. For example, US Pat. No. 4,542,214 describes that ammonium carbamate compounds can be prepared from carbon dioxide and primary amines, secondary amines, tertiary amines, or at least one of these mixtures. When 0.5 mol of water is further added per 1 mol of the amine, an ammonium carbonate compound is obtained. When 1 mol or more of water is added, an ammonium bicarbonate compound can be obtained. At this time, it is produced directly without using a special solvent at normal pressure or under pressure, or when a solvent is used, alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, etc. Glycols, ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as methyl ethyl ketone, acetone, hydrocarbons such as hexane, heptane, Examples include aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride, or mixed solvents thereof. Is carbon dioxide bubbled in the gas phase? To be able to use the solid phase dry ice, it can be reacted in supercritical (supercritical) state. For the production of the ammonium carbamate or ammonium carbonate derivative used in the present invention, any known method other than the above method may be used as long as the structure of the final substance is the same. That is, it is not necessary to specifically limit the solvent, reaction temperature, concentration or catalyst for production, and the production yield is not affected.

  An organic silver complex compound can be produced by reacting the thus produced ammonium carbamate or ammonium carbonate compound with a silver compound. For example, at least one silver compound represented by the general formula (1), at least one ammonium carbamate or ammonium carbonate derivative represented by the general formulas (2) to (4), and a mixture thereof. In a nitrogen atmosphere at normal pressure or under pressure without using a solvent, or when using a solvent, alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin Glycols such as ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane Of benzene, toluene Aromatic UNA, and chloroform and methylene chloride, and halogen-substituted solvents or a mixed solvent such as carbon tetrachloride can be used.

  For the production of the organic silver complex compound used in the present invention, in addition to the above-described method, after preparing a solution in which the silver compound of the general formula (1) and one or more amine compounds are mixed, carbon dioxide To produce an organic silver complex compound. As described above, the reaction can be performed directly without using a solvent in a normal pressure or pressurized state of a nitrogen atmosphere, or can be performed using a solvent. However, any known method may be used as long as the structure of the final material is the same.

  The method for producing the organic silver complex compound used in the present invention is described in JP-T-2008-530001, and is recognized by the structure of the following general formula (5).

General formula (5): Ag [A] _m
(In General formula (5), A is a compound of General formula (2)-(4), and m is 0.5-1.5.)
(Stabilizer)
On the other hand, examples of the stabilizer include amine compounds such as primary amines, secondary amines, and tertiary amines, ammonium carbamates, ammonium carbonates, ammonium bicarbonate compounds, phosphines, and phosphites. And a phosphorus compound such as phosphate, a sulfur compound such as thiol and sulfide, and at least one mixture thereof. Specific examples of amine compounds include, for example, methyl Amine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octyl Ruamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanol Amine, methoxyethylamine, 2-hydroxypropylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine , Dimethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, Perazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxy Examples include silane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, benzylamine and derivatives thereof, and amine compounds such as polymer compounds such as polyarylamine and polyethyleneimine and derivatives thereof.

  Specific examples of the ammonium carbamate, carbonate, and bicarbonate compound as the stabilizer include ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropyl. Carbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxy Ethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutyl ammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl decyl carbamate, hexamethylene imine ammonium hexamethylene imine carbamate, morpholinium morpholine carbamate, pyri Palladium ethylhexyl carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropylcarbo Nate, isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium Bicarbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, geo Tadecyl ammonium dioctadecyl carbonate, dioctadecyl ammonium bicarbonate, methyl decyl ammonium methyl decyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morpholine carbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbonate, Examples include pyridium bicarbonate, triethylenediaminium isopropyl carbonate, triethylenediaminium bicarbonate, and derivatives thereof.

As the phosphorus compounds of the general formula _R 3 P, include a phosphorus compound represented by _{(RO) 3} P or _(RO) 3 PO. Here, R represents an alkyl or aryl group having 1 to 20 carbon atoms, and specific examples include tributylphosphine, triphenylphosphine, triethyl phosphite, triphenyl phosphite, dibenzyl phosphate, triethyl phosphate and the like.

  Specific examples of the sulfur compound include butanethiol, n-hexanethiol, diethyl sulfide, tetrahydrothiophene, aryl disulfide, 2-mercaptobenzoazole, tetrahydrothiophene, and octylthioglycolate.

  The amount of such a stabilizer used is not particularly limited as long as it matches the ink characteristics of the present invention. However, the content is preferably 0.1% to 90% in terms of molar ratio with respect to the silver compound.

(Thin film adjuvant)
Moreover, as a thin film adjuvant, an organic acid and an organic acid derivative, or a mixture of at least one or more thereof can be used. Specifically, for example, acetic acid, butyric acid (valeric acid), pivalic acid (pivalic acid), hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid ( Lauric acid), stearic acid, naphthalic acid, and the like. Specific examples of organic acid derivatives include ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, and ammonium maleate. Organic acid ammonium salts such as ammonium oxalate and ammonium molybdate, Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, Os, I , Manganese oxalate, gold acetate, palladium oxalate, silver 2-ethylhexanoate containing metals such as Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th, Examples thereof include organic acid metal salts such as silver octanoate, silver neodecanoate, cobalt stearate, nickel naphthalate, and cobalt naphthalate. Although the usage-amount of the said thin film adjuvant is not specifically limited, 0.1-25% is preferable by molar ratio with respect to an organic silver complex compound.

(Reducing agent)
Examples of the reducing agent include Lewis acid or weak Bronsted acid, and specific examples thereof include hydrazine, hydrazine monohydrate, acetohydrazide, sodium borohydride or potassium borohydride, dimethylamine borane, Amine compounds such as butylamine borane, metal salts such as ferrous chloride and iron lactate, hydrogen, hydrogen iodide, carbon monoxide, aldehyde compounds such as formaldehyde, acetaldehyde and glyoxal, methyl formate, butyl formate, triethyl Examples thereof include a mixture of at least one formic compound such as o-formic acid, at least one reducing organic compound such as glucose, ascorbic acid, and hydroquinone.

