WO2011158665A1

WO2011158665A1 - Film mirror and reflective device for solar thermal power generation

Info

Publication number: WO2011158665A1
Application number: PCT/JP2011/062777
Authority: WO
Inventors: 鈴木　隆行
Original assignee: コニカミノルタオプト株式会社
Priority date: 2010-06-18
Filing date: 2011-06-03
Publication date: 2011-12-22

Abstract

Disclosed is a lightweight flexible film mirror having excellent weather resistance and good specular reflectance of solar heat, which can be suppressed in decrease in the specular reflectance even in cases when the film mirror is used in a harsh environment for a long period of time. The film mirror can be mass-produced and have a larger area, while being suppressed in the production cost. Also disclosed is a reflective device for solar thermal power generation, which uses the film mirror. The film mirror comprises a resin base and at least a silver reflective layer that is disposed on the resin base. The film mirror is characterized by comprising a layer that contains a compound that captures an amine and another layer that contains a silver complex compound that is obtained by having one or more silver compounds represented by general formula (1) below and at least one amine compound react with each other. Ag_nX (1)

Description

Film mirror and reflector for solar thermal power generation

The present invention relates to a film mirror having excellent weather resistance and good regular reflectance with respect to solar heat, and a solar power generation reflector using the film mirror.

In recent years, coal energy, biomass energy, nuclear energy, and natural energy such as wind energy and solar energy have been studied as alternative energy to replace fossil fuel energy such as oil and natural gas. The most stable and large amount of natural energy is considered to be solar energy.

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

On the other hand, it has been proposed to solve the problem of low energy density of solar energy by collecting solar energy with a huge reflector.

Since the reflection device is exposed to ultraviolet rays, heat, wind and rain, sandstorms, etc. due to solar heat, a glass mirror has been conventionally used. Glass mirrors are highly durable against the environment, but they are damaged during transportation or heavy, so there is a problem that the construction cost of the plant is increased because of the strength of the mount on which the mirrors are installed.

In order to solve the above problem, it has been considered to replace a glass mirror with a resin reflection sheet (for example, see Patent Document 1).

For the purpose of collecting solar heat, in terms of obtaining a high reflectance, the metal layer should be composed of silver having a higher reflectance in the visible light region than a commonly used aluminum reflective film. Is preferable (see, for example, Patent Document 2). However, the plating method using silver (Ag), chromium (Cr), etc. as the base material can obtain a reflective film having high-quality surface gloss and high reflectance, but the defect rate is high during production, Excessive costs are required for the plating process, and there are problems of air pollution and wastewater generation due to discharge of harmful substances in the plating process.

On the other hand, a method of forming a reflective film having a high reflectance by performing vacuum deposition using silver as a main component has been disclosed (for example, see Patent Document 3). After vacuum deposition using a highly reflective silver (Ag), aluminum (Al), nickel (Ni), rhodium (Rh) or other metal on the surface of a flexible substrate such as PET (PET), the substrate A reflective film can be manufactured by laminating the above metal, but in the case of vacuum deposition, a high vacuum chamber is required, and there are restrictions on the shape and size of the substrate, and coating The thickness is not uniform, and there is a problem due to high equipment costs.

As a method for solving the above problem, a technique for applying a coating solution containing a silver complex compound to form a highly reflective surface is disclosed (for example, see Patent Document 4). According to this manufacturing method, it is possible to manufacture a reflective film that can be mass-produced without causing air pollution and water pollution, has a simple process, has a low defect rate, and is inexpensive. However, when the reflective film described in the patent is used for a long time in a harsh environment of collecting solar heat, the problem has been found that the reflective film is colored and the regular reflectance is reduced.

JP 2005-59382 A JP-A-6-38860 JP 2002-129259 A Special table 2009-535661 gazette

This invention is made | formed in view of the said subject, Even if it is a case where it is a case where it is used for a long time under a severe environment as a film mirror for solar power generation, it suppresses the fall of a regular reflectance. A film mirror that is light and flexible, can be manufactured in a large area and mass-produced at a low cost, has excellent weather resistance, and has a good regular reflectance to solar heat, and the film mirror. The object is to provide a solar power generation reflector used.

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

1. In a film mirror having a resin base material and at least a silver reflective layer on the resin base material, a layer containing a compound for capturing an amine, and one or more silver compounds represented by the following general formula (1) A film mirror comprising a layer containing a silver complex compound obtained by reacting with at least one amine compound.

General formula (1)
Ag _n X
Wherein X is from oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrate, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, carboxylate, and derivatives thereof. A selected substituent, and n is an integer of 1 to 4.)
2. 2. The film mirror as described in 1 above, wherein the amine compound is at least one selected from the following general formulas (2) to (4).

Wherein R ¹ to R ⁶ are independently of each other hydrogen, a hydroxy group, a C1-C30 aliphatic alkyl group, an alicyclic alkyl group, an aryl group or an aralkyl group, and an alkyl group substituted with a functional group. Or a substituent selected from an aryl group, a heterocyclic compound group, a polymer compound, and derivatives thereof, and may form a ring with an adjacent group between R ¹ to R ^6. )
3. 3. The film mirror as described in 1 or 2 above, wherein the compound that captures the amine is an acid generator.

4. A reflector for solar power generation, wherein the film mirror according to any one of claims 1 to 3 is used.

By the above means of the present invention, even when used as a film mirror for solar power generation in a harsh environment for a long period of time, it is possible to suppress a decrease in regular reflectance, lightweight and flexible, To provide a film mirror having excellent weather resistance and good regular reflectance with respect to solar heat, and a reflector for solar thermal power generation using the film mirror, which can suppress the manufacturing cost and increase the area and mass production. I was able to.

As a result of intensive studies in view of the above problems, the present inventor applied a coating liquid containing a silver complex compound, manufactured a film mirror having a highly reflective surface, and was used in a harsh environment as a film mirror for solar power generation. When a durability test was performed assuming that it was used for a long time under the condition, fine black spot defects were formed on the mirror, and the number increased with the lapse of the durability test time, and the regular reflectance decreased. It has been found. When this cause was examined, it was estimated that the amine contained in a silver complex compound remained, and it was a cause. It turns out that sufficient heat treatment cannot be performed, and the remaining amount of amine increases and the decrease in specular reflectance increases as much as the resin base material and the material constituting the film mirror that are used have a lower heat resistance. did.

Therefore, as a result of intensive studies, the present inventor has found that a resin substrate and a film mirror having at least a silver reflective layer on the resin substrate, a layer containing a compound that captures amine, and the following general formula ( 1. A film mirror comprising a layer containing a silver complex compound obtained by reacting at least one silver compound represented by 1) with at least one amine compound. It has been found that even when used as a mirror in a harsh environment for a long period of time, it is possible to greatly suppress the formation of black point defects and suppress the decrease in regular reflectance. This makes it possible to select a resin base that is lightweight, flexible, and has low heat resistance, and found that a film mirror that can be manufactured in large areas and mass-produced while suppressing manufacturing costs can be obtained. It is up to the invention.

