JP2015190033A - Laminate, method for manufacturing the same, reflector, mirror film, antibacterial coat, conductive film and thermal conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a laminate obtained at a simple step without performing the step of synthesizing a complexing agent having a complicated structure and having a high light reflectance; a method for manufacturing the laminate; a reflector; a mirror film; an antibacterial coat: a conductive film; and a thermal conductor.SOLUTION: The laminate comprises a base material and a silver layer provided on the base material and formed by applying a solution including at least a silver compound represented by a formula (A), an amine compound represented by a formula (B) and water, where, X represents oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate and carboxylate, etc., n represents an integer of 1-4, and Rand Rindependently represent a hydrocarbon group having 1 to 12 carbon atoms. AgX...(A) R-CHR-CH-NH...(B)

Description

  The present invention relates to a laminate and a method for producing the same, and a reflector, a mirror film, an antibacterial coat, a conductive film, and a heat conductor.

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

  However, solar energy has a problem of low energy density. In order to solve this problem, in recent years, attempts have been made to collect sunlight using a huge reflector. As a manufacturing technique of the reflecting mirror, for example, a wet method such as a plating method such as an electroplating method or a silvering method using a silver mirror reaction, or a dry method such as a vacuum deposition method, a sputtering method, or an ion plating method is known. ing.

  In addition to the above, as a manufacturing technique of the reflecting mirror, a method using a silver complex compound obtained by reacting a silver compound with a carbamate-based or carbonate-based compound is disclosed (for example, Patent Documents 1 to 1). 2).

International Patent No. 2011/158665 Pamphlet Japanese Patent No. 5001860

  However, in the methods described in Patent Documents 1 and 2, when a silver complex compound is obtained, it is necessary to synthesize a carbamate-based or carbonate-based compound as a complexing agent in advance and then prepare a silver complex-containing solution. . Therefore, there is a problem that not only the structure of the complexing agent itself is complicated, but also the process is complicated and the number of steps is increased.

  The present invention has been made in view of the above, and is obtained through a simple process without a complexing step of a complexing agent having a complicated structure, and a laminate having excellent light reflectivity, a method for producing the same, and a conventional method. The object is to provide a high-quality reflector, mirror film, antibacterial coating, conductive film, and thermal conductor, and to achieve this object.

Specific means for achieving the above-described problems are as follows.
<1> Application of a solution comprising a substrate, a silver compound represented by the following formula (A), an amine compound represented by the following formula (B), and water, provided on the substrate. And a silver layer formed by the above.
Ag _n X (A)
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and It represents a substituent selected from these derivatives. n represents an integer of 1 to 4.
In formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

A <2> solution is a laminated body as described in <1> containing a polar solvent further.
<3> The laminate according to <2>, wherein the polar solvent is an alcohol solvent or an amine solvent.
<4> The solution has a polarity of 2 to 30 moles of the amine compound represented by the formula (B), 3 to 100 moles of water, and 1 mole of the silver compound represented by the formula (A). It is a laminated body as described in <2> or <3> containing 3 mol-100 mol of solvents.
<5> The silver compound is a laminate according to any one of <1> to <4>, which is at least one selected from silver oxide, silver carbonate, silver nitrate, and silver acetate.
A <6> solution is a laminated body as described in any one of <1>-<5> which contains a reducing agent further.
<7> The laminate according to <6>, wherein the reducing agent is a compound represented by the following formula (1).
R-COOH Formula (1)
In formula (1), R represents a hydrogen atom or a monovalent functional group having one or more aldehyde groups.
<8> The base material is a laminate according to any one of <1> to <7>, having an easy adhesion layer on at least one surface and a silver layer on the surface of the easy adhesion layer.
<9> A reflector including the laminate according to any one of <1> to <8>.
<10> An antibacterial coat including the laminate according to any one of <1> to <8>.
<11> A conductor including the laminate according to any one of <1> to <8>.
<12> A thermal conductor including the laminate according to any one of <1> to <8>.

<13> On the substrate, a solution containing at least a silver compound represented by the following formula (A), an amine compound represented by the following formula (B), and water is applied, dried, and silver. It is a manufacturing method of a layered product which has a process of forming a layer.
Ag _n X (A)
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and It represents a substituent selected from these derivatives. n represents an integer of 1 to 4.
In formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

A <14> solution is a manufacturing method of a layered product given in <13> containing a polar solvent further.
<15> The method for producing a laminate according to <14>, wherein the polar solvent is an alcohol solvent or an amine solvent.
<16> The solution has a polarity of 2 to 30 mol of the amine compound represented by the formula (B), 3 to 100 mol of water, and 1 mol of the silver compound represented by the formula (A). It is a manufacturing method of the laminated body as described in <14> or <15> containing 3-100 mol of a solvent.
A <17> silver compound is a manufacturing method of the laminated body as described in any one of <13>-<16> which is at least 1 sort (s) selected from silver oxide, silver carbonate, silver nitrate, and silver acetate.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in light reflectivity obtained by a simple process without passing through the synthetic | combination process of the complex agent with a complicated structure, and its manufacturing method are provided.
Moreover, according to this invention, a high quality reflector, a mirror film, an antibacterial coat, an electrically conductive film, and a heat conductor compared with the past are provided.

  Hereinafter, the laminate of the present invention and the manufacturing method thereof will be described in detail, and the reflector, mirror film, antibacterial coating, conductive film, and thermal conductor to which the laminate of the present invention and the manufacturing method thereof are applied will be described in detail. I decided to.