  Specific examples of the thermal decomposition reaction accelerator include, for example, ethanolamine, methyldiethanolamine, triethanolamine, propanolamine, butanolamine, hexanolamine, hydroxyalkylamines such as dimethylethanolamine, piperidine, and N-methylpiperidine. , Piperazine, N, N'-dimethylpiperazine, 1-amino-4methylpiperazine, pyrrolidine, N-methylpyrrolidine, amine compounds such as morpholine, acetone oxime, dimethylglyoxime, 2-butanone oxime, 2,3-butane Alkyl oximes such as dione monooxime, glycols such as ethylene glycol, diethylene glycol, and triethylene glycol, methoxyethylamine, ethoxyethylamine, methoxypropyl Alkoxyalkylamines such as ruamine, alkoxyalkanols such as methoxyethanol, methoxypropanol and ethoxyethanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ketone alcohols such as acetol and diacetone alcohol, Examples thereof include hydric phenol compounds, phenol resins, alkyd resins, pyrroles, and oxidatively polymerizable resins such as ethylenedioxythiophene (EDOT).

  In addition, a solvent may be required for adjusting the viscosity of the silver coating solution composition or for smooth thin film formation. Examples of the solvent that can be used in this case include water, methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, Ethyl hexyl alcohol, alcohols such as terpineol, ethylene glycol, glycols such as glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, acetates such as ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, diethyl Ethers such as ether, tetrahydrofuran and dioxane, methyl ethyl ketone, acetone, dimethylformamide, ketones such as 1-methyl-2-pyrrolidone, hexane, Hydrocarbons such as tan, dodecane, paraffin oil, mineral spirits, aromatics such as benzene, toluene, xylene, and halogen-substituted solvents such as chloroform, methylene chloride, carbon tetrachloride, acetonitrile, dimethyl sulfoxide, or these Or a mixed solvent thereof can be used.

(UV absorber-containing hard coat layer)
In the film mirror for solar power generation of the present invention, a UV absorber-containing hard coat layer is provided as the outermost layer. The UV absorber-containing hard coat layer according to the present invention contains a UV absorber, has high performance for preventing scratches and shielding ultraviolet rays, and can be easily formed.

  The UV absorber of the UV absorber-containing hard coat layer prevents the ultraviolet rays from reaching the silver reflecting layer by blocking the ultraviolet rays. This prevents the organic compound remaining in the silver reflecting layer from being decomposed and colored, and the adhesiveness between the silver reflecting layer and the adjacent layer from being lowered.

  The thickness of the UV absorber-containing hard coat layer is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoint of ultraviolet absorption and the like.

  The UV absorber-containing hard coat layer does not deteriorate the ability to absorb ultraviolet rays even when irradiated with ultraviolet rays for a long time, and the binder resin of the UV absorber-containing hard coat layer is oxidatively cleaved by ultraviolet rays. It is preferable to contain a triazine-based UV absorber or an inorganic UV absorber because of its high ability to prevent the above. Further, the UV absorber-containing hard coat layer contains both a triazine-based UV absorber and an inorganic UV absorber, so that the functions of preventing the oxidative cleavage of the resin and preventing the coloring and corrosion of the silver reflecting layer are long. It is preferable because the period can be maintained.

  The UV absorber-containing hard coat layer is prepared by UV curing or thermosetting using, for example, an acrylic resin, a urethane resin, a melamine resin, an epoxy resin, an organic silicate compound, a silicone resin, or the like as a binder. be able to. In particular, in the present invention, in order to avoid the deterioration of the planarity due to heat of the resin base material, it is preferable to prepare by UV curing. In particular, in the present invention, it is preferable to use an acrylic UV curable resin in terms of hardness and durability.

  The UV absorber-containing hard coat layer may contain a thermoplastic resin in addition to a resin produced by UV curing or thermosetting.

  In the UV absorber-containing hard coat layer, the resin solid content is a solid resin contained in the UV absorber-containing hard coat layer and a polymerizable component that becomes a solid resin by UV curing or heat curing. The polymerizable component means a polymerizable monomer or oligomer.

(Acrylic UV curable resin)
The acrylic resin preferably used as a binder for the UV absorber-containing hard coat layer is preferably formed by curing an acrylic UV curable resin with ultraviolet rays.

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

  Examples of the polyfunctional acrylate include trimethylolpropane tri (meth) acrylate, trimethylolpropane tris (hydroxyethyl (meth) acrylate), tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri ( Examples include (meth) acrylate resins mainly composed of (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyfunctional urethanized (meth) acrylate, and the like.

  Here, the polyfunctional urethanized (meth) acrylate is, for example, a polyisocyanate having at least two isocyanato groups (—NCO) in the molecule, such as isophorone diisocyanate or hexamethylene diisocyanate, and trimethylolpropane di ( A urethane bond and at least two compounds obtained by addition reaction of a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule, such as (meth) acrylate and pentaerythritol tri (meth) acrylate It is a compound having a (meth) acryloyl group.

  The said polyfunctional acrylate can be used individually or in mixture of 2 or more types. Moreover, it is also possible to combine and use the polyfunctional (meth) acrylate which does not have a urethane bond as mentioned above in polyfunctional urethanized (meth) acrylate.

  What is marketed can be used suitably as said polyfunctional acrylate. Specifically as a commercial item of polyfunctional acrylate, Kayalad DPHA (made by Nippon Kayaku Co., Ltd.), Kayalad DPCA-20 (made by Nippon Kayaku Co., Ltd.), Kayrad DPCA-30 (Nippon Kayaku Co., Ltd.) )), Kayrad DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad D-310 (manufactured by Nippon Kayaku Co., Ltd.), Kayrad D-330 (Manufactured by Nippon Kayaku Co., Ltd.), Kayalad PET-30 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad GPO-303 (manufactured by Nippon Kayaku Co., Ltd.), Kayrad TMPTA (manufactured by Nippon Kayaku Co., Ltd.), Kayarad THE-330 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-315 (manufactured by Toagosei Co., Ltd.), Aronix M-325 (亞 made of synthetic Co., Ltd.), and the like.

  The UV curable resin as described above is usually used by mixing with a photopolymerization initiator. As the photopolymerization initiator, for example, commercially available products such as Irgacure 907 (manufactured by BASF Japan), Irgacure 184 (manufactured by BASF Japan), and Lucillin TPO (manufactured by BASF Japan) are preferably used. Can be used.