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

[Silver complex compound]
The silver reflecting layer according to the present invention is characterized by containing a silver complex compound obtained by reacting one or more silver compounds represented by the general formula (1) with at least one amine compound. There is no restriction | limiting in particular as an amine compound, If it is a compound which forms a complex with silver, it can be used. For example, ammonia, substituted or unsubstituted alkylamine compounds such as propylamine, butylamine, monoethanolamine, 2-methylaminoethanol, diethanolamine, butoxypropylamine, diethylmethylamine, 2-dimethylaminoethanol, methyldiethanolamine, polyethylene Examples thereof include amine polymers of imine, polyallylamine, and polylysine. Particularly preferred are ammonium carbamate compounds, ammonium carbonate compounds, and ammonium bicarbonate compounds. More preferably, as the ammonium carbamate compound, ammonium carbonate compound, or ammonium bicarbonate compound, the general formula (2) described in JP-A-2009-535661 and JP-A-2010-5000047 is known. It is a compound represented by (4).

In the general formula (1), n is an integer of 1 to 4, and X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrate, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetra A substituent selected from fluoroborate, acetylacetonate, carboxylate, and derivatives thereof, specifically, for example, silver oxide, silver thiocyanate, silver sulfide, silver chloride, silver cyanide, silver cyanate, Silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoroborate, silver acetylacetonate, silver acetate, silver lactate, silver oxalate and its derivatives, etc. It is not limited to.

In the general formulas (2) to (4), the functional group to be substituted is preferably a hydroxy group, an alkoxy group, a cyano group, an amino group, a carboxy group, or an alkylsilyl group, and 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, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, hydroxy, methoxy, Hydroxyethyl, methoxyethyl, 2-hydroxypropyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperi , Piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and the like Derivatives, polymer compounds such as polyarylamine and polyethyleneamine, and derivatives thereof are exemplified, but not limited thereto.

Specific examples of the compound include ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutyl ammonium dibutyl carbamate, dioctadecyl ammonium dioct Decylcarbamate, methyldecylammonium, methyldecylcarbamate, hexamethyleneimineammonium, hexamethyleneiminecarbamate, morpholinium, morpholinecarbamate, pyridiumethylhexylcarbamate, triethylenediaminium isopropylbicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium, triethoxysilylpropyl Carbamate, ethylammonium carbonate, isopropylammonium carbonate, isopropylammonium bicarbonate, n-butylammonium carbonate, isobutylammonium carbonate, t-butylammonium carbonate, t-butylammonium bikerbo 2-ethylhexylammonium carbonate, 2-ethylhexylammonium carbonate, 2-methoxyethylammonium carbonate, 2-methoxyethylammonium carbonate, 2-cyanoethylammonium carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium carbonate, dibutylammonium Carbonate, dioctadecylammonium carbonate, dioctadecylammonium bicarbonate, methyldecylammonium carbonate, hexamethyleneimineammonium carbonate, morpholineammonium carbonate, benzylammonium carbonate, triethoxysilylpropylammonium carbonate And one or a mixture of two or more selected from tri-, pyridium bicarbonate, triethylenediaminium carbonate, triethylenediaminium carbonate, and derivatives thereof, but are not limited thereto.

On the other hand, the type and production method of the above ammonium carbamate compound, ammonium carbonate compound, or ammonium bicarbonate compound are not particularly limited. For example, in US Pat. No. 4,542,214 (1985.9.17), an ammonium carbamate compound is formed from carbon dioxide and primary amine, secondary amine, tertiary amine, or at least one mixture thereof. It is described that it can be produced. When 0.5 mole of water is further added per mole of the amine, an ammonium carbonate compound is obtained. When 1 mole or more of water is added, an ammonium bicarbonate compound is obtained. Can do. 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. In addition to the above method, any known method can be used for the production of the ammonium carbamate compound, ammonium carbonate compound, or ammonium bicarbonate compound used in the present invention as long as the structure of the final substance is the same. May be used. 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.

A silver complex compound can be produced by reacting the ammonium carbamate, ammonium carbonate compound, or ammonium bicarbonate compound thus produced with a silver compound. For example, at least one silver compound represented by the general formula (1) and at least one ammonium carbamate, ammonium carbonate compound, or ammonium represented by the general formulas (2) to (4) Bicarbonate-based compounds and mixtures thereof are reacted directly at normal pressure or under pressure in a nitrogen atmosphere without using a solvent, or when using a solvent, such as water, methanol, ethanol, isopropanol, butanol. Alcohols, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate and carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and acetone, hexane , Hepta Hydrocarbon such as can be used aromatic compounds such as benzene and toluene, and chloroform and methylene chloride, and the like halogenated solvent or a mixed solvent such as carbon tetrachloride.

For the production of the silver complex compound used in the present invention, in addition to the above 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 is used. A silver complex compound can also be produced by reaction. 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. That is, it is not necessary to specifically limit the solvent for the production, the reaction temperature, the concentration, the presence or absence of the catalyst, and the production yield is not affected.

The silver complex compound used in the present invention has its production method described in JP-T-2009-535661, and is recognized by the structure of the following general formula (5).

General formula (5)
Ag [A] _m
In the formula, A is a compound represented by the general formulas (2) to (4), and m is 0.5 to 1.5.

The silver coating liquid composition for producing the silver reflective layer according to the present invention contains the above silver complex compound, and if necessary, a solvent, a stabilizer, a leveling agent, a thin film auxiliary agent, a reducing agent, a thermal decomposition reaction. Accelerator additives can be included.

On the other hand, examples of the stabilizer include amine compounds such as primary amines, secondary amines, and tertiary amines, ammonium carbamate compounds, ammonium carbonate compounds, ammonium bicarbonate compounds, or phosphines, phosphites, and phosphates. A phosphorus compound such as thiol or a sulfur compound such as thiol or sulfide, and a mixture of at least one of these. Specific examples of the amine compound include methylamine, ethylamine, n-propylamine, and isopropylamine. , N-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hex Decylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanolamine, methoxyethylamine, 2-hydroxypropylamine, 2-hydroxy- 2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, dimethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine , Piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, trie Range amine, 2,2- (ethylenedioxy) bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline And amine compounds such as anisidine, aminobenzonitrile, benzylamine and derivatives thereof, and polymer compounds such as polyarylamine and polyethyleneimine and derivatives thereof.

Specific examples of the ammonium carbamate compound, carbonate compound, and bicarbonate compound include the compounds specifically mentioned in the general formulas (2) to (4).

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 thereof 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, octylthioglycolate, and the like.

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.

In addition, examples of the thin film auxiliary agent include organic acids and organic acid derivatives, or at least one mixture thereof. Specific examples include organic acids such as acetic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid, stearic acid, naphthalic acid, and organic acid derivatives. Specifically, for example, ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, ammonium maleate, ammonium oxalate, ammonium molybdate, and other organic acid ammonium salts, Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, Os, Ir, Al, Ga, Ge, In, Manganese oxalate, gold acetate, paraoxalate containing metals such as Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th , 2-ethylhexanoic, silver octane, silver neodecanoate, cobalt stearate, naphthalic acid nickel, an organic acid metal salts such as naphthalic acid cobalt. The amount of the thin film auxiliary used is not particularly limited, but is preferably 0.1 to 25% in terms of molar ratio with respect to the silver complex compound.

Examples of the reducing agent include Lewis acids or weak Bronsted acids, and specific examples include hydrazine, hydrazine monohydrate, acetohydrazide, sodium borohydride or potassium borohydride, dimethylamine borane, and butylamine borane. Amine compounds, 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-o-formic acid And a mixture thereof containing at least one reducing organic compound such as formic acid compound, glucose, ascorbic acid and hydroquinone.

