JP2012143955A - Coated body - Google Patents

Abstract

【Task】
To provide a coated body provided with an ultraviolet curable topcoat layer that protects a silver thin film and does not deteriorate the adhesion to the silver thin film for long-term light resistance, weather resistance, and moist heat resistance tests.
[Solution]
In a coated body in which a silver thin film layer and a topcoat layer are sequentially provided directly on the surface of the substrate or on the undercoat layer provided on the substrate, the topcoat layer is formed from a photopolymerization initiator and an ultraviolet curable resin. And a coated body comprising a (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound.
[Selection figure] None

Description

  The present invention relates to a coated body having a silver thin film layer excellent in long-term storage stability.

  Since a coated body having a silver thin film layer has an excellent metallic luster, it is processed into a metal or plastic surface and used as a designable material or a reflective material. In many cases, the silver thin film layer is provided with a hard coat material as a top coat layer on the surface because the surface is easily damaged and is easily deteriorated in the air. Furthermore, the silver thin film layer is difficult to adhere to the hard coat material, and discoloration of the silver thin film layer may occur due to long-term use. For this reason, there are cases where use outdoors, particularly exposed to light, humidity, etc., may be restricted, and it has not been freely used in a wide range of applications.

  In order to protect the silver thin film layer, it is known to provide a top coat layer made of a thermosetting resin as a hard coating agent on the silver thin film layer. As a top coat layer for protecting the silver thin film layer obtained by the vapor deposition method, Patent Document 1 discloses a modified silicone resin, Patent Document 2 includes an acrylic / isocyanate-cured transparent resin, and Patent Document 3 includes an acrylic resin. It is disclosed that a melamine-based resin is used. As a top coat layer for protecting the silver thin film layer obtained by the silver mirror reaction, it is patented in Patent Document 4 that liquid epoxy resin, unsaturated polyester resin, fluororesin, acrylic resin, melamine resin, and silicon resin are used. Document 5 discloses the use of a silicon acrylic resin, and Patent Document 6 discloses the use of a two-component curable polyurethane resin or an acrylic-modified silicon resin. These are all thermosetting resins, and need to be placed in a high-temperature environment for a long time of about 60 ° C. or more for about 60 minutes in order to sufficiently perform drying or polymerization. For this reason, there exists a problem that the process time for forming a topcoat layer becomes long. In order to shorten the process time, it is conceivable to use an ultraviolet curable resin. In Patent Document 7 and Patent Document 8, although there is a description that an ultraviolet curable resin or an electron beam curable resin may be used as a top coat layer for protecting the silver thin film layer, there is no example actually used. . This is because UV curable resin is inferior in adhesion to the silver thin film layer, so there is much room for improvement such as inferior durability such as heat resistance, weather resistance, and light resistance, and it can be used in a wide range of applications that require long-term use. It is because it has not reached.

  On the other hand, in order to improve the light resistance of resins and the like, it is generally known to add ultraviolet absorbers, antioxidants, light stabilizers, etc., but even if these materials are used, the resin layer Regarding the adhesion between the silver thin film layer and the silver thin film layer, it was not possible to improve the durability after a long-term test such as wet heat resistance, weather resistance, and light resistance. In addition, in order to prevent bleeding out of a compound having an ultraviolet absorbing site and an antioxidant site, an ultraviolet absorber and an antioxidant having a (meth) acryloyl group that reacts directly with an ultraviolet curable resin are also generally known. A compound.