  Further, from the viewpoint of obtaining a UV absorber-containing hard coat layer having a sufficiently high hardness and capable of sufficiently suppressing curling due to curing shrinkage, silica fine particles may be added to the UV curable resin. In this case, examples of the silica fine particles include powdery silica and colloidal silica, and those having an average particle diameter in the range of 0.01 to 20 μm are preferably used. Further, the silica fine particles are preferably those that do not affect the light transmittance of the hard coat film, and for that purpose, the primary particle diameter is preferably in the range of 10 to 350 nm, and in the range of 10 to 50 nm. More preferably, it is within. The average particle size of the silica fine particles described above can be measured, for example, by observing with a transmission electron microscope, and the primary particle size of the silica fine particles is, for example, dispersed in a solvent such as isopropyl alcohol, The dispersion can be measured by a Coulter particle size distribution measurement method, a laser diffraction scattering method, a dynamic light scattering method, or the like. Among these, the Coulter particle size distribution measurement method is general.

The shape of the silica fine particles may be spherical, hollow, porous, rod-like, plate-like, fiber-like, or indefinite, but in order to disperse the particles appropriately without agglomerating in the ultraviolet curable resin. Is preferably spherical. Further, from the viewpoint of maintaining the hardness and flatness of the UV absorber-containing hard coat layer 3, it is preferable that the specific surface area of the silica fine particles is in the range of 0.1~3000m ² / g, more ^{1 m} 2 / g above, especially ^{10 m} 2 / g or more, more preferably 1500 m ² / g or less.

  Such silica fine particles are also commercially available. Examples of commercially available silica fine particles include methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.), IPA-ST (manufactured by Nissan Chemical Industries, Ltd.), MEK-ST (manufactured by Nissan Chemical Industries, Ltd.). ), NBA-ST (manufactured by Nissan Chemical Industries, Ltd.), XBA-ST (manufactured by Nissan Chemical Industries, Ltd.), DMAC-ST (manufactured by Nissan Chemical Industries, Ltd.), ST-UP (Nissan Chemical Industries, Ltd.) ST-OUP (Nissan Chemical Industry Co., Ltd.), ST-20 (Nissan Chemical Industry Co., Ltd.), ST-40 (Nissan Chemical Industry Co., Ltd.), ST-C (Nissan Chemical Industry) ST-N (manufactured by Nissan Chemical Industries, Ltd.), ST-O (manufactured by Nissan Chemical Industries, Ltd.), ST-50 (manufactured by Nissan Chemical Industries, Ltd.), ST-OL (Nissan) Chemical Industry Co., Ltd.).

  Examples of powdered silica include Aerosil 130 (manufactured by Nippon Aerosil Co., Ltd.), Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.), Aerosil 380 (manufactured by Nippon Aerosil Co., Ltd.), Aerosil TT600 (manufactured by Nippon Aerosil Co., Ltd.). ), Aerosil OX50 (produced by Nippon Aerosil Co., Ltd.), Sildex H31 (produced by Asahi Glass Co., Ltd.), Sildex H32 (produced by Asahi Glass Co., Ltd.), Sildex H51 (produced by Asahi Glass Co., Ltd.), Sildex H52 (produced by Asahi Glass Co., Ltd.) Asahi Glass Co., Ltd.), Sildex H121 (Asahi Glass Co., Ltd.), Sildex H122 (Asahi Glass Co., Ltd.), E220A (Nihon Silica Industry Co., Ltd.), E220 (Nihon Silica Industry Co., Ltd.) , Silicia 470 (manufactured by Fuji Silysia Co., Ltd.), SG flake (manufactured by Nippon Sheet Glass Co., Ltd.), and the like.

(Triazine UV absorber)
The triazine-based UV absorber is represented by the following general formula (I).

General formula ^{(I) Q 1} -Q 2 -OH
In the formula, Q ¹ represents a 1,3,5-triazine ring. Q ² represents an aromatic ring, preferably a benzene ring.

  More preferred as the general formula (I) is a compound represented by the following general formula (IA).

In the formula, R ¹ is an alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenyl group, a hydroxy group, and 1 carbon atom. to 18 alkoxy groups, cycloalkoxy group having a carbon number of 5-12, an alkenyloxy group having 3 to 18 carbon atoms, a halogen ^{atom, -COOH, -COOR 4, -O-} CO-R 5, -O-CO _{^{-O-R 6, -CO-NH}} 2, -CO-NHR 7, -CO-N (R 7) (R 8), CN, NH 2, NHR 7, -N (R 7) (R 8), _{-NH-CO-R 5,} a phenoxy group, a phenoxy group substituted with an alkyl group having 1 to 18 carbon atoms, phenyl - alkoxy group having 1 to 4 carbon atoms, bicycloalkyl cycloalkoxy group having 6 to 15 carbon atoms, 6 to 15 carbon atoms A bicycloalkylalkoxy group, a bicycloalkenylalkoxy group having 6 to 15 carbon atoms, or an alkyl group having 1 to 18 carbon atoms substituted with a tricycloalkoxy group having 6 to 15 carbon atoms; hydroxy group, 1 carbon atom An -4 alkyl group, an alkenyl group having 2 to 6 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms substituted with -O-CO-R ⁵ ; a glycidyl group; -CO-R ⁹ or -SO ₂ or represents -R ^10; or R ¹ is one or more oxygen atoms in interrupted and / or hydroxy group, a phenoxy group or has been carbon atoms 3 to 50 substituted with an alkyl phenoxy group having a carbon number of 7 to 18 or an alkyl group; or ^{R 1} is ^{_{-A; -CH 2 -CH (XA)}} -CH 2 -O-R 12; -CR 13 R '13 - (CH 2) _{^{-X-A; -CH 2 -CH (}} OA) -R 14; -CH 2 -CH (OH) -CH 2 -XA;

_{^{-CR 15 R '15 -C (=}} CH 2) -R "15; -CR 13 R' 13 - (CH 2) m -CO-X-A; -CR 13 R '13 - (CH 2) m - CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ or —CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ (wherein A represents —CO represents a ^{-CR 16 = CH-R 17.} ) represents one of definitions represented by.

R ² is independently of each other an alkyl group having 6 to 18 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; COOR ₄ ; CN; —CO—R ⁵ ; a halogen atom; a trifluoromethyl group; —O—R ³ is represented.

R ³ represents the definition given for R ¹ .

R ⁴ represents an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; Or R ⁴ may be interrupted by one or more —O—, —NH—, —NR ⁷ —, —S— and substituted with OH, a phenoxy group or an alkylphenoxy group having 7 to 18 carbon atoms; It represents a good alkyl group having 3 to 50 carbon atoms.