<Laminated body and its manufacturing method>
The laminate of the present invention comprises a base material, a silver compound represented by the following formula (A), an amine compound represented by the following formula (B), and water. And a silver layer formed by application of a solution containing it.
Ag _n X (A)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and The substituent selected from these derivatives is represented.
n represents an integer of 1 to 4.
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In the formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

Conventionally, since a silver complex using a carbamate-based or carbonate-based compound is, for example, a carbamate-based compound itself is a decomposable substance, a step of synthesizing carbamate in advance, A process for appropriately adding 2-ethylhexylamine and adjusting it to become ethylhexylammonium-2-ethylhexylcarbamate is required, and simplification has been demanded because the process is complicated.
In the present invention, a solution obtained by dissolving a specific primary amine compound together with a silver compound in water is used for forming the silver layer. This makes it possible to synthesize and adjust carbamate-based or carbonate-based compounds that are complex complexing agents, without going through the complicated steps of adjusting, and with a simple process, a silver layer with a high light reflectance equivalent to or higher than conventional Can be formed.

Hereinafter, the silver layer and the base material constituting the laminate of the present invention will be described in detail.
-Silver layer-
The laminate of the present invention is configured by providing a silver layer formed by applying a solution containing a silver compound represented by the formula (A), an amine compound represented by the formula (B), and water. ing. The silver layer in the present invention functions as a light reflection layer by metallic silver formed by applying a solution containing a silver compound and a specific amine compound and heating the solution.

  The solution used for coating can be prepared by mixing a silver compound, a specific amine compound, water, and, if necessary, a silver reducing agent and various additives. The solution in the present invention contains a silver complex compound obtained by reacting the silver compound represented by the formula (A) and the amine compound represented by the formula (B).

(Silver compound)
The solution or silver layer used for coating and forming the silver layer contains at least one silver compound represented by the formula (A). The silver compound may be included as a silver complex.
Ag _n X (A)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and The substituent selected from these derivatives is represented.
n represents an integer of 1 to 4.

Specific examples of the silver compound represented by the formula (A) include silver oxide, silver thiocyanate, silver sulfide, silver chloride, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, and silver phosphate. Silver perchlorate, silver tetrafluoride borate, silver acetylacetonate, silver acetate, silver lactate, silver oxalate and derivatives thereof. However, it is not limited to these.
Among these, silver oxide, silver carbonate, silver nitrate, and silver acetate are preferable, and silver carbonate and silver oxide are more preferable in that the reflectance is more excellent.

  As content of the silver compound represented by Formula (A) in a solution, 3 mass%-50 mass% are preferable with respect to the total mass of a solution, and 5 mass%-30 mass% are more preferable. When the content of the silver compound represented by the formula (A) is 3% by mass or more, the light reflectance is more excellent. Moreover, it is advantageous at the point of the crack at the time of coating-film drying that content of the silver compound represented by Formula (A) is 50 mass% or less.

(Amine compound)
The solution or silver layer used for forming and coating the silver layer contains at least one amine compound represented by the following formula (B). This amine compound is a primary amine compound having a branched β-position. The amine compound may be included as a silver complex.
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In the formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

The hydrocarbon group having 1 to 12 carbon atoms represented by R ¹¹ and R ¹² may be either an unsubstituted alkyl group or a substituted alkyl group.
As an unsubstituted alkyl group, a C1-C8 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.
As the substituent of the substituted alkyl group, an aryl group (eg, phenyl group, naphthyl group), an alkoxy group (methoxy group, ethoxy group, etc., preferably 1 to 4 carbon atoms), a halogen atom (eg, chlorine atom, bromine atom) Etc.), cyano group, amino group, heterocyclic group (eg, cyclic groups such as nitrogen-containing heterocyclic groups such as pyrrolidine ring, pyrrole ring and imidazole ring, and oxygen-containing heterocyclic groups such as furan ring and tetrahydrofuran ring) Is mentioned.
Examples of the substituted alkyl group include an arylalkyl group (C1-C4 of the alkyl moiety), a cyanoalkyl group (C1-C4 of the alkyl moiety), and a halogenated alkyl group (C1-C4 of the alkyl moiety). And cycloolefin-bonded alkyl is preferred.
Of the above, at least one of R ¹ and R ² is preferably an ethyl group. The reason for this point is not always clear and speculated, but the two carbon atoms of the ethyl group and the nitrogen atom and hydrogen atom of the amino group form a 6-membered ring, so that HOMO can move from the nitrogen atom to the ethyl group. It is thought that the complex formation is stabilized due to the spread.
Furthermore, it is more preferable that R ¹¹ is a butyl group and R ¹² is an ethyl group.

Examples of the amine compound represented by the formula (B) include the following compounds.
Of these, isobutylamine, 2-ethylbutylamine, and 2-ethylhexylamine are preferable, and 2-ethylbutylamine and 2-ethylhexylamine are more preferable.

  The molecular weight of the amine compound represented by the formula (B) is preferably in the range of 70 to 400, more preferably in the range of 80 to 300, and particularly preferably in the range of 90 to 200. A molecular weight of 70 or more is advantageous in terms of wettability during coating, and a molecular weight of 400 or less is advantageous in terms of solubility in polar solvents.

  As content of the amine compound represented by Formula (B) in a solution, 2 mol-30 mol are preferable with respect to 1 mol of silver compounds in a solution, 3 mol-25 mol are more preferable, 3 mol- More preferred is 20 moles. When the content of the amine compound represented by the formula (B) is 3 mol or more, dissolution of the silver compound becomes better. Further, when the content of the amine compound represented by the formula (B) is 30 mol or less, the light reflectivity is more excellent.

(water)
The solution used for the coating formation of the silver layer contains water. Since it contains water, the solution is used as an aqueous coating solution.
As content of the water in a solution, 3 mol-100 mol are preferable with respect to 1 mol of silver compounds in a solution, 5 mol-50 mol are more preferable, and 5 mol-30 mol are still more preferable. When the water content is 3 mol or more, dissolution of the silver compound becomes better. Further, when the water content is 30 mol or less, the light reflectance is more excellent.