  As an example of the use of the (meth) acryloyl group-containing ultraviolet absorbing compound, for example, in Patent Document 9, it is used as an additive in the ultraviolet curable resin of the hard coat layer, that is, added as an ultraviolet absorber, light or It is described that an effect of suppressing discoloration due to heat, particularly yellowing can be expected. Patent Document 10 discloses a copolymer obtained by copolymerization of a polymerizable unsaturated monomer such as a benzotriazole type, a benzophenone type, or a benzophenol type with a (meth) acryloyl group introduced therein. A photocurable coating composition containing a polymer is used, and unlike the conventional photocurable coating composition containing a low molecular weight UV absorber, the problem of bleeding out of the UV absorber is solved. There is a description. In Patent Document 11, an undercoat layer in the case of painting on a plastic surface is composed of a UV-absorbing silicone coating film, which is formed by copolymerization of an organosilane oligomer and a (meth) acrylic acid ester having a UV-absorbing group. It is formed from an ultraviolet absorbing silicone coating material resin composition containing an acrylic resin, a silanol group-containing polyorganosiloxane, silica, and a curing catalyst. In Patent Document 12, as a film composition, for example, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole as an ultraviolet absorbing monomer and an unsaturated monomer A film obtained by copolymerizing a monomer composition containing cyclohexyl methacrylate as a polymer is disclosed.

  Thus, (meth) acryloyl group-containing UV-absorbing compounds are generally used as UV-absorbing agents and prevent bleeding out because the apparent molecular weight increases by reacting with polymerizable unsaturated monomers in advance. Although the effect as is known, the effect as an ultraviolet absorber is not much different from other ultraviolet absorbers, the resin layer containing them is applied to the top coat layer of the silver thin film layer, Furthermore, there has been no mention of an effect of improving durability with respect to adhesion to the silver thin film layer.

JP 2000-106017 A Japanese Patent Application Laid-Open No. 2004-77643 JP 2009-286100 A JP 2000-129448 A JP 2003-155580 A JP 2002-256445 A JP 2008-110101 A JP 2008-176050 A JP 2007-58101 A JP 2007-238823 A JP 2001-270044 A JP-A-9-3134

  The present invention provides a coated body having a silver thin film layer that has a short manufacturing process time and is excellent in light resistance, weather resistance, wet heat resistance, etc. by providing a top coat layer made of an ultraviolet curable resin on the silver thin film layer. Is to provide.

  As a result of various studies to solve the above problems, in a coated body in which a silver thin film layer and a topcoat layer are sequentially provided directly on the surface of the substrate or on the undercoat layer provided on the surface of the substrate. The top coat layer is composed of a photopolymerization initiator and an ultraviolet curable resin, and contains a (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound, so that the production process time is short and the light resistance and weather resistance are Thus, it was possible to provide a coated body having a silver thin film layer that can withstand long-term storage, and so on, and solved the problem.

  The silver thin film layer is preferably composed of a silver thin film layer formed by a silver mirror reaction. Further, the (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound is preferably 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole. Furthermore, it is preferable to contain 1-10 mass% of this ultraviolet absorptive compound with respect to ultraviolet curable resin in a topcoat layer.

  According to the present invention, it was possible to obtain a coated body having a stable adhesion between the silver thin film layer and the top coat layer even for a long-term weather resistance, light resistance and wet heat resistance test. In particular, it can be used without any restrictions even outdoors exposed to light and humidity. Thereby, it can be widely used indoors and outdoors as a metal base material, a material having excellent metallic luster on the surface of a plastic base material, an excellent design property, a reflective material, an electromagnetic shielding material, or the like.

  The inventors have used an ultraviolet curable resin capable of shortening the manufacturing time of the top coat layer, and in studying a top coat material whose adhesion to the silver thin film layer does not decrease even under long-term storage, By using a (meth) acryloyl group-containing benzotriazole-type UV-absorbing compound in combination with the resin, we found the effect of maintaining adhesion to the silver thin film layer under long-term storage that was not seen with ordinary UV absorbers. . Furthermore, it was an unexpected effect that adhesion was maintained not only in the light resistance test and the weather resistance test but also in the moist heat resistance test.