R ⁵ is H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; A bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkenyl group having 6 to 15 carbon atoms; and a tricycloalkyl group having 6 to 15 carbon atoms.

R ⁶ is H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; To express.

R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 12 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a dialkylaminoalkyl group having 4 to 16 carbon atoms; or the number of carbon atoms Represents a cycloalkyl group having 5 to 12; or R ⁷ and R ⁸ together represent an alkylene group having 3 to 9 carbon atoms, an oxaalkylene group having 3 to 9 carbon atoms, or an aza having 3 to 9 carbon atoms. Represents an alkylene group.

R ⁹ is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a phenyl group; a cycloalkyl group having 5 to 12 carbon atoms; a phenylalkyl group having 7 to 11 carbon atoms; A bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkylalkyl group having 6 to 15 carbon atoms, a bicycloalkenyl group having 6 to 15 carbon atoms; or a tricycloalkyl group having 6 to 15 carbon atoms.

R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms; a phenyl group; a naphthyl group; or an alkylphenyl group having 7 to 14 carbon atoms.

R ¹¹ is independently of each other H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a halogen atom; Represents an alkoxy group of ˜18.

R ¹² represents an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 3 carbon atoms. Represents a phenyl group substituted 1 to 3 times with an alkenoxy group of ˜8, a halogen atom or a trifluoromethyl group; or a phenylalkyl group of 7 to 11 carbon atoms; a cycloalkyl group of 5 to 12 carbon atoms; A tricycloalkyl group having 6 to 15 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkylalkyl group having 6 to 15 carbon atoms; a bicycloalkenylalkyl group having 6 to 15 carbon atoms; It represents R ^5; or ^{R 12} is one or more -O -, - NH -, - NR 7 -, - and interrupted by S- OH, phenoxy or -C 7-18 Alkylphenoxy may be substituted with a group, an alkyl group having a carbon number of 3 to 50.

R ¹³ and R ′ ¹³ each independently represent H; an alkyl group having 1 to 18 carbon atoms; a phenyl group.

R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a phenyl group; a phenyl-alkyl group having 1 to 4 carbon atoms.

R ¹⁵ , R ′ ¹⁵ and R ″ ¹⁵ each independently represent H or CH ₃ .

R ¹⁶ represents H; —CH ₂ —COO—R ⁴ ; an alkyl group having 1 to 4 carbon atoms; or CN.

R ¹⁷ represents H; —COOR ⁴ ; an alkyl group having 1 to 17 carbon atoms; or a phenyl group.

X represents —NH—; —NR ⁷ —; —O—; —NH— (CH ₂ ) _p —NH—; or —O— (CH ₂ ) _q —NH—.

  The index m represents the number 0 to 19; n represents the number 1 to 8; p represents the number 0 to 4; and q represents the number 2 to 4.

However in the general formula the general formula ^(I-A), at least one of R 1, ^{R 2} and ^{R 11} includes two or more carbon atoms.

  The use amount of the triazine-based UV absorber is preferably 0.1 to 10% by mass with respect to the resin solid content of the UV absorber-containing hard coat layer. If it is 10 mass% or less, adhesiveness is favorable, and if it is 1 mass% or more, the deterioration by sunlight can be suppressed strongly.

(Inorganic UV absorber)
The inorganic UV absorber is preferably a metal oxide pigment, and when dispersed in an acrylic resin at a concentration of 20% by mass or more to form a film having a thickness of 6 μm, a UV-B region (290-320 nm) region. It is a compound provided with the function which makes the light transmittance in 10% or less. The inorganic UV absorber applicable to the present invention is particularly preferably selected from titanium oxide, zinc oxide, iron oxide, cerium oxide or a mixture thereof.

  Further, from the viewpoint of improving the transparency of the inorganic UV absorber-containing layer, the number average particle diameter is preferably an average basic particle diameter between 5 nm and 150 nm, particularly preferably an average between 10 nm and 100 nm. Metal oxide particles having a basic particle size and a maximum particle size distribution of 150 nm or less. Such coated or uncoated metal oxide pigments are described in more detail in patent application EP-A-0 518 773.

  Examples of the inorganic UV absorber include Sicotrans Red L2815 (iron oxide; manufactured by BASF Japan Ltd.), CeO-X01 (cerium oxide; manufactured by Iox Corporation), NANOFINE-50 (zinc oxide; manufactured by Sakai Chemical Industry Co., Ltd.). STR-60 (titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.), CM-1000 (iron oxide chemilite industry Co., Ltd.), CERIGUARD S-3018-02 (cerium oxide manufactured by Daito Kasei Kogyo Co., Ltd.), MZ-300 ( Zinc oxide (Taika Co., Ltd.), MT-700B (Titanium oxide (Taika Co., Ltd.)) and the like are commercially available.

  The particle size of the inorganic UV absorber can be measured by LB-550 (Horiba, Ltd.) which is a dynamic light scattering particle size distribution measuring device, and the number average particle size can be calculated from the output of the measurement result. Can be sought.

  The amount of the inorganic UV absorber used is preferably 1 to 50% by mass, more preferably 5 to 25% by mass, and most preferably 10 to 20% by mass with respect to the resin solid content of the UV absorber-containing hard coat layer. . If it is 50 mass% or less, adhesiveness will be favorable, and if it is 1 mass% or more, degradation by sunlight can be suppressed strongly.

  When the inorganic UV absorber is used in combination with the organic UV absorber, the amount of the inorganic UV absorber used is 3 to 20% by mass, preferably 5 to 5%, based on the resin solid content of the UV absorber-containing hard coat layer. The amount of the organic UV absorber used is 0.1 to 10% by mass, preferably 0.5 to 5% by mass. When an inorganic UV absorber and an organic UV absorber are used in combination within the above-mentioned range of use, the transparency of the UV absorbing layer is high and the weather resistance is also good.

(Surface coating)
In the present invention, from the viewpoint of suppressing the oxidative degradation action of the adjacent resin due to the photocatalytic ability of the inorganic oxide, the inorganic UV absorber is surface-coated with a coating layer, and the number average particle size (including the coating layer) is Inorganic UV absorber fine particles of 10 nm or more and 100 nm or less are preferable. Further, since the coating layer has an effect of improving the dispersibility of the inorganic UV absorber particles, it is still preferable to have the coating layer. The coating layer mentioned here is amino acid, beeswax, fatty acid, fatty alcohol, anionic surfactant, lecithin, sodium salt of potassium, zinc salt, iron salt or aluminum salt, metal alkoxide (titanium or aluminum) , Containing compounds such as polyethylene, silicone, protein (collagen, elastin), alkanolamine, silicon oxide, metal oxide or sodium hexametaphosphate, one of chemical, electronic, mechanochemical or mechanical It can be provided on the surface of the inorganic UV absorber by a plurality of means.