(solvent)
The solution or silver layer used for coating formation of the silver layer can contain a solvent, and preferably contains a polar solvent.
As the solvent, for example, the solvent described in paragraph No. [0040] of JP2012-181301A can be used as long as the effects of the present invention are not impaired. Among them, it is preferable to select and use a polar solvent from the viewpoint of further improving the effects of the present invention, and the polar solvent can be appropriately selected according to the silver compound and the like.

Examples of the polar solvent include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as formic acid and acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, Amide solvents such as dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, glycol solvents, Ammonia, plutamine, isopropylamine, butylamine, monoethanolamine, 2-methylaminoethanol, diethanolamine, butoxypropylamine, di Chill methylamine, 2-dimethylaminoethanol, amine solvents such as methyl diethanolamine, thiols solvents, sulfoxide solvents, a halogen-based solvent.
Among these, alcohol solvents, amide solvents, ketone solvents, nitrile solvents, sulfoxide solvents, and amine solvents are preferable, and alcohol solvents and amine solvents are more preferable.
Specifically, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, acetone, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, dimethyl sulfoxide, ammonia, Propylamine, isopropylamine, butylamine, monoethanolamine, 2-methylaminoethanol, diethanolamine, butoxypropylamine, diethylmethylamine, 2-dimethylaminoethanol, and methyldiethanolamine are more preferable. Further, methanol, ethanol, isopropanol, 1-methoxy-2-propanol, acetone, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, ammonia, isopropylamine, butylamine, and monoethanolamine are preferable. , Methanol, ethanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, and isopropylamine are more preferable.

Specifically, when silver carbonate, silver nitrate, or silver acetate is used as the silver compound, the polar solvent is an alcohol solvent (preferably methanol, ethanol, isopropanol, 1-methoxy-2-propanol), acid (preferably formic acid). , Acetic acid), or a mixed solvent thereof.
When silver oxide is used as the silver compound, the polar solvent is preferably an amine solvent (preferably isopropylamine, butylamine, monoethanolamine).

  As content of the polar solvent in a solution, 3 mol-100 mol are preferable with respect to 1 mol of silver compounds in a solution, 5 mol-60 mol are more preferable, 10 mol-40 mol are still more preferable. When the content of the polar solvent is 3 mol or more (particularly 10 mol or more), the light reflectivity is excellent, and the dissolution rate is also improved. Moreover, when content of a polar solvent is 100 mol or less, it is advantageous at the point of liquid stability.

(Reducing agent)
The solution preferably contains a reducing agent for silver reduction. By containing the reducing agent, the silver reduction reaction is promoted, and the light reflectance can be further improved.
Examples of reducing agents include hydrazine, acetate hydrazide, trisodium citrate, methyldiethanolamine, dimethylamineborane and other amine compounds, formaldehyde, acetaldehyde and other aldehyde compounds, glucose, ascorbic acid, salicylic acid, tannic acid, pyrogallol, hydroquinone and the like. Inorganic compounds such as organic compounds, metal salts such as sodium, potassium borohydride, ferrous chloride, and iron sulfate, hydrogen iodide, and carbon monoxide.

In this invention, it is preferable to contain the compound represented by following formula (1) as a reducing agent. The compound represented by the formula (1) is formic acid, or has both a carboxyl group and an aldehyde group in the molecule, so that the reducing action of the silver component and the adjacent during storage and production The stabilizing effect of the silver component itself at the layer interface appears.
R-COOH Formula (1)

  In formula (1), R represents a hydrogen atom or a monovalent functional group having one or more aldehyde groups. Examples of the “monovalent functional group having one or more aldehyde groups” represented by R include an aldehyde group, an alkyl group having 1 to 20 carbon atoms having one or more aldehyde groups, and one or more aldehydes. Examples thereof include an aryl group having 5 to 20 carbon atoms having a group, an amino group having one or more aldehyde groups, and a heterocyclic group having 5 to 20 carbon atoms having one or more aldehyde groups. Preferred are an aldehyde group, a methyl group having one or more aldehyde groups, an ethyl group having one or more aldehyde groups, a benzene ring having one or more aldehyde groups, and the like.

Examples of the compound represented by the formula (1) include formic acid, 2-methyl-3-oxopropanoic acid, 3-oxopropanoic acid, phthalaldehyde acid, isophthalaldehyde acid, terephthalaldehyde acid and the like.
Among these, formic acid is preferable in that the light reflectance is more excellent.
In addition, the compound represented by Formula (1) may be used individually by 1 type, and may use 2 or more types together.

The content of the compound represented by the formula (1) in the solution is preferably in the following range.
When the solution contains the compound represented by the formula (1), the content of the compound represented by the formula (1) in the solution is 0.01 to 20% by mass with respect to the total mass of the solution. Preferably, 0.1-10 mass% is more preferable. When the content of the compound represented by the formula (1) is 0.01% by mass or more, reducibility is exhibited and the effect of improving light reflectance is high. When the content of the compound represented by the formula (1) is 20% by mass or less, it is advantageous in terms of liquid stability when storing the coating liquid.

The solution may contain additives such as a stabilizer, a leveling agent, a thin film auxiliary agent, and a thermal decomposition reaction accelerator, if necessary, in addition to the above-described silver compound, amine compound, and solvent.
For details of the additive, reference can be made to the description of paragraph numbers [0037] to [0040] of JP2012-181301.