  The (meth) acryloyl group-containing benzotriazole type UV-absorbing compound used in the present invention is a compound having a benzotriazole structure and a (meth) acryloyl group in the molecule, such as 2- [2′-hydroxy-5 ′. -(Methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-( [Acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxy) Propyl) phenyl] -2H-benzotriazole, 2- [2 -Hydroxy-5 '-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 '-(acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-( Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5' -(Methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [ '-Hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-t-butyl-2H -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, 2- [2'-hydroxy-3'-(2-propenyl) -5 '-T-butylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-(2-propenyl) -5'-t-octylphenyl) benzotriazole, 2- [2'-hydroxy-3 '-Isopropenyl-5'-t-butylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-isopro Penyl-5'-t-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-2- (2-methacryloyloxyethoxycarbonyl) ethylphenyl] -2H- Benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-2- (2-acryloyloxyethoxycarbonyl) ethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 ' -(Β-Methacryloyloxyethoxy) -3'-t-butylphenyl] -4-t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(β-methacryloyloxyethoxy) -3' -T-butylphenyl] -5-t-butyl-2H-benzotriazole and the like. These can be used appropriately, but 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole is particularly preferably used. The addition amount is preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass with respect to the ultraviolet curable resin. If it is less than 0.5% by mass, the adhesion between the silver thin film layer and the topcoat layer may not be sufficiently improved during storage, and if it exceeds 15% by mass, the effect may be saturated and not greatly improved. Further, since an extra material is used, it is not preferable in terms of cost.

  The method for producing the coated body having the silver thin film layer of the present invention is not particularly limited. For example, the surface of the base material is surface-treated as necessary, or an anchor agent is applied to the base material, and the adhesion is achieved. After the treatment for improving the property, an undercoat layer is provided. A silver thin film layer is provided on the surface of the undercoat layer. By providing the top coat layer according to the present invention on the surface of the silver thin film layer, a coated body having a silver thin film layer that is stable for a long period of time can be obtained.

This will be described in more detail.
As the base material used in the present invention, various plastics, metals, glasses, rubbers and the like are used. Examples of the plastics include polycarbonate resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin, phenol resin, polyethylene terephthalate (PET) resin, polyester resin such as polybutylene terephthalate (PBT) resin, fluorine resin, polypropylene ( PP) resin, a resin obtained by compounding these, and fiber reinforced plastic (FRP) reinforced with organic fibers such as nylon fiber and pulp fiber may be mentioned, but not particularly limited. Examples of the metal include, but are not limited to, iron, aluminum, stainless steel, copper, and brass. The glass is not particularly limited, such as inorganic glass or plastic glass.

  A pretreatment may be performed in order to improve the adhesion between these base materials and the undercoat layer. As the pretreatment method, a wet process such as a cleaning process using detergent, solvent cleaning or ultrasonic cleaning, or a dry process such as corona treatment, ultraviolet irradiation or electron beam irradiation is performed. In addition, a paint (anchor agent) having adhesiveness is provided on both the base material and the undercoat layer.

  The undercoat layer is required to have good adhesion to the substrate and excellent adhesion to the silver thin film provided on the undercoat layer. It is also required to form a smooth surface. Examples of undercoat materials include alkyd polyols, polyester polyols, acrylic polyols and the like, polyol-based paints in which isocyanate compounds are mixed as curing agents with polymers or oligomers having terminal hydroxyl groups, and epoxy resins in which amine compounds are mixed as curing agents. A system paint or the like is selected based on the properties required for the substrate and the coated body. The thickness of the undercoat layer is preferably 5 to 30 μm, but is not particularly limited.

  As a method of forming a silver thin film layer on the undercoat layer, vapor deposition or sublimation is performed by heating and evaporating or sublimating metallic silver in a vacuum vessel to form a silver thin film by adhering to the surface of the substrate, and argon in the vacuum vessel. A sputtering method in which a gas is filled, a high voltage is applied between the substrate and the target, ionized argon collides with the target, and the repelled metal atoms are formed on the substrate, and a silver thin film is previously formed on the surface of a film or the like. There are dry methods such as a transfer method for transferring to a substrate, and wet methods such as plating for forming a metal by a chemical reaction. The optimum method is selected depending on the application.

  The wet method is preferably used because it is not necessary to form a silver thin film in a vacuum vessel, and thus it can be processed continuously with other steps and productivity can be improved.

  The thickness of the silver thin film layer is preferably 20 to 300 nm, and more preferably 50 to 250 nm. If the thickness is less than 20 nm, the reflectivity may not be sufficient because the film thickness of silver is not sufficient, and even if the film thickness exceeds 300 nm, the reflectivity is almost constant, and extra silver is used, which is costly. Is also not preferable.