Specific examples of the thermal decomposition reaction accelerator include 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, triethylene glycol, methoxyethylamine, ethoxyethylamine, methoxypropyl Alkoxyalkylamines such as pyramine, 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 some cases, a solvent is required for adjusting the viscosity of the silver coating liquid composition and for forming a smooth thin film. 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, dioxane, methyl ethyl ketone, acetone, dimethylformamide, ketones such as 1-methyl-2-pyrrolidone, hexane, Hydrocarbons such as pentane, 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.

[Compound that captures amine]
The present invention is characterized in that it contains a compound that captures an amine generated during the formation of the silver reflective layer. The compound that traps amine is not particularly limited as long as it has a function of trapping amine, but a compound that can exist stably in a resin is preferable.

Examples of the compound that traps amines include general organic acids, organic acid derivatives, thermal acid generators, photoacid generators, epoxy compounds, or at least one or a mixture thereof. Specific examples of organic acids include organic acids such as acetic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid, stearic acid, naphthalic acid, and alkylsulfonic acid. Specific examples of organic acid derivatives include, for example, ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, ammonium maleate, ammonium oxalate, ammonium molybdate, toluene Examples thereof include ammonium salts of sulfonic acids and organic acid ammonium salts such as nonafluorobutanesulfonate triethylamine salts.

Among them, the acid generator is neutral in a normal state and thus has no reactivity with the resin, and releases an acidic substance when energy is applied. In the present invention, the heat treatment at the time of forming the silver reflective layer is performed from the silver complex compound. This is preferable in that the generated amine is captured. That is, it is particularly preferable that the compound that traps amine is an acid generator.

The thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 80 ° C. to 250 ° C., preferably 100 ° C. to 200 ° C. It is a compound that generates a low nucleophilic acid such as acid or disulfonylimide. There is no restriction | limiting in particular as this thermal acid generator, The application of the salt and ester compound of various acids, and the below-mentioned photo-acid generator is also possible. Various acids and salts used as curing agents for urea resins, melamine resins and the like can also be used. For example, known onium salts such as aromatic diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, salts of various aliphatic sulfonic acids, salts of various aliphatic carboxylic acids such as citric acid, acetic acid, maleic acid, Salts of various aromatic carboxylic acids such as benzoic acid and phthalic acid, salts of various alkylbenzene sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, salts of polymer type fluorosulfonic acid, salts of polymers having acidic groups Examples of the salt include ammonium salts, pyridine salts, and various metal salts. Examples thereof include organic halogen compounds such as trihaloalkyl compounds and imide sulfonate compounds such as N-hydroxyimide sulfonate.

Specifically, for example, as the sulfonium salt, 4-hydroxyphenyldimethylsulfonium triflate, benzyl-4-hydroxyphenylmethylsulfonium triflate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium triflate, 4-methylbenzyl-4 -Hydroxyphenylmethylsulfonium triflate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium triflate, 4-methoxycarbonyloxyphenyldimethylsulfonium triflate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium triflate, 4-acetoxyphenyl Benzylmethylsulfonium triflate, 4-acetoxyphenylmethyl-4-methylbenzylsulfoni Triflate, 4-acetoxyphenyldimethylsulfonium triflate, 4-hydroxyphenyldimethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, benzyl-4-methoxycarbonyloxyphenyl Methylsulfonium hexafluoro Sulfate, 4-acetoxyphenylbenzylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, benzyl -4-Hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylmethyl- 1-naphthylmethylsulfonium hexafluo Loantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylmethyl-4- Examples include methylbenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the aromatic diazonium salt include chlorobenzene diazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, dimethylaminonaphthyldiazonium tetrafluoroborate and the like.

Commercial products can be used as they are, and as typical examples of thermal acid generators, for example, commercial products available under the trade names Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, and Sun-Aid SI-150L. (Manufactured by Sanshin Chemical Co., Ltd.), commercial products (manufactured by Adeka) available under the trade names Adeka Opton CP-66, Adeka Opton CP-77, and the like.

The photoacid generator generates acid when exposed to radiation, where exposure is irradiation with active actinic radiation (radiation), for example, infrared light, high-pressure mercury lamp light source, electron beam, X-ray And so on. In general, visible light such as a wavelength of 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or a mixed line, ultraviolet rays, or the like is used. Photoacid generators include ionic compounds and nonionic compounds. Examples of the ionic photoacid generator include known onium salts and the like. Specific examples thereof include triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfone. Acid salts, 1-dimethylthionaphthalene methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, 1-dimethylthio-4-hydroxynaphthalenemethanesulfonate, p-toluenesulfonate , Trifluoromethanesulfonate, camphorsulfonate, 1-dimethylthio-4,7-dihydroxynaphthalene, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, diaryliodonium salt ,Thoria Ruhosuhoniumu salts, trialkyl sulfonium salts, diaryl sulfonium salts, triaryl sulfonium Mi um salts, dialkyl phenacyl sulfonium salts, diaryl Yu de salts, aryl diazonium salts.

Nonionic photoacid generators include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, diazomethane compounds, quinonediazide compounds, sulfone compounds, sulfonate ester compounds, carboxylic acid ester compounds, sulfonimide compounds, diazo ketone compounds And sulfonebenzotriazole compounds.

1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane as the haloalkyl group-containing hydrocarbon compound, and 2-phenyl-4,6-bis (trichloromethyl) as the haloalkyl group-containing heterocyclic compound -S-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, and the like. As the trihaloalkyl compound, for example, trihalomethyl-s-triazine compounds, oxadiazole compounds, tribromomethylsulfonyl compounds and the like described in US Pat. No. 4,239,850 are preferable.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl). Diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) And diazomethane.

Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like. Preferred examples of the sulfone compound include 4-trisphenacyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl-4-methylphenyl disulfone compound, and the like.

Specific examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Preferred specific examples include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, etc., and specific examples of iminosulfonate include benzyl monooxime tosylate. Benzyl monooxime-p-dodecylbenzene sulfonate, benzyl monooxime hexadecane sulfonate, 4-nitroacetophenone oximutosylate, 4,4'-dimethylbenzyl monooximutosylate, 4,4'-dimethylbenzyl monooxime-p- Dodecylbenzenesulfonate, dibenzylketone oximutosylate, ethyl-α-tolyloxyimino-cyanoacetate, furylmonooxime-4-acetamidobenzenesulfonate , Acetone oxime-p-benzoylbenzenesulfonate, 3-benzylsulfonyloxyimino-acetylacetone, bis (benzylmonooxide) dioctylnaphthalenedisulfonate, α- (p-toluenesulfonyloxyimino) benzyl cyanide, α- (p-toluene) Sulfonyloxyimino) -4-methoxybenzylcyanide (trade name: PAI-101 (manufactured by Midori Kagaku)), α- (camphor-10-sulfonyloxyimino) -4-methoxybenzylcyanide (trade name: PAI- 106 (manufactured by Midori Chemical Co., Ltd.)), (5- (4-methylphenyl) sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (trade name: CGI-1311 (manufactured by BASF) ).

Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenyl). Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) dipheny Maleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (tri Fluoromethylsulfonyloxy) -7-oxabici B [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2 2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyl Imido, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [ 2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- ( 4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethyl) Sulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethyl Sulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) Examples include naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

Specific examples of the diazo ketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like. Preferred diazo ketone compounds include 1,2-naphthoquinonediazide-5-sulfonic acid or esters of 1,2-naphthoquinonediazide-4-sulfonic acid with 2,3,4,4′-tetrahydroxybenzophenone, 1,2- Examples thereof include esters of naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid with 1,1,1-tris (4-hydroxyphenyl) ethane.