-Base material-
The laminate of the present invention is configured by providing a base material.
As a base material, from the viewpoint of flexibility and weight reduction, resin films such as glass epoxy, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, and liquid crystal polymer are formed into a film, glass film, paper, etc. Can be used.
The resin is not particularly limited as long as it is a resin that can be formed into a film. For example, a phenol resin, an epoxy resin, an imide resin, a bismaleimide triazine (BT) resin, a polyphenylene ether (PPE) resin, a tetrafluoroethylene resin, Liquid crystal resin, polyester resin, polyethylene naphthalate (PEN), aramid resin, polyamide resin, polyether sulfone, triacetyl cellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, polyacetylene, and the like are preferable.
A particularly suitable substrate is a polyester film or a polyimide film.

The shape of the substrate may be any shape as long as it is a shape required as a film substrate depending on various uses such as a flat surface, a diffusion surface, a concave surface, and a convex surface.
The thickness of the substrate is preferably about 10 μm to 5 mm. When the thickness is less than 10 μm, handling during production becomes difficult, and when the thickness exceeds 5 mm, molding becomes difficult. A more preferable thickness is 20 μm to 1 mm, and a more preferable range is 25 μm to 500 μm.

The base material preferably has an easy-adhesion layer on at least one surface. The easy-adhesion layer may be formed by, for example, applying and drying a composition containing a water-dispersed latex as a binder component.
And it is preferable that the silver layer is provided in the surface of the easily bonding layer of a base material. Since the silver layer is in contact with the surface of the easy adhesion layer, the adhesion of the silver layer can be further improved.

  The thickness of the easy adhesion layer is preferably 0.05 μm to 10 μm from the viewpoint of adhesion.

  Examples of the substrate having such an easy-adhesion layer include Toyobo Cosmo Shine A-4100 (polyethylene terephthalate film) and Cosmo Shine A-4300 (polyethylene terephthalate film).

Moreover, in order to make it easy to form the below-mentioned undercoat on a base material, you may surface-treat to a base material previously.
Surface treatment includes UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment, and other surface activation treatments, hydrazine, N-methylpyrrolidone, sodium hydroxide solution, alkaline solution such as potassium hydroxide solution And treatment with an acidic solution such as sulfuric acid, hydrochloric acid and nitric acid. Examples of the treatment for removing and cleaning the substrate surface include treatment with an organic solvent such as methanol, ethanol, toluene, ethyl acetate, and acetone, and washing with water to remove the attached dust. These surface treatments may be performed in combination of a plurality of types.

  The substrate may include an ultraviolet absorber. Moreover, you may contain the plasticizer for maintaining a softness | flexibility, the antioxidant which prevents deterioration of the film itself, a radical scavenger, etc.

(Antioxidant)
Preferable examples of the antioxidant include phenol-based antioxidants, thiol-based antioxidants, and phosphite-based antioxidants.
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-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-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) propionate ,bird Tylene 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-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene and the like.
In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

Examples of the thiol antioxidant include distearyl-3,3′-thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate).
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′-biphenylenedi Examples thereof include phosphonite and 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite.

  As content in the case of using antioxidant for a base material, it is preferable that it is the range of 0.1 mass part-10 mass parts with respect to 100 mass parts of resin which comprises the base material in a base material.

(UV absorber)
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, phenyl salicylate UV absorbers, hindered amine UV absorbers, cyanoacrylate UV absorbers, and titanium oxide. Preferred examples include inorganic particle type ultraviolet absorbers.

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 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 triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine and the like.
Examples of the phenyl salicylate ultraviolet absorber include phenylsulcylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

  In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet light into vibrational energy in the molecule and releasing the vibrational energy as thermal energy. In addition, a substance that exhibits an effect when used in combination with an antioxidant or a colorant, or a light stabilizer called a quencher that acts as a light energy converter can be used in combination.

  As content in the case of using a ultraviolet absorber for a base material, it is preferable that it is the range of 0.1 mass part-10 mass parts with respect to 100 mass parts of resin which comprises the base material in a base material.

-First adjacent layer-
The laminate of the present invention can be constituted by providing a first adjacent layer formed by coating between a base material and a silver layer. By providing this 1st adjacent layer, the adhesiveness between a base material and a silver layer improves more. In addition, the light reflectance can be further improved by including the compound represented by the above-described formula (1) in the first adjacent layer.

The first adjacent layer may be provided as an undercoat layer of the base material, for example. The first adjacent layer may have a single layer configuration or a plurality of layers of two or more layers.
When providing as an undercoat layer, it is preferable that the same resin as the resin constituting the base material or a resin having an affinity with the resin constituting the base material is included from the viewpoint of adhesion to the adjacent base material.
Examples of the resin contained in the undercoat layer include a thermosetting resin and a thermoplastic resin, and the thermosetting resin and the thermoplastic resin may be used alone or in combination.

  Examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, polyurethane resins, bismaleimide resins, melamine resins, and isocyanate resins. Examples of the thermoplastic resin include polyolefin resin, phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.

  In the first adjacent layer, a compound having a polymerizable double bond (for example, an acrylate compound or a methacrylate compound) may be used in order to promote crosslinking within the layer. In particular, it is preferable to use a polyfunctional compound. Examples of the compound having a polymerizable double bond also include a thermosetting resin or a thermoplastic resin, and specific examples include an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, A resin obtained by partially methacrylic acid using methacrylic acid or acrylic acid may be used.

  In addition, the first adjacent layer can be provided with a reducing agent so as to increase the formation rate of the silver layer and to obtain a high reflectance even at a low temperature in a short time.

  Various additives such as an adhesion-imparting agent, a silane coupling agent, an antioxidant, a surfactant, and an ultraviolet absorber are added to the first adjacent layer as necessary, as long as the effects of the present invention are not impaired. You may add 1 type (s) or 2 or more types.

  In general, the thickness of the first adjacent layer is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.1 μm to 5 μm in terms of adhesion.