  Next, a method for forming a silver thin film layer by a chemical plating method (electroless plating method) using a silver mirror reaction, which is preferable as a method for forming a silver thin film layer, will be described.

  In order to deposit silver on the surface of the undercoat layer, first, stannous ions are supported on the surface of the undercoat layer using an activation treatment liquid containing stannous chloride or the like as a catalyst. As the method, there are a method of immersing a substrate provided with an undercoat layer in an activation treatment solution, a method of applying an activation treatment solution containing stannous chloride or the like on the surface of the undercoat layer, and the like. Although it can select arbitrarily by the shape of a base material etc., as an application | coating method, the spray application which does not choose the shape of a base material especially is suitable. Further, the activation treatment liquid adhering to the surface of the undercoat layer is washed with deionized water or purified distilled water.

  Next, treatment with an aqueous metal salt solution is preferably performed. Silver is preferably used as the metal, and an aqueous silver nitrate solution is preferred as the aqueous metal salt solution. A silver nitrate concentration of about 0.01 mol / L is made into a more dilute solution, and this is brought into contact with the surface subjected to the activation treatment alone. This treatment step is performed by immersing the substrate that has been activated in the aqueous solution of the metal salt compound or by applying an aqueous solution of the metal salt compound to the surface that has been activated. In particular, spray coating is preferred.

  Next, by applying two liquids of an ammoniacal silver nitrate solution containing silver nitrate and ammonia and a reducing agent solution containing a reducing agent and a strong alkali component so as to be mixed on the treated surface, an oxidation-reduction reaction occurs. Metallic silver is deposited and a silver coating is formed to form a silver thin film layer.

  As the reducing agent solution, an aldehyde compound such as glucose or glyoxal, an organic compound such as a hydrazine compound such as hydrazine sulfate, hydrazine carbonate or hydrazine hydrate, or an aqueous solution such as sodium sulfite or sodium thiosulfate is preferably used.

  Several additives may be added to the aqueous silver solution in order to produce good silver. For example, monoethanolamine, tris (hydroxymethyl) aminomethane, 2-amino-2-hydroxymethyl-1,3-propanediol, 1-amino-2-propanol, 2-amino-1-propanol, diethanolamine, diisopropanol Examples include amino alcohol compounds such as amine, triethanolamine and triisopropanolamine, amino acids such as glycine, alanine and sodium glycine, and salts thereof, but are not particularly limited.

  As a method of applying the two solutions of the ammoniacal silver nitrate solution and the reducing agent solution so as to be mixed on the surface of the undercoat layer, two kinds of aqueous solutions are mixed in advance, and this mixed solution is used with a spray gun or the like. A method of spraying on the surface of the coating layer, a method of spraying using a concentric spray gun having a structure in which two types of aqueous solutions are mixed and immediately discharged in the head of the spray gun, and a two-head spray having two spray nozzles for the two types of aqueous solutions There are a method of spraying and spraying each from a gun, a method of spraying two kinds of aqueous solutions simultaneously using two separate spray guns, and the like. These can be arbitrarily selected according to the situation.

  Subsequently, the surface of the silver thin film layer is washed with deionized water or purified distilled water, and after removing the silver mirror reaction solution and the like remaining on the surface, in order to stabilize the deposited metallic silver, If necessary, a treatment such as immersion in a solution containing an organic compound having a reaction or affinity with silver or coating the solution can be performed.