(Antioxidant)
Moreover, in order to prevent the adhesiveness at the interface between the UV absorber-containing hard coat layer and the adjacent resin layer from being deteriorated by sunlight irradiation, the UV absorber-containing hard coat layer may contain an antioxidant. preferable.

  The antioxidant applicable to the present invention can be selected from the group of antioxidants such as hindered phenol compounds, hindered amine compounds, and phosphorus compounds, and among them, hindered amine compounds are preferable.

  The antioxidant is preferably contained in an amount of 0.1 to 5% by mass with respect to the total mass of the UV absorber-containing hard coat layer. If it is 0.1% by mass or more, oxidative cleavage of the resin chain and decomposition of the UV absorber can be suppressed, and if it is 5% by mass or less, the adhesion is good.

(Hindered phenolic compounds)
Specific examples of the hindered phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate and n-octadecyl 3- (3,5-di-t-butyl. -4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3 , 5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t-butyl -4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, Utadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n -Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n- Octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2- Hydroxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t-butyl) 4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 2- (2-stearoyloxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl) -4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-tert-butyl-4-hydro Cyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate-2,3-bis- (3 5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol tetrakis- [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis- {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ruethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) ) Propionate, 2-stearoyloxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t- Butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinname) Included). The phenol compound of the above type is commercially available from BASF Japan, for example, under the trade names “IRGANOX1076” and “IRGANOX1010”.

(Hindered amine compounds)
Specific examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6- Tramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, and the like.

  Further, it may be a polymer type compound. As specific examples, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, di Polycondensate of butylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3 -Tetramethylbutyl) amino-1,3,5-tri Gin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], Between 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine Polycondensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6 , 6-tetramethyl-4-piperidyl) imino]], etc., high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton; dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine ester Polymer with diol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) (Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like, and the like are exemplified by compounds in which a piperidine ring is bonded through an ester bond, but the present invention is not limited thereto. It is not a thing.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, etc. Those having a molecular weight (Mn) of 2,000 to 5,000 are preferred.

  The above type of hindered amine compounds are commercially available from BASF Japan, for example, under the trade names of “TUNUVIN 144” and “TUNUVIN 770” and ADEKA Corporation under the name “ADK STAB LA-52”.

  The hindered amine compound is preferably contained in an amount of 0.1 to 5% by mass with respect to the total mass of the UV absorber-containing hard coat layer. If it is 0.1% by mass or more, oxidative cleavage of the resin chain and decomposition of the UV absorber can be suppressed, and if it is 5% by mass or less, the adhesion is good.

(Phosphorus compounds)
Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-). t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine Monophosphite compounds such as pin and tridecyl phosphite; 4,4'-butylidene-bis (3-methyl-6-t-butyl) Diphosphite compounds such as phenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); triphenylphosphonite, tetrakis (2,4- Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) [1,1-biphenyl]- Phosphonite compounds such as 4,4'-diylbisphosphonite; phosphinite compounds such as triphenylphosphinite and 2,6-dimethylphenyldiphenylphosphinite; triphenylphosphine and tris (2,6-dimethoxyphenyl) Phosphine compounds such as phosphine; and the like.

  Phosphorus compounds of the above type are, for example, from Sumitomo Chemical Co., Ltd., “Sumizer GP”, from ADEKA Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, BASF Japan ) From “IRGAFOS P-EPQ” and “GSY-P101” from Sakai Chemical Industry Co., Ltd.

(UV absorber containing layer)
By providing a UV absorber-containing layer between the UV absorber-containing hard coat layer and the silver reflecting layer, it is possible to reduce the ultraviolet rays reaching the silver reflecting layer and improve the durability of the ultraviolet blocking ability, Scratch resistance after UV irradiation in a hot and humid environment can be increased, and regular reflectance after UV irradiation in a hot and humid environment can be increased.

  The UV absorber-containing layer preferably contains the triazine-based UV absorber or the inorganic UV absorber in the same manner as the UV absorber-containing hard coat layer.

(Corrosion inhibitor containing layer)
The corrosion inhibitor-containing layer is preferably provided adjacent to the silver reflective layer. The corrosion inhibitor contains a corrosion inhibitor. The molecular weight of the corrosion inhibitor is preferably 800 or less. By adding such a low molecular weight corrosion inhibitor, the corrosion inhibitor is likely to move to the interface with the silver reflection layer, and the corrosion prevention function is considered to be improved, thereby suppressing deterioration. .

  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 content of the corrosion inhibitor is preferably in the range of 0.01 to 1.0 g / m ² although the optimum amount varies depending on the compound used.

<Corrosion inhibitor>
The corrosion inhibitor preferably has an adsorptive group for silver.

  Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole Desirably, the compound is selected from a compound having a ring, copper chelate compounds, thioureas, a compound having a mercapto group, at least one naphthalene-based compound, or a mixture thereof.

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

  Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, and N-phenyl-3. , 4-diformyl-2,5-dimethylpyrrole, 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) benzo A triazole etc. or these mixtures are mentioned.

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

  Examples of 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- Formylimidazole, 4-methyl-5-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methyl-4-formylimidazole, 2-mercaptobenzimidazole, etc., or These mixtures are mentioned.

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

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

  Examples of the naphthalene type include thionalide.

(Resin base material)
The substrate of the present invention is resinous, and a conventionally known resin film can be used as the substrate.

  For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, an acrylic film, and a polyimide film or the like.

  Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable. In particular, it is preferable to use a polyester film or a cellulose ester film, and it may be a film manufactured by melt casting or a film manufactured by solution casting.

  Moreover, when the baking temperature for depositing silver is high, it is preferable that a resin base material is a polyimide film.

  It is important that the resin base material is low in cost, and a PET film is preferable from the viewpoint of cost and heat resistance.

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

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.