-Second adjacent layer-
The laminate of the present invention can be constituted by providing a second adjacent layer formed by coating on the side opposite to the side (side facing the substrate) where the first adjacent layer of the silver layer is provided. . By providing this second adjacent layer on the light incident side of the silver layer, it is possible to prevent deterioration or breakage of the silver layer, the resin support, or the undercoat layer provided as desired by sunlight, rainwater, dust, etc. In addition, the mirror surface can be stabilized. In addition, the light reflectance can be further improved by including the compound represented by the above-described formula (1) in the first adjacent layer.

  The second adjacent layer may be provided as a layer for the purpose of protecting the surface of the silver layer on the substrate, for example. The second adjacent layer may be composed of a single layer or may be composed of two or more layers.

  The second adjacent layer can be formed using a resin material. As the resin material, a resin capable of forming a film or a layer is preferable, and a resin having strength, durability, air and moisture blocking properties, adhesion to an adjacent layer (for example, a silver layer), and transparency is preferable. In particular, a resin having a light-transmitting property with respect to light having a wavelength required according to the use of the laminate is preferable.

Examples of the resin include a photocurable resin (for example, urethane (meth) acrylate resin, polyester (meth) acrylate resin, silicone (meth) acrylate resin, epoxy (meth) acrylate resin, etc.), thermosetting resin (for example, Urethane resin, phenol resin, urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin, and the like.
The resins may be used alone or in combination of two or more.
In addition, "(meth) acrylate" represents that both an acrylate and a methacrylate are included.

Among these, as the resin used for the second adjacent layer, a photocurable resin is preferable, and a resin having a urethane bond is more preferable. Furthermore, the resin of the second adjacent layer is preferably a urethane (meth) acrylate resin in terms of easy adjustment of the hardness of the laminate.
As a urethane (meth) acrylate resin, for example, a polyester polyol (A) and a polyisocyanate (B) are reacted to synthesize an isocyanate group-terminated urethane prepolymer, and then a hydroxyl group-containing (meth) acrylate compound (C) is reacted. The product obtained by making it suitable is suitable.
Here, the polyester polyol (A) is obtained by reacting a polybasic acid and a polyhydric alcohol. Specific examples thereof include polytetramethylene glycol (PTMG), polyoxypropylene diol (PPG), and polyoxy. And ethylene diol. The polyisocyanate (B) is not particularly limited as long as it has two or more isocyanate groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexa Examples include methylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and xylylene diisocyanate (XDI). Examples of the hydroxyl group-containing (meth) acrylate compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycidol di (meth) acrylate. And pentaerythritol tri (meth) acrylate.

  A commercially available product may be used as the urethane (meth) acrylate resin synthesized using the above-described polyester polyol (A), polyisocyanate (B), and hydroxyl group-containing (meth) acrylate compound (C). Examples of commercially available products include UV curable urethane acrylate resins (eg, UV1700B, UV6300B, UV7600B, etc.) manufactured by Nippon Gosei Co., Ltd., and polymer acrylates (eg, Unidic V-6840, Unidic V-) manufactured by DIC. 6841, Unidic WHV-649, Unidic EKS-675, etc.).

In addition to the above, examples of resins that can be used for the second adjacent layer include cellulose ester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyether sulfone) resins, and polyester resins (for example, polyethylene). Terephthalate, polyethylene naphthalate, etc.), olefinic resins (eg, polyethylene, polypropylene, etc.), cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl alcohol Resin, ethylene vinyl acetate resin, ethylene acrylate copolymer, polycarbonate, norbornene resin, polymethylpentene resin, polyamido , Fluorine-based resins, polymethyl methacrylate, acrylic resins, polyurethane resins, and silicone resins.
Among these, from the viewpoint of adhesion between the second adjacent layer and the silver layer, the resin contained in the second adjacent layer is an acrylic resin, a vinyl butyral resin, an ethylene vinyl acetate resin, or an ethylene acrylate copolymer. One or more resins selected from the following are preferred.

The second adjacent layer may further contain a crosslinking agent. By including a cross-linking agent, the cross-linked structure is formed in the second adjacent layer, thereby providing an advantage that the strength is further improved and the adhesion with the adjacent silver layer is further improved.
The crosslinking agent may be selected depending on the correlation with the resin constituting the second adjacent layer, and examples thereof include carbodiimide compounds, isocyanate compounds, epoxy compounds, oxetane compounds, melamine compounds, bisvinylsulfone compounds, and the like. In this respect, at least one crosslinking agent selected from the group consisting of carbodiimide compounds, isocyanate compounds, and epoxy compounds is preferred.

  In addition to the above-described components, the second adjacent layer includes additives such as an ultraviolet absorber, a photopolymerization initiator, an antistatic agent, a coating aid (leveling agent), an antioxidant, and an antifoaming agent. May be contained. The second adjacent layer may further contain a reducing agent from the viewpoint that reduced silver is generated from the upper layer by reducing an insufficiently reduced silver layer and high light reflectance is obtained. .

  The thickness of the second adjacent layer is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 5 μm or more, and more preferably 10 μm or more in terms of being superior to the dust resistance and adhesion resistance of the laminate. Is particularly preferred. Although there is no restriction | limiting in particular in the upper limit of thickness, Usually, it is 100 micrometers or less, and it is preferable that it is 50 micrometers or less.

The coating solution for forming the second adjacent layer may contain a solvent. The solvent is not particularly limited. For example, alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketones such as acetone, methyl ethyl ketone, and cyclohexanone. Solvents, amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, Aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like.
Among them, amide solvents, ketone solvents, nitrile solvents, carbonate solvents, and aromatic hydrocarbon solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propionitrile. N-methylpyrrolidone, dimethyl carbonate and toluene are preferred.

  The second adjacent layer may further contain an additive. Examples of the additive include a photopolymerization initiator, an antistatic agent, a surface conditioner (for example, a leveling agent and a fluorine-based antifouling additive), a surfactant, an ultraviolet absorber, a light stabilizer, an antioxidant, Examples include foaming agents, thickeners, anti-settling agents, pigments, dispersants, and silane coupling agents.