Commercially available products can be used as they are, and typical examples of photoacid generators include trade names CI-1370, CI-2064, CI-2397, CI-2624, CI-2539, CI-2734, CI-2758. , CI-2823, CI-2855 and commercial products available under CI-5102 (all manufactured by Nippon Soda Co., Ltd.), commercial products available under the trade name PHOTOINITIATOR 2074 (manufactured by Rhodia), trade name UVI- Commercial products available under 6974 and UVI-6990 (both manufactured by Union Carbide), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172 A commercially available product (manufactured by Adeka Co., Ltd.) can be listed below.

The epoxy compound is preferably a compound having an epoxy group as described in US Pat. No. 4,137,201. Such epoxy compounds are known and include diglycidyl ethers of various polyglycols, especially polyglycols derived by condensation of about 8 to 40 moles of ethylene oxide per mole of polyglycol, diglycidyl ethers of glycerol, etc. Metal epoxy compounds (such as those conventionally utilized in and together with vinyl chloride polymer compositions), epoxidized ether condensation products, diglycidyl ethers of bisphenol A (ie, 4,4'- Dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid esters (especially esters of alkyls of about 2 to 2 carbon atoms of fatty acids of 2 to 22 carbon atoms, such as butyl epoxy stearate), and various epoxies Long chain fatty acid triglyceride Epoxidized vegetable oils and other unsaturated natural oils (which are sometimes referred to as epoxidized natural glycerides or unsaturated fatty acids), which can be represented and exemplified by compositions of Lido etc. (eg epoxidized soybean oil, epoxidized linseed oil, etc.) These fatty acids generally contain 12 to 22 carbon atoms). As commercially available epoxidized fatty acid compounds, VIKOFLEX 7000 series, VIKOFLEX 9000 series (manufactured by ARKEMA), Adeka Sizer O series, Adeka Sizer D series (manufactured by Adeka), and as commercially available epoxy group-containing resin compounds, Epiclon 830, 830- S, 830-LVP, 835, 835-LV, Epilon 840, 840-S, 850, 850-S, 850-CRP, 850-LC, HP-4032, HP-4032D (manufactured by DIC), Epon 824, 826 , 828, Epon Resin 862 (Resolution Performance Product), RE-304S, RE-310S (Nippon Kayaku), Rica Resin BPO-20E, BEO-60E (New Nippon Rika) It is.

The total amount of the amine-capturing compound is usually in the range of 0.1 to 20% by mass, preferably 0.5 to 10% by mass when the total amount of the composition excluding the organic solvent is 100% by mass. %, More preferably in the range of 1 to 10% by mass. Moreover, you may use together the compound which capture | acquires 2 or more types of amines as needed.

[Configuration of film mirror]
The film mirror of the present invention has a resin substrate, a layer containing a compound that captures at least an amine on the resin substrate (hereinafter also referred to as an amine compound capturing layer), and a silver reflective layer. In addition to this, it is also a preferable aspect to provide special functional layers such as a silver protective layer, a barrier layer, a protective film layer, and a scratch-preventing layer. The resin base material, the silver protective layer, the barrier layer, the protective film layer, the scratch preventing layer, and the like may contain a silver corrosion inhibitor and a deterioration inhibitor described later.

(Resin base material)
Various conventionally known resin films can be used as the resin base material according to the present invention. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, 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, a polyarylate film, or a cellulose ester film, and it may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation. .

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

(Silver reflection layer and amine compound capture layer)
The silver reflective layer according to the present invention is a layer having a function of reflecting sunlight. The regular reflectance of the silver reflective layer is preferably 80% or more, more preferably 90% or more. Further, a layer made of a metal oxide such as SiO ₂ or TiO ₂ may be provided in this order on the silver reflective layer to further improve the regular reflectance. The regular reflectance can be measured at a wavelength of 400 to 800 nm. The regular reflectance can be measured by a known method.

The method for forming the silver reflecting layer and the amine compound capturing layer according to the present invention will be described in detail.

The method for producing a film mirror according to the present invention comprises (i) an amine-capturing layer (hereinafter also referred to as an undercoat layer) that contains (i) a compound that captures an amine on a resin substrate and further enhances the adhesion of silver. It is preferable to include a step of forming, and (ii) a step of forming a silver reflecting surface that forms a highly reflective silver mirror surface on the layer using the coating liquid containing the silver complex compound according to the present invention. (Iii) After the step (ii), at least a transparent overcoat layer (hereinafter also referred to as a silver protective layer) that protects the silver reflecting surface and increases heat resistance, salt water resistance, and weather resistance. It may further include a step of forming one or more kinds. Alternatively, a compound for capturing an amine may be added to the silver protective layer that protects the silver reflecting surface to give an amine compound capturing function.

The layer containing the amine-capturing compound is preferably formed adjacent to the layer containing the silver complex compound as described above, and is a layer adjacent to the resin substrate side of the layer containing the silver complex compound. More preferably. That is, it is preferable that the layer containing the compound for capturing an amine in the step (i) is an undercoat layer.

The formation of a layer (undercoat layer) containing a compound that captures amine in step (i), which is the preferred embodiment, will be described.

The undercoat layer preferably contains a resin as a main component and the compound that traps the amine compound. Furthermore, the resin base material and the silver reflecting layer are brought into close contact with each other. Therefore, the undercoat layer is important for the function of capturing the amine-based compound, the adhesiveness for closely adhering the resin substrate and the silver reflective layer, and the smoothness for drawing out the high reflection performance inherent in the silver reflective layer.

The resin used for the undercoat layer is not particularly limited as long as it satisfies the above adhesiveness, heat resistance, and smoothness conditions. Polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide Resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin or the like, or a mixed resin thereof can be used. From the viewpoint of weather resistance, a polyester resin and a melamine resin mixed resin are preferable. It is more preferable to use a thermosetting resin mixed with a curing agent. The thickness of the undercoat layer is preferably from 0.01 to 10 μm, more preferably from 0.1 to 5 μm.

Further, a leveling agent, a wetting agent, an adhesion promoter, an anti-degradation agent, a colorant, and the like can be included as necessary. In addition, leveling agents and wetting agents may be used to prevent pinholes and craters affecting the highly reflective mirror surface, and to form a smooth undercoat. For example, Air Product's Surfynol series, Degussa's TEGOwet series, BYK's BYK series, Degussa's Glide series, and EFKA. ) EFKA3000 series from Cognis, DSX series from Cognis, Powdermate series from Troy, acrylic oligomer from KSCNT, etc. can be used as adhesion promoters , Wax emulsion, amide wax, canauba wax, PE wax, etc., and silane coupling agents such as trimethoxypropylsilane, vinyltriethoxysilane and mercaptopropyltrimethoxysilane, or titanium-based, zirconium-based and aluminum-based cups A ring agent can also be used. Further, as the deterioration preventing agent described later, an antioxidant described later, a light stabilizer described later, and an ultraviolet absorber described later can be used. Typically, TINUVIN series, IRGANOX series, and Chimassorb series of BASF Corporation can be used. Can be used.

As a method for forming the undercoat layer, conventionally known coating methods such as spray, tip and roll coating methods can be used, and preferred examples include a gravure coating method, a reverse coating method, and a die coating method. .

The formation of the silver reflecting surface in the step (ii) will be described.