(Preparation of silver coating solution composition)
In a 500 ml Schlenk flask equipped with a stirrer, 65.0 g (215 mmol) of 2-ethylhexylammonium 2-ethylcarbamate was dissolved in 150.0 g of isopropanol, and then 20.0 g (86.2 mmol) of silver oxide. Was added and reacted at room temperature. The reaction solution was initially reacted with a black suspension (Slurry), and as the complex compound was formed, it was observed that the color gradually faded and changed to transparent. Solution was obtained. To this solution was added 2.5 g of 2-hydroxy-2-methylpropylamine as a stabilizer, 85.0 g of n-butanol and 50.0 g of amyl alcohol as a solvent and stirred, and then a 0.45 micron membrane filter. As a result of filtering and thermal analysis (TGA) using a (membrane) filter, a silver coating liquid composition having a silver content of 4.87% by mass was produced.

《Preparation of solar power reflectors》
[Preparation of Sample 1: Example 1]
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 100 μm) was used as the resin substrate. On one side of the polyethylene terephthalate film, Esper 9940A (manufactured by Hitachi Chemical Co., Ltd., polyester resin), MM-A (manufactured by Panasonic Electric Works Co., Ltd., melamine resin), tolylene diisocyanate (manufactured by Mitsui Chemicals Fine Co., Ltd., diisocyanate crosslinking) Agent), hexamethylene diisocyanate (HMDI) (manufactured by Mitsui Chemicals Fine Co., Ltd.) in a resin solid content ratio of 20: 1: 1: 2: is coated by a gravure coating method and has a thickness of 0.1 μm. An anchor layer was formed. On the anchor layer, the silver coating liquid composition was applied so that the film thickness of the silver after heat drying was 80 nm, and then heat-dried at 100 ° C. for 3 minutes in a dry oven to form a silver reflective layer. .

Subsequently, vinyl roll 92T (made by Showa Polymer Co., Ltd.), which is an acrylic resin adhesive, is coated as an adhesive layer on the silver reflective layer with a thickness of 10 μm, and the acrylic resin contains a UV absorber on the adhesive layer. A film (KORAD CLRAR05005, manufactured by Polymer Excluded Products) 50 μm was laminated. Subsequently, Tinuvin 477 (manufactured by BASF Japan) is used as a triazine-based UV absorber on Rioduras LCH (UV curable acrylic resin; manufactured by Toyo Ink) as a UV absorber-containing hard coat layer on the acrylic resin film. 0.05% by mass, zinc oxide NANOFINE-50 (manufactured by Sakai Chemical Industry Co., Ltd., number average particle size 20 nm) as an inorganic UV absorber is added in an amount of 10% by mass, and wet film thickness is obtained by gravure coating. The film mirror for solar power generation was produced by providing a hard coat layer containing a UV absorber by applying with a UV conveyor (light source: high-pressure mercury lamp, illuminance: 100 mW / cm ² ).

  Furthermore, SE-6010 (manufactured by Showa Polymer Co., Ltd.), which is an acrylic resin adhesive, is coated on the resin substrate as an adhesive layer with a thickness of 10 μm, and is 0.1 mm thick, 4 cm long and 5 cm wide. On the aluminum plate (made by Sumitomo Light Metal Co., Ltd.), the above sample was pasted through an adhesive layer to prepare Sample 1 which is a solar power generation reflecting device.

[Preparation of Sample 2: Example 2]
Similarly to the preparation of Sample 1, Sample 2 which is a reflector for solar power generation was prepared, except that Tinuvin 477 added to the UV absorber-containing hard coat layer was changed to 0.1% by mass with respect to the resin solid content. .

[Production of Sample 3: Example 3]
Similarly to the preparation of Sample 1, Sample 3 which is a solar power generation reflecting device was similarly prepared except that Tinuvin 477 added to the UV absorber-containing hard coat layer was changed to 1.5% by mass with respect to the resin solid content. .

[Preparation of Sample 4: Example 4]
Similarly, in the production of Sample 1, Sample 4 which is a reflector for solar thermal power generation was produced except that Tinuvin 477 to be added to the UV absorber-containing hard coat layer was changed to 6.5% by mass with respect to the resin solid content. .

[Preparation of Sample 5: Example 5]
Similarly to the preparation of Sample 1, Sample 5 which is a solar power generation reflection device was similarly manufactured except that Tinuvin 477 added to the UV absorber-containing hard coat layer was changed to 10% by mass with respect to the resin solid content.

[Preparation of Sample 6: Example 6]
Sample 6 which is a reflector for solar thermal power generation was prepared in the same manner as Sample 1 except that Tinuvin 477 added to the UV absorber-containing hard coat layer was changed to 11% by mass with respect to the resin solid content.

[Preparation of Sample 7: Example 7]
In the preparation of Sample 1, solar heat was similarly applied except that zinc oxide NANOFINE-50 was not added to the UV absorber-containing hard coat layer, and the addition amount of Tinuvin 477 was changed to 1.5% by mass with respect to the resin solid content. Sample 7 which is a reflection device for power generation was produced.

[Preparation of Sample 8: Example 8]
In the production of Sample 1, Tinuvin 477 was not added to the UV absorber-containing hard coat layer, and, except for this, Sample 8 which was a solar power generation reflection device was produced.

[Preparation of Sample 9: Comparative Example 1]
In the preparation of Sample 1, Tinuvin 477 and NANOFINE-50 were not added to the UV absorber-containing hard coat layer, and Sample 9 which was a solar power generation reflection device was prepared in the same manner.

[Production of Sample 10: Comparative Example 2]
In the preparation of Sample 1, Tinuvin 477 and NANOFINE-50 were not added to the UV absorber-containing hard coat layer, but Tinuvin 234 was added as a benzotriazole-based UV absorber in an amount of 1.5% by mass based on the resin solid content. A sample 10 which is a reflector for solar thermal power generation was prepared.

[Production of Sample 11: Comparative Example 3]
In the production of Sample 10, Sample 11 which is a solar power generation reflector is similarly produced except that 5% by mass of Tinuvin 234 (manufactured by BASF Japan Ltd.) as a benzotriazole UV absorber is added to the resin solid content. did.

[Production of Sample 12: Comparative Example 4]
In the preparation of Sample 1, Tinuvin 477 and NANOFINE-50 were not added to the UV absorber-containing hard coat layer, and CHIMASSORB 81 (manufactured by BASF Japan Ltd.) as a benzophenone UV absorber was 1. Sample 12 which is a solar power generation reflection device was prepared in the same manner except that 5% by mass was added.