-Surface coating layer-
The laminate of the present invention may further have a surface coating layer on the surface of the silver layer or on the second adjacent layer on the silver layer. The surface coating layer can be provided as the outermost layer. By having the surface coating layer, the weather resistance and scratch resistance of the laminate are further improved.
The surface coating layer is not particularly limited as long as it can prevent physical or chemical damage to the surface of the laminate by being provided on the second adjacent layer (preferably as the outermost layer). The surface coating layer can be formed by arbitrarily using a known resin layer or the like. That is, the surface coating layer may be a soft layer having a hardness of 100 N / mm ² or less and an elastic recovery rate of 60% or more, or provided as a so-called hard coat layer having a hard surface. Also good.

When the surface coating layer is a soft layer, the thickness of the surface coating layer is not particularly limited, but from the viewpoint that the scratch resistance of the laminate becomes better, and the haze value and the maintenance factor of the reflectance become higher, 1 μm to 50 μm Is preferable, and 3 μm to 30 μm is more preferable.
When the surface coating layer is a hard layer, the thickness of the surface coating layer is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 15 μm, from the viewpoint of antifouling properties and scratch resistance.

  The total thickness of the laminate of the present invention may be 0.1 mm or more from a practical point, but is 0.2 mm to 5.0 mm in terms of strength, durability, and workability. preferable.

The laminate of the present invention can be configured in an embodiment having the following laminate structure. Among them, (a), (c), (g) are excellent in interlayer adhesion and light reflectance. ) Or (f) is preferred.
(A) Substrate / silver layer (b) Substrate / adhesive layer of substrate / silver layer (c) substrate / first adjacent layer / silver layer (d) substrate / silver layer / second adjacent Layer (e) Base material / Adhesive layer of base material / Silver layer / Second adjacent layer (F) Base material / First adjacent layer / Silver layer / Second adjacent layer

<Method for producing laminate>
Next, the manufacturing method of the laminated body of this invention is demonstrated.
In the method for producing a laminate of the present invention, a solution containing at least a silver compound represented by the formula (A), an amine compound represented by the formula (B), and water is applied on a substrate. And a step of forming a silver layer by drying (hereinafter also referred to as “silver layer forming step”).
Ag _n X (A)
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and The substituent selected from these derivatives is represented. n represents an integer of 1 to 4.
In formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.
The details of the silver compound represented by formula (A), the amine compound represented by formula (B), and the solution are as described above.

~ Silver layer formation process ~
In the first aspect, a solution containing at least a silver compound represented by the formula (A), an amine compound represented by the formula (B), and water is applied and dried to form a silver layer. A silver layer forming step;
In addition, the details regarding the silver compound represented by the formula (A), the amine compound represented by the formula (B), and the solution containing them are as described above.

  The coating can be performed by a coating method using a conventionally known coating apparatus such as a gravure coater, a reverse coater, a die coater, a blade coater, a roll coater, an air knife coater, a screen coater, a bar coater, or a curtain coater.

  In the present invention, heating for drying and reduction of the coating film may be performed simultaneously, or heating may be performed for reduction after drying of the coating film. The heating method may be any method as long as the heating can be performed, for example, a method in which warm air or hot air is blown to the film to heat, a method in which radiant heat is applied to the film to increase the film temperature, and a base A method of heating the material to heat the film, a method combining these, or the like can be selected as appropriate.

Moreover, the silver layer formed by application | coating and drying of the solution containing a silver complex compound may be heat-processed after the 2nd adjacent layer formation process is complete | finished.
The drying conditions are not particularly limited, and any conditions may be used as long as the solvent is dried.
The heat treatment conditions are preferably 15 minutes or more in the temperature range of 80 ° C. to 120 ° C., 5 minutes or more in the temperature range of 121 ° C. to 150 ° C., or 1 minute or more in the temperature range of 151 ° C. to 200 ° C., 165 More preferably, it is 1 minute and 30 seconds or more in the temperature range of ℃ to 200 ℃.

  After the silver layer forming step, a first adjacent layer forming step in which a first coating liquid is applied to the surface of the base material and dried to form a first adjacent layer, or the side of the silver layer having the base material On the opposite side, a second adjacent layer forming step in which the second coating liquid is applied and dried to form a second adjacent layer, or a first adjacent layer forming step and a second adjacent layer forming step can be provided. .

-1st adjacent layer formation process-
In the case of having the first adjacent layer forming step, in this step, the first adjacent layer is formed by applying and drying the first coating liquid on the surface of the base material before the solution containing the silver complex compound is applied. Form. Thereby, for example, an undercoat layer can be provided on the substrate.

The first coating liquid is prepared by mixing the above-described photocurable resin or thermosetting resin, and, if necessary, a solvent, a reducing agent, a compound having a polymerizable double bond, and various additives. can do.
The solid content concentration of the coating solution is preferably 1% by mass to 30% by mass from the viewpoint of forming the first adjacent layer having excellent adhesion with uniformity.

Although the formation method of a 1st adjacent layer is not specifically limited, The method etc. of apply | coating and drying a 1st coating liquid on the base-material surface, and also making it harden | cure by ultraviolet irradiation or heating are mentioned.
Application and drying can be performed by applying the same method as in the silver layer forming step.
The ultraviolet irradiation can be performed using a light source such as an ultraviolet lamp or a mercury lamp.
The heating can be performed by, for example, a method of applying radiant heat to the coating film, a method of heating the substrate, or the like.