In this step, the silver reflective layer coating solution according to the present invention is applied to the undercoat layer formed in the step (i) and then heat-treated to form a reflective surface of the silver mirror. The silver reflective layer coating solution composition is as described above.

As the coating method, the silver reflective layer coating solution according to the present invention is applied by brushing, spray coating, dip coating, dip coating, roll coating, or spin coating. It may be coated by any method, such as using a printing method such as inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexographic printing, litho printing, etc. Can be selected according to the form and material.

A silver mirror surface can be formed on the base material coated in this manner through oxidation or reduction treatment other than heat treatment and irradiation treatment such as infrared rays, ultraviolet rays, electron beams, and lasers. Further, these processes may be combined.

For example, when there is a silver complex compound that has not been completely treated by heat treatment, it can be treated using a reducing agent. Specific examples of the reducing agent used include hydrazine, acetate hydrazide, Sodium or potassium borohydride, trisodium citrate, and amine compounds such as methyldiethanolamine and dimethylamineborane, metal salts such as ferrous chloride and iron sulfate, hydrogen, hydrogen iodide, carbon monoxide, formaldehyde Aldehyde compounds such as acetaldehyde, organic compounds such as glucose, ascorbic acid, salicylic acid, tannic acid, pyrogallol and hydroquinone can be used.

The above treatment process can be heat-treated under a normal inert atmosphere, but if necessary, in air, nitrogen, carbon monoxide, or a mixed gas of hydrogen and air or other inert gas. Processing is possible. The heat treatment is preferably performed at 80 to 400 ° C., preferably 90 to 250 ° C., more preferably 100 to 150 ° C. In addition, heat treatment may be performed in two or more stages at low and high temperatures within the above range. For example, the treatment may be performed at 80 to 120 ° C. for 1 to 30 minutes and at 150 to 200 ° C. for 1 to 30 minutes.

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

In the present invention, the silver reflective layer may be on the light incident side or on the opposite side with respect to the resin base material. However, since the base material is a resin, the purpose is to prevent resin deterioration due to light rays. It is preferable to be positioned on the light incident side.

The formation of the silver protective layer in the step (iii) will be described.

This step is a step of applying a transparent coating for protecting the silver reflecting surface formed as described above, and the coating liquid used for forming the silver protective layer is not particularly limited. That is, as long as it meets the object of the present invention, any known material may be used. However, after coating or coating, the transparency of the coating film is 90% or more, heat resistance, weather resistance, corrosion resistance and salt water resistance. It only has to be excellent.

The silver protective layer used in the film mirror of the present invention is adjacent to the side of the silver reflective layer far from the resin base material, and preferably contains a corrosion inhibitor to prevent silver corrosion deterioration and to prevent damage to the silver reflective layer. It contributes to the improvement of the adhesive strength with the barrier layer and the scratch-preventing layer formed outside the protective layer.

The resin used as a binder for the silver protective layer can be a polyester resin, an acrylic resin, a melamine resin, an epoxy resin, or a mixture of these resins. From the viewpoint of weather resistance, a polyester resin or an acrylic resin can be used. A resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable. Isocyanate is a mixture of one or more of various conventionally used isocyanates such as TDI (tolylene diisocyanate), XDI (xylene diisocyanate), MDI (methylene diisocyanate), and HMDI (hexamethylene diisocyanate). Can be used. Moreover, it is preferable to further mix a silane coupling agent with the thermosetting resin because weather resistance is further improved. Of these, mixing a silane coupling agent having an amino group is more preferable from the viewpoint of weather resistance.

The thickness of the silver protective layer is preferably from 0.1 to 20 μm, more preferably from 1 to 10 μm, from the viewpoints of adhesion, weather resistance and the like.

As a method for forming the silver protective layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.

In addition, it is preferable to use a silver corrosion inhibitor, which will be described later, and a deterioration inhibitor, for the silver protective layer, an antioxidant which will be described later, a light stabilizer which will be described later, and an ultraviolet absorber which will be described later. Typically, BASF's TINUVIN series, IRGANOX series, and Chimassorb series can be used.

Separately, a reducing agent can also be included, such as hydrazine, acetic hydrazide, sodium or potassium borohydride, trisodium citrate, and amine compounds such as methyldiethanolamine and dimethylamineborane, chloride Metal salts such as ferrous iron, iron sulfate, hydrogen, hydrogen iodide, carbon monoxide, aldehyde compounds such as formaldehyde and acetaldehyde, organic compounds such as glucose, ascorbic acid, salicylic acid, tannic acid, pyrogallol and hydroquinone Is mentioned.

(Silver corrosion inhibitor)
The corrosion inhibitor for the silver reflective layer used in the film mirror of the present invention is roughly classified into a corrosion inhibitor and an antioxidant having an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which silver is chemically or electrochemically eroded or deteriorated in material by the environmental material surrounding it (see JIS Z0103-2004).

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

(Corrosion inhibitor having an adsorptive group for silver)
Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole It is preferably 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-ethoxychrysoidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexane carboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate, or mixtures thereof.

Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, N-phenyl-3, 4-diformyl-2,5-dimethylpyrrole or the like, 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'-hydroxy3'5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) benzotriazole 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 compounds having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or a mixture thereof.

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 a compound having a mercapto group, mercaptoacetic acid, thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto can be used by adding the above-described materials. -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, butanediol bisthioglycol, trimethylolpropane tristhioglycolate, pentaerythritol Tetrakisthioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, triethylene glycol dimercaptan, etc., or a mixture thereof.

Examples of naphthalene-based compounds include thionalide.

In the film mirror of the present invention, an antioxidant described later can be added. It is preferable that any one of the constituent layers provided on the resin base material contains an antioxidant.

An antioxidant may be used as the corrosion inhibitor for the silver reflective layer used in the film mirror of the present invention.

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

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

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

Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol. Diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-diphosphonite 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like.

In the film mirror of the present invention, a light stabilizer described later can be added. It is preferable that a light stabilizer is contained in any one of the constituent layers provided on the resin substrate.

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

As the corrosion inhibitor for the silver reflective layer used in the film mirror of the present invention, a light stabilizer can also be used.

<Light stabilizer>
Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl- 8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethyl Piperidine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, triethylenediamine, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione.

Other nickel-based UV stabilizers include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, etc. can also be used.

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

In the film mirror of the present invention, an ultraviolet absorber described later can be added. It is preferable that any one of the constituent layers provided on the resin substrate contains an ultraviolet absorber.

As the corrosion inhibitor for the silver reflection layer used in the film mirror of the present invention, an ultraviolet absorber can also be used.

(UV absorber)
Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and triazine.

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

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

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

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

In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers that act as light energy conversion agents, 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.

In the case of using an ordinary ultraviolet light inhibitor, it is effective to use a photopolymerization initiator that generates radicals with visible light.

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

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

The barrier layer is intended to prevent deterioration of humidity, especially deterioration of the resin base material and various functional elements protected by the resin base material due to high humidity, but with special functions and applications. As long as the above characteristics are maintained, various types of barrier layers can be provided. In the present invention, it is preferable to provide a barrier layer on the light source side of the silver reflective layer.

As the moisture resistance of the barrier layer, the water vapor permeability at 40 ° C. and 90% RH is 100 g / m ² · day / μm or less, preferably 50 g / m ² · day / μm or less, more preferably 20 g / m ² · It is preferable to adjust the moisture resistance of the barrier layer so as to be not more than day / μm. The oxygen permeability is 0.6 cm ³ / m ² / day / atm or less (1 atm is 1.01325 × 10 ⁵ Pa) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH. It is preferable.