[Production of Sample 13: Comparative Example 5]
In the production of Sample 12, Sample 13 which is a solar power generation reflector is similarly produced except that CHIMASSORB 81 (manufactured by BASF Japan Ltd.) as a benzophenone-based UV absorber is added in an amount of 5% by mass with respect to the resin solid content. did.

[Preparation of Sample 14: Example 9]
Similarly to the preparation of Sample 3, Sample 14 which is a reflector for solar power generation was prepared, except that NANOFINE-50 added to the UV absorber-containing hard coat layer was changed to 25% by mass with respect to the resin solid content. .

[Preparation of Sample 15: Example 10]
Similarly to the preparation of Sample 3, Sample 15 which is a reflector for solar power generation was prepared except that NANOFINE-50 added to the UV absorber-containing hard coat layer was changed to 40% by mass with respect to the resin solid content. .

[Production of Sample 16: Example 11]
The resin base material / anchor layer / silver reflective layer were prepared in the same manner as in Sample 1, and then Esper 9940A (made by Hitachi Chemical Co., Ltd., polyester resin) and tolylene diisocyanate (Mitsui Chemicals) were formed on the silver reflective layer. MM-A (manufactured by Panasonic Electric Works Co., Ltd., melamine resin, molecular weight 50, as a corrosion inhibitor) in a resin in which a resin solid content ratio (mass ratio) was mixed at 10: 2 with a fine isocyanate diisocyanate crosslinking agent) 000) was added in an amount of 10% by mass based on the resin solid content, and coated by a gravure coating method to form a corrosion prevention layer (top coat lower layer) having a thickness of 0.1 μm.

  Subsequently, Esper 9940A (manufactured by Hitachi Chemical Co., Ltd., polyester resin) and tolylene diisocyanate (manufactured by Mitsui Chemicals Fine Co., Ltd., diisocyanate cross-linking agent) are mixed on this corrosion prevention layer with a resin solid content ratio (mass ratio). Into the resin mixed at 10: 2, Tinuvin 477 (manufactured by BASF Japan) as a UV absorber was added in an amount of 1.5% by mass with respect to the resin solid content, and the thickness was coated by the gravure coating method. A 3 μm UV absorbing layer (topcoat upper layer) was formed.

Subsequently, vinylol 92T (made by Showa Polymer Co., Ltd.), which is an acrylic resin adhesive, is coated as an adhesive layer on the topcoat layer with a thickness of 10 μm, and an acrylic resin containing a UV absorber on the adhesive layer. A film (KORAD CLRAR05005, manufactured by Polymer Excluded Products) 50 μm was laminated. Subsequently, on the acrylic resin film as a UV absorber-containing hard coat layer, Rioduras LCH (UV curable acrylic resin; manufactured by Toyo Ink Co., Ltd.) and Tinuvin 477 (manufactured by BASF Japan Ltd.) as a triazine-based UV absorber are resin solids. 1.5% by mass with respect to the minute, zinc oxide NANOFINE-50 (manufactured by Sakai Chemical Industry Co., Ltd.) as an inorganic UV absorber is added in an amount of 10% by mass, and applied with a gravure coat with a wet film thickness of 40 μm. A film mirror for solar power generation was prepared by providing a UV absorbent-containing hard coat layer by UV irradiation using a UV conveyor (light source: high-pressure mercury lamp, illuminance: 100 mW / cm ² ).

  Furthermore, SE-6010 (manufactured by Showa Polymer Co., Ltd.), which is an acrylic resin adhesive, is coated on the base resin as an adhesive layer with a thickness of 10 μm, a thickness of 0.1 mm, 4 cm long × 5 cm wide. The sample was pasted on an aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd.) via an adhesive layer, and sample 16 as a solar power generation reflecting device was produced.

[Preparation of Sample 17: Example 12]
In preparation of the sample 16, Tinuvin 477 (manufactured by BASF Japan Ltd.) was not added as a UV absorber to the upper layer of the top coat, and the sample 17 which was a solar power generation reflection device was prepared in the same manner.

[Preparation of Sample 18: Example 13]
In preparation of the sample 16, Tinuvin 234 (manufactured by BASF Japan Ltd., molecular weight 447.6) is 10% by mass with respect to the resin solid content as a corrosion inhibitor in the top coat lower layer, and Tinuvin 477 (in the top coat upper layer as a UV absorber). BASF Japan Co., Ltd.) was added in an amount of 1.5% by mass with respect to the resin solid content, and a sample 18 that was a solar thermal power generation reflector was prepared in the same manner.

[Preparation of Sample 19: Example 14]
In the preparation of Sample 16, Tinuvin234 (manufactured by BASF Japan Ltd.) as a corrosion inhibitor was added to the topcoat lower layer in an amount of 10% by mass with respect to the resin solid content, and Tinuvin477 (BASF Japan) was added to the topcoat upper layer. Sample 19 which is a reflector for solar thermal power generation was prepared in the same manner.

[Preparation of Sample 20: Example 15]
Similarly to the preparation of Sample 18, Sample 20 which is a reflector for solar thermal power generation except that 1% by mass of hindered amine compound Tinuvin 152 as an antioxidant was added to the UV absorber-containing hard coat layer based on the resin solid content. Was made.

[Preparation of Samples 21 to 24: Examples 16 to 19]
In preparation of the sample 20, NANOFINE-50 added to the UV absorber-containing hard coat layer is an inorganic UV absorber having a number average particle diameter of 20 nm, Sicotrans Red L2815 (iron oxide; manufactured by BASF Japan Ltd.), CeO-X01 (cerium oxide; manufactured by Iox Co., Ltd.), NANOFINE-50 (zinc oxide; manufactured by Sakai Chemical Industry Co., Ltd.), STR-60 (titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.) Samples 21 to 24, which are solar power generation reflectors, were prepared in the same manner except that the solid content of the resin was changed to 15% by mass as described in 2.

[Preparation of Samples 25 to 28: Examples 20 to 23]
In the preparation of the sample 20, NANOFINE-50 added to the UV absorber-containing hard coat layer is CM-1000 (iron oxide; manufactured by Chemilite Industry Co., Ltd.), CERIGUARD, which is an inorganic UV absorber having a number average particle size of 150 nm. S-3018-02 (cerium oxide; manufactured by Daito Kasei Kogyo Co., Ltd.), MZ-300 (zinc oxide; manufactured by Teika Co., Ltd.), MT-700B (titanium oxide; manufactured by Teika Co., Ltd.) Samples 25 to 28, which are solar power generation reflection devices, were prepared in the same manner except that the solid content of the resin was changed to 15% by mass as described in 2.