  As the organic compound, a nitrogen-containing heterocyclic compound having a mercapto group or a thione group is effectively used. Speaking of the heterocyclic ring of the nitrogen-containing heterocyclic compound, there are imidazole, imidazoline, thiazole, thiazoline, oxazole, oxazoline, pyrazoline, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Imidazole, triazole and tetrazole are preferred. Specific examples include 2-mercapto-4-phenylimidazole, 2-mercapto-1-benzylimidazole, 2-mercapto-benzimidazole, 1-ethyl-2-mercapto-benzimidazole, 2-mercapto-1-butyl-benzimidazole. 1,3-diethyl-benzimidazoline-2-thione, 1,3-dibenzyl-imidazolidine-2-thione, 2,2'-dimercapto-1,1'-decamethylene-diimidazoline, 2-mercapto-4- Phenylthiazole, 2-mercapto-benzothiazole, 2-mercaptonaphthothiazole, 3-ethyl-benzothiazoline-2-thione, 3-dodecyl-benzothiazoline-2-thione, 2-mercapto-4,5-diphenyloxazole, 2 -Mercaptobenzoxazole, -Pentyl-benzoxazoline-2-thione, 1-phenyl-3-methylpyrazolin-5-thione, 3-mercapto-4-allyl-5-pentadecyl-1,2,4-triazole, 3-mercapto-5-nonyl 1,2,4-triazole, 3-mercapto-4-acetamido-5-heptyl-1,2,4-triazole, 3-mercapto-4-amino-5-heptadecyl-1,2,4-triazole, 2- Mercapto-5-phenyl-1,3,4-thiadiazole, 2-mercapto-5-phenyl-1,3,4-thiadiazole, 2-mercapto-5-n-heptyl-oxathiazole, 2-mercapto-5-n Heptyl-oxadiazole, 2-mercapto-5-phenyl-1,3,4-oxadiazole, 2-heptadecyl-5-thio Nyl-1,3,4-oxadiazole, 5-mercapto-1-phenyl-tetrazole, 2-mercapto-5-nitropyridine, 1-methyl-quinoline-2 (1H) -thione, 3-mercapto-4- Methyl-6-phenyl-pyridazine, 2-mercapto-5,6-diphenyl-pyrazine, 2-mercapto-4,6-diphenyl-1,3,5-triazine, 2-amino-4-mercapto-6-benzyl- Examples include 1,3,5-triazine, 1,5-dimercapto-3,7-diphenyl-s-triazolino [1,2-a] -s-triazoline.

  Since the metallic silver thus formed is easily damaged, a top coat layer is further provided on the surface of the silver thin film layer. As the topcoat resin composition constituting the topcoat layer, a thermosetting resin is generally used, but in the present invention, an ultraviolet curable resin having a short manufacturing process time is used. The topcoat resin composition basically comprises an ultraviolet curable resin, a photopolymerization initiator, and a (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound according to the present invention, but does not adversely affect the effects of the present invention. Within the range, various additives may be included in the resin composition as necessary.

  As the ultraviolet curable resin used in the present invention, a monomer and an oligomer compound mainly containing an ethylenically unsaturated group are preferably used, which include an electron curable resin and is cured with ultraviolet rays and an electron beam. Specific examples include amide monomers, (meth) acrylate monomers, urethane (meth) acrylates, polyester (meth) acrylates, and epoxy (meth) acrylates. Examples of amide monomers include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine. Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxy-3-phenylpropyl acrylate as (meth) acrylate monomers; phenoxyethyl (meth) acrylate, etc. Acrylates of phenolic alkylene oxide adducts and their halogen nucleus substitutes; mono- or di (meth) acrylates of ethylene glycol, mono (meth) acrylates of methoxyethylene glycol, mono- or di (meth) acrylates of tetraethylene glycol, Mono- or di (meth) acrylates of glycols such as mono- or di (meth) acrylate of tripropylene glycol; trimethylolpropane tri (meth) acrylate, pentae Polyols such as sitolitol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, and (meth) acrylic acid ester of alkylene oxide thereof, isocyanuric acid EO modified di- or tri (meth) acrylates, etc. Can be mentioned.