Regarding the barrier layer, there is no particular limitation on the formation method thereof, but a method of forming an inorganic oxide film by applying a ceramic precursor of an inorganic oxide film and then heating and / or irradiating ultraviolet rays is preferably used. It is done.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As said halogen ion, a fluorine ion and / or a chlorine ion are mentioned suitably. That is, fluorine ions alone, chlorine ions alone or a mixture thereof may be used. The compound to be used is not particularly limited as long as it generates fluorine ions and / or chlorine ions in the reaction solution. For example, as the fluorine ion source, ammonium hydrogen fluoride (NH ₄ ) HF ₂ , sodium fluoride NaF or the like is suitable. Preferred examples of the chlorine ion source include ammonium chloride NH ₄ Cl.

The concentration of the halogen ions in the reaction solution varies depending on the film thickness of an inorganic composition having an inorganic matrix to be produced and other conditions, but generally the reaction solution containing a catalyst. Is preferably in the range of 0.001 to 2 mol / kg, particularly 0.002 to 0.3 mol / kg. If the halogen ion concentration is lower than 0.001 mol / kg, hydrolysis of the organometallic compound does not proceed sufficiently, and film formation becomes difficult. Alternatively, when the concentration of the rogen ion exceeds 2 mol / kg, the generated inorganic matrix (metal oxide glass) tends to be non-uniform, which is not preferable.

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

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

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

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

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

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

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

Formula (II):-(SiR ¹¹ (R ¹² ) -NR ¹³ ) _n11-
In which R ¹¹ , R ¹² and R ¹³ are the same or different and independently of one another hydrogen or a substituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, preferably hydrogen, A group selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl) Where n11 is an integer and n11 is defined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

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

In one of the preferable embodiments, a solution containing perhydropolysilazane in which all of R ¹¹ , R ¹² , and R ¹³ are hydrogen atoms is used.

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

General formula (III)
-(SiR ²¹ (R ²² ) -NR ²³ ) _n21- (SiR ²⁴ (R ²⁵ ) -NR ²⁶ ) p-
In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent hydrogen or a substituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. Here, n21 and p are integers, and n21 is determined so that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

Particularly preferred are compounds wherein R ²¹ , R ²³ and R ²⁶ represent hydrogen and R ²² , R ²⁴ and R ²⁵ represent methyl, R ²¹ , R ²³ and R ²⁶ represent hydrogen, and R ²² , A compound in which R ²⁴ represents methyl and R ²⁵ represents vinyl, R ²¹ , R ²³ , R ²⁴ and R ²⁶ represent hydrogen and R ²² and R ²⁵ represent methyl.

A solution containing at least one polysilazane represented by the following general formula (IV) is also preferable.

Formula (IV)
^{^{^{_{- (SiR 31 (R 32)}}}} -NR 33) n31 - (SiR 34 (R 35) -NR 36) p 31 -
-(SiR ³⁷ (R ³⁸ ) -NR ³⁹ ) q-
In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are independently of each other hydrogen or a substituted alkyl group, aryl group, vinyl group or Represents a (trialkoxysilyl) alkyl group, wherein n31, p31 and q are integers, and n31 is determined so that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

Particularly preferred are R ³¹ , R ³³ and R ³⁶ representing hydrogen and R ³² , R ³⁴ , R ³⁵ and R ³⁸ representing methyl, R ³⁹ representing (triethoxysilyl) propyl and R ³⁷ Is a compound in which represents alkyl or hydrogen.

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

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

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

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

By using the method of the present invention, a dense glass-like layer having an excellent barrier action against gas can be produced because there are no cracks and holes.

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

(Adhesive layer)
The film mirror of the present invention preferably has an adhesive layer. The adhesive layer is not particularly limited as long as it has a function of enhancing the adhesion between the silver reflective layer, the silver protective layer or the barrier layer and the protective film layer, but is preferably made of a resin.

The resin used as the binder for the adhesive layer is not particularly limited as long as it satisfies the above conditions of adhesiveness, weather resistance, and smoothness. Polyester resin, acrylic resin, melamine resin, epoxy resin Resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin or the like can be used alone or a mixed resin thereof. From the viewpoint of weather resistance, a mixed resin of polyester resin and melamine resin is preferable. It is more preferable to use a thermosetting resin mixed with a curing agent such as isocyanate.

The thickness of the adhesive layer is preferably from 0.01 to 20 μm, more preferably from 0.1 to 10 μm, from the viewpoints of adhesiveness, smoothness, reflectance of the reflecting material, and the like.

As a method for forming the adhesive layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.

In addition, it is preferable that the adhesive layer contains a corrosion inhibitor or an ultraviolet absorber as described later depending on the purpose.

Generally, adhesives are used for the adhesive layer, but these adhesives need not be particularly limited. That is, any known material may be used as long as it conforms to the present invention, but it is only necessary that the reflective film does not undergo thermal deformation after laminating and has excellent adhesive strength. As the adhesive, a polyester-based adhesive, an epoxy-based adhesive, an acrylic adhesive, a cyanoacrylic adhesive, or the like can be used.

As the adhesive, polyester adhesives, epoxy adhesives, acrylic adhesives, cyanoacrylic adhesives, and the like can be used.

(Protective film layer)
The film mirror of the present invention preferably has a protective film layer. The protective film layer may be any film that can impart film mirror protection, and examples thereof include an acrylic film, a polycarbonate film, a polyarylate film, a polyethylene naphthalate film, and a polyethylene terephthalate film.

When there is a silver reflective layer or a barrier layer, the protective film layer is preferably provided on the sunlight incident side.

A preferable film material for the protective film layer preferably contains, for example, polyester, polyethylene terephthalate, polyethylene naphthalate, acrylic, polycarbonate, polyolefin, cellulose, or polyamide in terms of flexibility and weight reduction. Among these, an acrylic copolymer excellent in weather resistance and particularly copolymerized with at least two kinds of acrylic monomers is preferable.

Specific examples of suitable acrylic copolymers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Mainly one or more monomers selected from monomers having no functional group in the side chain (hereinafter referred to as non-functional monomer) such as alkyl (meth) acrylate such as cyclohexyl methacrylate and 2-ethylhexyl methacrylate One or more monomers selected from monomers such as 2-hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, and itaconic acid Combination of one or more monomers having functional groups such as OH and COOH in the side chain (hereinafter referred to as functional monomers), solution polymerization method, suspension polymerization method, emulsion polymerization method, bulk polymerization method Examples thereof include acrylic copolymers having a weight average molecular weight of 40,000 to 1,000,000, preferably 100,000 to 400,000, obtained by copolymerization by a polymerization method such as ethyl acrylate, methyl acrylate, 2-ethylhexyl. 50 to 90% by mass of a non-functional monomer that gives a polymer having a relatively low Tg such as methacrylate, and 10 to 50% by mass of a non-functional monomer that gives a polymer having a relatively high Tg such as methyl methacrylate, isobutyl methacrylate, or cyclohexyl methacrylate , 2-hydroxyethyl methacrylate, acrylic acid, itaconic acid, etc. Acrylic polymers such as the monomer contains 0 to 10% by weight is most preferred.

The shape of the film may be a shape required as a surface covering material for various film mirrors such as a flat surface, a diffusion surface, a concave surface, a convex surface, and a trapezoid.

The thickness of the film substrate is preferably 10 to 125 μm.