-Second adjacent layer forming step-
In the case of having the second adjacent layer forming step, after forming the silver layer on the surface of the base material or the surface of the first adjacent layer on the base material, in this step, the side opposite to the side having the base material of the silver layer Then, a second coating liquid is applied and dried to form a second adjacent layer. Thereby, for example, when the second adjacent layer is the outermost layer, it can be a layer for the purpose of surface protection of the silver layer.

The second coating liquid is prepared by mixing the above-described photocurable resin or thermosetting resin, and, if necessary, a solvent, a reducing agent, a compound having a polymerizable double bond, and various additives. can do.
The solid content concentration of the coating solution is preferably 1% by mass to 30% by mass from the viewpoint of forming the first adjacent layer having excellent adhesion with uniformity.

The method for forming the second adjacent layer is not particularly limited, and examples thereof include a method in which the second coating liquid is applied to the surface of the silver layer, dried, and further cured by ultraviolet irradiation or heating.
Application and drying can be performed by applying the same method as in the silver layer forming step.
The ultraviolet irradiation can be performed using a light source such as an ultraviolet lamp or a mercury lamp.
The heating can be performed by, for example, a method of applying radiant heat to the coating film, a method of heating the substrate, or the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(Example 1)
-Formation of silver layer-
Silver prepared by the following method on the surface (S1 surface) of the polyethylene terephthalate (PET) film (Toyobo Co., Ltd., Cosmo Shine A-4100, thickness: 100 μm) prepared as a base material on the side not subjected to easy adhesion treatment The layer forming coating solution was applied by a bar coating method and dried at 165 ° C. for 2 minutes to prepare a light reflecting film which is a laminate of the present invention. The application was performed by adjusting the bar number so that the thickness after drying was about 0.1 μm.

(Preparation of silver layer forming coating solution)
As a silver complexing agent, 12.9 parts of 2-ethylhexylamine (2EHA), 2.7 parts of silver carbonate, and 18 parts of water were mixed and stirred to prepare a coating solution for forming a silver layer.

(Example 2)
In Example 1, light reflection was performed in the same manner as in Example 1 except that the coating of the silver layer forming coating solution was changed from the S1 surface to the surface (S2 surface) on which the PET film was easily adhered. A film was prepared.

(Example 3)
In Example 2, the amount of water in the silver layer-forming coating solution was changed from 18 parts to 1.8 parts, and a light reflecting film was prepared in the same manner as in Example 2 except that 9.6 parts of methanol was added. Produced.

Example 4
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that the amount of 2EHA was changed as shown in Table 1.

(Example 5)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that the amount of 2EHA was changed as shown in Table 1.

(Example 6)
In Example 3, a light reflecting film was produced in the same manner as Example 3 except that the amount of water was changed as shown in Table 1.

(Example 7)
In Example 3, the light reflection film was produced like Example 3 except having changed the quantity of water.

(Example 8)
A light reflecting film was produced in the same manner as in Example 3 except that the amount of methanol was changed as shown in Table 1 in Example 3.

Example 9
A light reflecting film was produced in the same manner as in Example 3 except that the amount of methanol was changed as shown in Table 1 in Example 3.

(Example 10)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that methanol was changed to ethanol.

(Example 11)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that methanol was changed to isopropanol.

(Example 12)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that methanol was changed to 1-methoxy-2-propanol.

(Example 13)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that methanol was changed to acetone.

(Example 14)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that methanol was changed to ethyl methyl ketone.

(Example 15)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was changed to 2-ethylbutylamine (2EBA).

(Example 16)
-Formation of undercoat layer-
An undercoat layer aqueous composition having the following composition was applied to the S1 surface of a PET film (Toyobo Co., Ltd., Cosmo Shine A-4100) by the bar coating method, dried at 150 ° C. for 2 minutes, A layer was formed. The application was performed by adjusting the bar number so that the thickness after drying was about 0.1 μm. The undercoat layer forming surface of the PET film having this undercoat layer is referred to as “S3 surface”.
Then, in Example 3, a light reflecting film was produced in the same manner as in Example 3 except that the coating of the silver layer forming coating solution was changed from the S1 surface to the S3 surface of the PET film having an undercoat layer. did.
<Composition of aqueous composition for undercoat layer>
-Tin oxide fine particle dispersion (fine particle solid content: 20% by mass) ... 8 parts (FS-10D, manufactured by Ishihara Sangyo Co., Ltd.)
・ Polyurethane: 2.8 parts (Mitsui Chemicals, Takelac WS-5100)
Crosslinking agent: 4.2 parts (manufactured by Nisshinbo Chemical Co., Ltd., 10% by weight diluted solution of Carbodilite V-02-L2)
Surfactant A: 0.2 part (manufactured by Sanyo Chemical Industries, 10% by weight aqueous solution of sanded BL, anionic)
・ Surfactant B: 0.2 part (manufactured by Sanyo Chemical Industries, 10% by weight diluted solution of NAROACTY CL-95, nonionic)
・ Water: 84.6 parts

(Example 17)
In Example 16, a light reflecting film was produced in the same manner as in Example 16 except that methanol was replaced with isopropylamine.

(Example 18)
In Example 17, a light reflecting film was produced in the same manner as in Example 17 except that silver carbonate was replaced with silver oxide.

(Example 19)
In Example 16, a light reflecting film was produced in the same manner as in Example 16 except that silver carbonate was replaced with silver nitrate.

(Example 20)
In Example 16, a light reflecting film was produced in the same manner as in Example 16 except that silver carbonate was replaced with silver acetate.

(Example 21)
In Example 19, a light reflecting film was produced in the same manner as in Example 19 except that 0.1 part of formic acid was further added.

(Example 22)
In Example 20, a light reflecting film was produced in the same manner as in Example 20 except that 0.1 part of formic acid was further added.