[Preparation of Samples 29 to 32: Examples 24 to 27]
In the preparation of Sample 20, NANOFINE-50 added to the UV absorber-containing hard coat layer is a silica-coated inorganic UV absorber having a number average particle diameter of 20 nm (including a coating thickness of 5 nm), Concelight BP-10S ( Iron oxide; manufactured by JGC Catalysts & Chemicals Co., Ltd., CERIGUARDSC-6683 (cerium oxide; manufactured by Daito Kasei Kogyo Co., Ltd.), FINEX-50W-LP2 (zinc oxide; manufactured by Sakai Chemical Industry Co., Ltd.), STR-100A-LP (oxidized) Titanium (made by Sakai Chemical Industry Co., Ltd.), and the amount added was changed to 15% by mass with respect to the resin solid content as shown in Table 2. Similarly, it is a solar power generation reflector. Samples 29 to 32 were prepared.

[Production of Sample 33: Comparative Example]
As described in Example 1 of Japanese Patent Application Laid-Open No. 2010-237415, a method for forming a silver reflective layer in the preparation of the sample 20 is performed by an electroless silver mirror reaction in which a silver plating solution containing an aqueous ammoniacal silver nitrate solution is reduced with glucose. A sample 33, which is a solar power generation reflecting device, was prepared in the same manner except that silver was deposited on the surface of the anchor layer.

  As a result of measuring the regular reflectance of the produced sample 33 by the following method, the initial regular reflectance was low as shown in Table 3, and thus no further durability test was performed.

<< Evaluation of Reflector for Solar Power Generation >>
About the produced solar power generation reflective apparatus, the scratch resistance after wet heat treatment and the scratch resistance after UV deterioration treatment were evaluated according to the following methods.

[Abrasion resistance test after UV irradiation under wet heat environment (steel wool JIS test)]
Each sample was irradiated with ultraviolet rays for 1000 W 96 hours in an environment of 65 ° C. and 60% relative humidity using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and then the outermost layer surface of the film mirror was applied to # 0000 steel wool at 500 g / After applying reciprocating friction 10 times at a stroke of 50 mm and a speed of 500 mm / min with a load of cm ² , the scratch resistance after wet heat treatment and after UV degradation treatment was evaluated according to the following criteria.

◎: Number of scratches is 0 ○: Number of scratches is 1 to 5 △: Number of scratches is 6 to 10 ×: Number of scratches is more than 10 [Measurement of specular reflectance after UV irradiation under wet heat environment]
Each sample was irradiated with ultraviolet rays for 96 hours under an environment of 65 ° C. and 60% relative humidity using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and the following measurements were performed.

The spectrophotometer U-4100 manufactured by Shimadzu Corporation was remodeled with an integrating sphere reflection accessory attached, and the incident light incident angle was adjusted to 5 ° with respect to the normal of the reflecting surface. The regular reflectance of each sample at a reflection angle of 5 ° was measured. The average reflectance from 400 nm to 700 nm was measured, and the regular reflectance after UV deterioration treatment was evaluated according to the following criteria.
7: The average value of regular reflectance is 90% or more 6: The average value of regular reflectance is 85% or more and less than 90% 5: The average value of regular reflectance is 80% or more and less than 85% Yes 4: The average value of regular reflectance is 75% or more and less than 80% 3: The average value of regular reflectance is 70% or more and less than 75% 2: The average value of regular reflectance is 65% or more Less than 70% 1: The average value of regular reflectance is less than 65%. The above evaluation results are shown in Tables 1 and 2.

  From Tables 1 and 2, it can be seen that the solar power generation reflector using the film mirror of the present invention has a higher initial regular reflectance than the sample 33 in which silver is precipitated from ammoniacal silver nitrate. Since the initial performance of the sample 33 was insufficient, the evaluation by UV irradiation in a humid heat environment was not performed. In addition, the solar power generation reflecting device using the film mirror of the present invention has a high regular reflectance after UV irradiation in a humid heat environment as compared with the comparative example in which the UV absorber is not contained in the UV absorber-containing hard coat layer. It can be seen that the film has excellent performance in the scratch resistance test after the lower UV irradiation.

Claims (13)

  In a film mirror having at least one silver reflection layer formed by applying and baking a coating solution containing an organic silver complex compound on a resin substrate, the resin substrate is separated from the silver reflection layer. A film mirror comprising a UV-absorbent-containing hard coat layer at a position.   The film mirror according to claim 1, comprising the resin base material, the silver reflection layer, the corrosion inhibitor-containing layer, the UV absorber-containing layer, and the UV absorber-containing hard coat layer in this order.   The film mirror according to claim 1 or 2, wherein a molecular weight of the corrosion inhibitor contained in the corrosion inhibitor-containing layer is 800 or less.   The film mirror according to claim 1, wherein the UV absorber-containing hard coat layer contains a triazine-based UV absorber or an inorganic UV absorber.   The UV absorber-containing hard coat layer contains an antioxidant and a resin, and the antioxidant is contained in an amount of 0.1 to 5% by mass with respect to the resin solid content. The film mirror of any one.   The film according to any one of claims 1 to 5, wherein the UV absorber-containing hard coat layer contains a triazine-based UV absorber in an amount of 0.1 to 10% by mass with respect to the resin solid content. mirror.   The UV absorber-containing hard coat layer contains 1 to 50% by mass of an inorganic UV absorber based on the resin solid content, and the inorganic UV absorber is titanium oxide, zinc oxide, cerium oxide or iron oxide. The film mirror according to claim 1, wherein the film mirror is characterized.   The film mirror according to any one of claims 4 to 7, wherein the inorganic UV absorber is a fine particle having a number average particle diameter of 10 nm to 100 nm.   The film mirror according to any one of claims 4 to 8, wherein the fine particles of the inorganic UV absorber are surface-coated with a substance other than the UV absorber.   The film mirror according to claim 1, wherein the UV absorber-containing hard coat layer contains a resin obtained by curing an acrylic UV curable resin.   The film mirror according to any one of claims 5 to 10, wherein the antioxidant is a hindered amine compound.   The film mirror according to claim 1, wherein the silver reflective layer contains silver and an organic silver complex compound.   The solar power generation reflective apparatus formed by bonding the film mirror of any one of Claims 1-12, and a metal support body through an adhesive layer.