The surface of the polymer film layer may be subjected to corona discharge treatment, plasma treatment or the like.

The film substrate preferably contains any one of benzotriazole, benzophenone, triazine, cyanoacrylate, and polymer type ultraviolet absorbers.

(Scratch prevention layer)
In the present invention, it is preferable to provide a scratch preventing layer as the outermost layer of the film mirror.

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

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

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

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

Commercially available polyfunctional acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” series, etc.), Shin-Nakamura Chemical Co., Ltd. (trade name) (“NK ester” series, etc.), DIC; (trade name “UNIDIC” series, etc.), Toa Synthetic Chemical Co., Ltd. (trade name “Aronix” series, etc.), NOF Corporation; Products such as Nippon Kayaku Co., Ltd. (trade name “KAYARAD” series, etc.), Kyoeisha Chemical Co., Ltd. (trade names “light ester” series, “light acrylate” series, etc.) can be used.

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

The leveling agent is particularly effective in reducing surface irregularities when a scratch-preventing layer is applied. As the leveling agent, for example, a dimethylpolysiloxane-polyoxyalkylene copolymer (for example, SH190 manufactured by Toray Dow Corning) is suitable as the silicone leveling agent.

(Thickness of the entire film mirror)
The total thickness of the film mirror according to the present invention is preferably 75 to 300 μm, more preferably 100 to 200 μm, from the viewpoints of prevention of deflection of the mirror, regular reflectance, handling properties, and the like.

(Sunlight reflection mirror)
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 solar light collecting mirror with a single film mirror, more preferably, through a pressure-sensitive adhesive layer coated on the surface of the resin substrate opposite to the side having the silver reflective layer with the resin substrate interposed therebetween The film mirror is stuck on the holding member, particularly on the metal support, and used as a solar reflective mirror.

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 a plurality of 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 or the like is used.

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

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

(Holding member)
In the reflecting device of the present invention, it is preferable to use a metal support as a member for holding the film mirror, for example, a steel plate, a copper plate, an aluminum plate, an aluminum plated steel plate, an aluminum alloy plated steel plate, a copper plated steel plate, a tin plated steel plate. Metal materials having high thermal conductivity such as chrome-plated steel plates and stainless steel plates can be used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate or the like having good corrosion resistance.

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

(Production Example 1 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 using a (membrane) filter and thermal analysis (TGA), a silver coating solution composition (Ag-1) having a silver content of 5.0% by mass was produced.

(Production Example 2 of silver coating solution composition)
In a 500 ml Schlenk flask equipped with a stirrer, 33.8 g (112 mmol) of 2-ethylhexylammonium 2-ethylhexylcarbamate and 30.4 g (146 mmol) of isobutylammonium carbonate were dissolved in 16.0 g of isopropanol. 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, 2.5 g of 2-hydroxy-2-methylpropylamine as a stabilizer was added and stirred, then filtered using a 0.45 micron membrane filter, and thermal analysis (TGA). As a result, a silver coating liquid composition (Ag-2) having a silver content of 21% by mass was produced.

(Production Example 3 of silver coating solution composition)
In a 500 ml beaker, 40 g of silver nitrate, 37.9 g of butylamine and 200 ml of methanol were added, stirred for 1 hour, filtered using a 0.45 micron membrane filter, and subjected to thermal analysis (TGA). As a result, the silver content was 17% by mass. A silver coating solution composition (Ag-3) was prepared.

[Production of film mirror]
(Production of film mirror (F-1))
(I) A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate. On one side of the polyethylene terephthalate film, polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical Co., Ltd.), melamine resin (Super Becamine J-820, manufactured by DIC), TDI-based isocyanate (2,4-tolylene diisocyanate) ), HDMI-based isocyanate (1,6-hexamethylene diisocyanate), and Sun-Aid SI-100L (manufactured by Sanshin Chemical Co., Ltd.) as a compound for scavenging amines at a solid content ratio of 20: 1: 1: 2: 1, solid content A coating solution mixed in toluene so as to have a concentration of 10% by mass was coated by a gravure coating method to form an amine compound capturing layer (undercoat layer) having a thickness of 0.2 μm.

(Ii) On the undercoat layer, the silver coating solution composition (Ag-1) was applied to the film on which the undercoat layer was formed using a gravure printing machine, and heat-treated in an oven at 120 ° C. for 2 minutes. Thereafter, a silver reflective layer having a thickness of 0.1 μm was obtained.

(Iii) A polyester resin and a TDI (tolylene diisocyanate) -based isocyanate in a resin solid content ratio of 10: 2 and a solid content concentration of 20% by mass in toluene on the silver reflective layer as a silver protective layer. The mixed coating solution was coated by a gravure coating method to form a silver protective layer having a thickness of 5.0 μm.

Next, a transparent acrylic film (Acryprene HBS010P, Mitsubishi Rayon Co., Ltd., thickness 75 μm) was bonded as a protective film layer by a dry lamination process on the silver protective layer.

Further, an acrylic pressure-sensitive adhesive (BPS-5296, curing agent BXX4773, manufactured by Toyo Ink Co., Ltd.) was applied to the silicon release sheet so that the thickness after drying was 25 μm, and then dried at 100 ° C. for 2 minutes, and then this pressure-sensitive adhesive layer The sheet was bonded to the back surface of the polyester film of the resin base material to obtain the film mirror (F-1) of the present invention.

(Production of film mirror (F-2))
In the production of the film mirror (F-1), the film mirror (F-) of the present invention was prepared in the same manner except that tetrabutylammonium bis (trifluoromethylsulfonium) imide (manufactured by Aldrich) was used as the amine-capturing compound. 2) was obtained.

(Production of film mirror (F-3))
A film mirror (F-3) of the present invention was obtained in the same manner except that PAI-101 (manufactured by Midori Chemical Co., Ltd.) was used as the compound for capturing an amine in the production of the film mirror (F-1).

(Production of comparative film mirror (HF-1))
In the production of the film mirror (F-1), a film mirror (HF-1) of Comparative Example was obtained in the same manner except that the compound for capturing an amine was not added.

(Production of film mirror (F-4))
A film mirror (F-4) of the present invention was obtained in the same manner as in the production of the film mirror (F-1) except that the silver coating liquid composition was (Ag-2).

(Production of comparative film mirror (HF-4))
A film mirror (HF-4) of a comparative example was obtained in the same manner except that the compound for capturing an amine was not added in the production of the film mirror (F-4).

(Production of film mirror (F-5))
In the production of the film mirror (F-1), the present invention was similarly performed except that an amount adjusted to 0.5 g / m ² after applying glycol dimercaptoacetate as a corrosion inhibitor to the silver protective layer was added. Film mirror (F-5) was obtained.

(Production of comparative film mirror (HF-5))
In the production of the film mirror (F-5), a film mirror (HF-5) of a comparative example was obtained in the same manner except that the compound for capturing an amine was not added.

(Production of film mirror (F-6))
In the production of the film mirror (F-1), the present invention was similarly applied except that an amount adjusted to 0.5 g / m ² after adding T-234 as a corrosion inhibitor was added to the silver protective layer. A film mirror (F-6) was obtained.

(Production of comparative film mirror (HF-6))
In the production of the film mirror (F-6), a film mirror (HF-6) of a comparative example was obtained in the same manner except that the compound for capturing an amine was not added.