(Comparative Example 1)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that the silver layer forming coating solution was replaced with the following silver layer forming coating solution.
(Preparation of silver layer forming coating solution)
As a silver complexing agent, 1.64 parts of n-butylamine, 0.34 part of silver nitrate, and 6.88 parts of methanol were mixed, stirred, and then stirred to prepare a coating solution for forming a silver layer.

(Comparative Example 2)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that the silver layer forming coating solution was replaced with the following silver layer forming coating solution.
(Preparation of silver layer forming coating solution)
As a silver complexing agent, 7.3 parts of n-butylamine, 0.34 part of silver nitrate, 1.8 parts of water, and 9.6 parts of methanol are mixed, stirred, and then stirred to form a silver layer forming coating. A liquid was prepared.

(Comparative Example 3)
In Example 2, a light reflecting film was produced in the same manner as in Example 2 except that water and a polar solvent (methanol) were not added.

(Comparative Example 4)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that water was not added.

(Comparative Example 5)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was replaced with diethylamine.

(Comparative Example 6)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was replaced with n-butylamine.

(Comparative Example 7)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was replaced with triethylamine.

(Comparative Example 8)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was replaced with isopropylamine.

(Comparative Example 9)
In Example 3, a light reflecting film was produced in the same manner as in Example 3 except that 2EHA was replaced with hexylamine.

(Evaluation)
-1. Reflectivity (reflectance at a specific wavelength)-
About the light reflection film in which the silver layer was formed as a light reflection layer on the PET film, the reflectance of the silver layer (the reflectance of the light reflection film) was measured. Specifically, using an ultraviolet-visible near-infrared spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), an aluminum (Al) substrate is measured as a reference, and the wavelength of the silver layer is 400 nm based on the literature value of Al. The light reflectance (%) was calculated.
If the reflectance is 20% or more, a light reflection function can be obtained, but a range exceeding 85% is preferable, and a range exceeding 90% is more preferable.

-2. Adhesiveness
About the light reflection film in which the silver layer was formed as a light reflection layer on PET film, the adhesiveness in a high-humidity environment was evaluated. Specifically, the light reflection film was stored in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 240 hours, and the presence or absence of peeling of the silver layer from the PET film as the substrate was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: No peeling was observed.
B: Peeling occurred only at the end.
C: Peeling was observed on the entire surface.

As shown in Table 1, in the Examples, a high light reflectance was obtained and the adhesion to the substrate was excellent. In Example 18 in which silver carbonate was replaced with silver oxide, isopropylamine was used as the polar solvent, and good light reflectance was obtained. Further, in Examples 19 and 20 in which silver carbonate was replaced with silver nitrate or silver acetate, the light reflectance was about 20%. However, by adding formic acid, the light reflectance almost equal to that of the other examples was obtained. Obtained.
On the other hand, in the comparative example, only a light reflectance of less than 10% was obtained.

  The laminate of the present invention and the manufacturing method thereof can be suitably used in various fields such as a reflector (for example, a reflector) that reflects light such as sunlight, a mirror film, an antibacterial coating, a conductive film, and a heat conductor. it can. As a suitable specific example of the laminate of the present invention and the method for producing the same, use as a reflecting mirror for collecting sunlight (so-called sunlight collecting film mirror) can be mentioned.

Claims (17)

A substrate;
A silver layer provided on a substrate and formed by application of a solution containing at least a silver compound represented by the following formula (A), an amine compound represented by the following formula (B), and water; ,
A laminate having
Ag _n X (A)
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and The substituent selected from these derivatives is represented. n represents an integer of 1 to 4.
In formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.   The laminate according to claim 1, wherein the solution further contains a polar solvent.   The laminate according to claim 2, wherein the polar solvent is an alcohol solvent or an amine solvent.   The solution contains 3 mol to 30 mol of the amine compound represented by the formula (B), 3 mol to 30 mol of water, and 1 mol of the silver compound represented by the formula (A). The laminate according to claim 2 or 3, comprising 10 to 100 mol of a polar solvent.   The laminate according to any one of claims 1 to 4, wherein the silver compound is at least one selected from silver oxide, silver carbonate, silver nitrate, and silver acetate.   The laminate according to any one of claims 1 to 5, wherein the solution further contains a reducing agent. The laminate according to claim 6, wherein the reducing agent is a compound represented by the following formula (1).
R-COOH Formula (1)
In formula (1), R represents a hydrogen atom or a monovalent functional group having one or more aldehyde groups.   The laminate according to any one of claims 1 to 7, wherein the base material has an easy-adhesion layer on at least one surface, and has the silver layer on a surface of the easy-adhesion layer.   The reflecting plate provided with the laminated body of any one of Claims 1-8.   The antibacterial coat provided with the laminated body of any one of Claims 1-8.   The conductor provided with the laminated body of any one of Claims 1-8.   The heat conductor provided with the laminated body of any one of Claims 1-8. On the substrate, a solution containing at least a silver compound represented by the following formula (A), an amine compound represented by the following formula (B), and water is applied and dried to form a silver layer. The manufacturing method of the laminated body which has a process to do.
Ag _n X (A)
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (B)
In formula (A), X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetate, acetylacetonate, carboxylate, and The substituent selected from these derivatives is represented. n represents an integer of 1 to 4.
In formula (B), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.   The method for producing a laminate according to claim 13, wherein the solution further contains a polar solvent.   The method for producing a laminate according to claim 14, wherein the polar solvent is an alcohol solvent or an amine solvent.   The solution contains 3 mol to 30 mol of the amine compound represented by the formula (B), 3 mol to 30 mol of water, and 1 mol of the silver compound represented by the formula (A). The manufacturing method of the laminated body of Claim 14 or Claim 15 containing 10-100 mol of polar solvents.   The said silver compound is at least 1 sort (s) selected from silver oxide, silver carbonate, silver nitrate, and silver acetate, The manufacturing method of the laminated body of any one of Claims 13-16.