(Production of film mirror (F-7))
In the production of the film mirror (F-1), an amount adjusted to 0.5 g / m ² after adding T-234 as a corrosion inhibitor to the silver protective layer was added, and further after applying Tinuvin 1577 as an ultraviolet absorber. A film mirror (F-7) of the present invention was obtained in the same manner except that an amount adjusted to 0.5 g / m ² was added.

(Production of comparative film mirror (HF-7))
A film mirror (HF-7) of a comparative example was obtained in the same manner except that the compound for capturing an amine was not added in the production of the film mirror F7.

(Production of film mirror (F-8))
In the production of the film mirror (F-1), a silicon oxide barrier layer having a thickness of 100 nm was formed on the silver protective layer by the following vacuum deposition process before the protective film layer was bonded. Thus, a film mirror (F-8) of the present invention was obtained.

(Barrier layer by vacuum evaporation)
After exhausting until the ultimate vacuum of the chamber reaches 3.0 × 10 ⁻⁵ torr (4.0 × 10 ⁻³ Pa) using a vacuum deposition apparatus, oxygen gas is placed in the vicinity of the coating drum and the pressure in the chamber Is maintained at 3.0 × 10 ⁻⁴ torr (4.0 × 10 ⁻² Pa), and silicon monoxide is evaporated by heating at a power of about 10 kw with a piercing electron gun. A silicon oxide barrier layer having a thickness of 100 nm was formed on a polyester film running on a drum at a speed of 120 m / min.

(Production of comparative film mirror (HF-8))
In the production of the film mirror (F-8), a comparative film mirror (HF-8) was obtained in the same manner except that the compound for capturing an amine was not added.

(Production of film mirror (F-9))
In the production of the film mirror (F-7), a silicon oxide barrier layer having a thickness of 100 nm was formed on the silver protective layer by the vacuum deposition process before the protective film layer was bonded. Thus, a film mirror (F-9) of the present invention was obtained.

(Production of film mirror (F-10))
In the production of the film mirror (F-9), the film mirror (F-) of the present invention was produced in the same manner except that the following scratch-preventing layer (hard coat layer) was applied on the transparent acrylic film used for the protective film layer. 10) was obtained.

(Scratch prevention layer)
A coating solution for a scratch-preventing layer having the following composition was prepared as a coating solution, applied on the transparent acrylic film using a microgravure coater so that the film thickness after curing was 3 μm, and the solvent was evaporated and dried. It hardened | cured by the ultraviolet irradiation of 0.2 J / cm < ² > using the high pressure mercury lamp, and obtained the hard coat film.

<Scratch prevention layer coating solution>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator (Irgacure 184, manufactured by BASF) 4 parts by weight Ethyl acetate 150 parts by weight Propylene glycol monomethyl ether 150 parts by weight Silicone compound (BYK-307, (By Big Chemie Japan)
0.4 parts by mass (production of film mirror (F-11))
A film mirror (F-11) of the present invention was obtained in the same manner as in the production of the film mirror (F-1) except that the silver coating liquid composition was (Ag-3).

(Production of comparative film mirror (HF-9))
In the production of the film mirror (F-11), a film mirror (HF-9) of a comparative example was obtained in the same manner except that the compound for capturing an amine was not added.

Table 1 shows the contents of the produced film mirror.

[Preparation of solar power generation reflector]
(Production of solar power generation reflectors 1 to 11, H-1, H-4 to H-9)
The produced film mirrors (F-1) to (F-11) and comparative film mirrors (HF-1, HF-4 to HF-9) were cut into a length of 4 cm and a width of 4 cm, and the thickness was 0.1 mm. A 4 cm long x 5 cm wide aluminum plate and an adhesive layer were bonded together to obtain solar power generation reflectors 1 to 11 and comparative solar power generation reflectors H-1 and H-4 to H-9, respectively.

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

(Measurement of regular reflectance)
A spectrophotometer “UV265” manufactured by Shimadzu Corporation was modified with an integrating sphere reflection accessory, and the incident angle of incident light was adjusted to 5 ° with respect to the normal of the reflecting surface. The regular reflectance at a reflection angle of 5 ° was measured. Evaluation was measured as an average reflectance from 350 nm to 800 nm.

(Weight resistance test of regular reflectance)
The regular reflectance after standing for 1500 hours under the conditions of 85 ° C. and 85% RH is measured by the same method as the above-mentioned light reflectance measurement, and the forced reflectance is calculated from the regular reflectance before forced degradation and the regular reflectance after forced degradation. The rate of decrease in regular reflectance due to deterioration was calculated, and the weather resistance was evaluated according to the following criteria.

5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Decrease rate of regular reflectance is 20% or more (Light resistance test of regular reflectance)
After performing UV irradiation for 300 hours under conditions of 60 ° C. and 60% RH using an ISUPAKI Electric Eye Super UV tester, the regular reflectance was measured by the above method, and the decrease rate of regular reflectance before and after ultraviolet irradiation was measured. The light resistance was calculated and evaluated according to the following criteria.

5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Decrease rate of regular reflectance is 20% or more (yellow change)
After performing ultraviolet irradiation for 300 hours under the conditions of 60 ° C. and 60% RH using an Isuperi UV tester manufactured by Iwasaki Electric Co., Ltd., yellow change was visually observed and evaluated according to the following criteria.

5: The difference in color is not visible at all. 4: The difference in color is visible. 3: The difference in color is visible. However, it is at a level where there is no practical problem. The difference is clearly visible and is at a practically problematic level. 1: Significant color difference is significant (regular reflectance salt spray test)
Spraying salt water (pH; 6.5 to 7.2) for 2 hours at a temperature of 25 ° C. and letting it stand at 60 ° C. for 24 hours as one cycle was conducted 10 times, and the salt water resistance was evaluated according to the following criteria.

5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: Decrease rate of regular reflectance is 20% or more (pencil hardness test)
Based on JIS-K5400, the pencil hardness of each sample at 45 ° inclination and 1 kg load was measured. The evaluation results are shown in Table 2.

As is clear from Table 2, it can be seen that the various characteristics of the solar power generation reflecting device using the film mirror of the present invention are superior to the comparative example. That is, in the comparative example, even when an additive for improving weather resistance and light resistance is contained, when the test is conducted for a long time under a harsh environment, the effect is reduced. Then, it turned out that the film mirror which has a favorable regular reflectance with respect to sunlight, and a solar power generation reflective apparatus using the same can be provided, maintaining light resistance and a weather resistance.

Claims

In a film mirror having a resin base material and at least a silver reflective layer on the resin base material, a layer containing a compound for capturing an amine, and one or more silver compounds represented by the following general formula (1) A film mirror comprising a layer containing a silver complex compound obtained by reacting with at least one amine compound.
General formula (1)
Ag n X
Wherein X is from oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrate, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, carboxylate, and derivatives thereof. A selected substituent, and n is an integer of 1 to 4.)
The film mirror according to claim 1, wherein the amine compound is at least one selected from the following general formulas (2) to (4).

Wherein R 1 to R 6 are independently of each other hydrogen, a hydroxy group, a C1-C30 aliphatic alkyl group, an alicyclic alkyl group, an aryl group or an aralkyl group, and an alkyl group substituted with a functional group. Or a substituent selected from an aryl group, a heterocyclic compound group, a polymer compound, and derivatives thereof, and may form a ring with an adjacent group between R 1 to R 6. )
The film mirror according to claim 1 or 2, wherein the compound that captures the amine is an acid generator.
A reflector for solar power generation, wherein the film mirror according to any one of claims 1 to 3 is used.