  Examples of urethane (meth) acrylates include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a reaction product of a polyol and an organic polyisocyanate. Here, examples of the polyol include a low molecular weight polyol, a polyether polyol, and a polyester polyol. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexane dimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol, and examples of the polyester polyol include these low molecular weight polyols and / or polyether polyols, adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. Examples thereof include a reaction product with an acid component such as a dibasic acid such as an acid or an anhydride thereof. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

  Examples of the polyester (meth) acrylates include a dehydration condensate of a polyester polyol and (meth) acrylic acid. Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and these And a reaction product from a polyol such as an alkylene oxide adduct and an acid component such as a dipic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or an anhydride thereof. Epoxy (meth) acrylates are those obtained by addition reaction of unsaturated carboxylic acid such as (meth) acrylic acid to epoxy resin. Epoxy (meth) acrylate, phenol or cresol novolac type epoxy resin of bisphenol A type epoxy resin And (meth) acrylic acid addition reactant of diglycidyl ether of polyether.

  Properties required for the photopolymerization initiator used in the present invention include good stability, low yellowing and low odor. Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2. Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one , Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone, 2,4-dimethylthio Thioxanthones such as sandton, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylpyroxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Monoacylphosphine oxides such as bisacylphosphine oxides, benzophenones such as benzophenone, and xanthones. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator. The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.

  In order to cure the topcoat layer having the above composition, irradiation with an electron beam, ultraviolet rays or the like may be performed, but ultraviolet irradiation is generally used from the viewpoint of cost. The light source used for ultraviolet irradiation preferably has a light emission distribution at a wavelength of 420 nm or less. For example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, or a low pressure mercury lamp. And laser light sources such as argon ion laser, YAG laser, excimer laser, and nitrogen laser. The amount of ultraviolet irradiation is appropriately selected as necessary.

  The thickness of the top coat layer is preferably in the range of 1 to 15 μm. If the top coat layer is too thin, the function of protecting the silver thin film layer cannot be obtained. Conversely, if the top coat layer is too thick, the light transmission distance becomes longer, resulting in increased light loss and reduced reflectance. It is not preferable.

  Further, various additives that may be added to the topcoat layer as necessary include, for example, coloring materials, fine particles, antioxidants, other ultraviolet absorbers, viscosity modifiers, silane coupling agents, and the above silver thin films. And nitrogen-containing heterocyclic compounds having a mercapto group or thione group, thiol-based compounds, phosphite-based compounds, and other nitrogen-containing heterocyclic compounds.

  As the color material, pigments and dyes are used. It is more preferable that the absorption wavelength of the color material does not include the absorption wavelength of the photopolymerization initiator because it does not hinder the activity of the photopolymerization initiator. In addition, it is more preferable to use a highly transparent pigment or dye because a bright hue can be obtained. A pigment is preferably used when long-term storage stability is desired.

  Examples of pigments include organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and hansa yellow; inorganics such as titanium oxide, aluminum oxide, calcium carbonate, barium sulfate, mica, petal, and composite metal oxides. Examples thereof include, but are not limited to, pigments. One or a combination of two or more selected from these pigments can be used. The pigment is preferably used in a fine particle dispersed state. In order to obtain a fine particle dispersed state, there is no particular limitation in the case of a powder pigment in a method of directly dispersing in fine particles at the time of synthesis. In addition, there is a method in which pigment powder is finely dispersed directly by a paint shaker, a sand mill, a ball mill, a kneader, a dissolver, a homogenizer, ultrasonic vibration, a stirrer, or the like. At the time of dispersion, it is possible to use a dispersant, a dispersion aid, a thickener, a coupling agent and the like. The amount of pigment added is not particularly limited because the concealability varies depending on the type of pigment, but is preferably 0.01 to 10 parts by mass, and more preferably 0 to 100 parts by mass of the total solid content of each composition. .1 to 5 parts by mass. If the added amount of the pigment is less than 0.01 parts by weight, the color is light and a vivid hue may not be obtained. If the added amount exceeds 10 parts by mass, a vivid hue may not be obtained due to the dark color and the coating film may be obtained. The smoothness of the may deteriorate.

  Examples of dyes include azo, anthraquinone, indoidoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, and nitroso dyes. Although it is mentioned, it is not limited to these. One or a combination of two or more selected from these dyes can be used. The amount of the dye added is not particularly limited because the concealability varies depending on the type of the dye. For example, the total amount of each composition is 100 to 10 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0. .1 to 5 parts by mass. If the added amount of the pigment is less than 0.01 parts by weight, the color is light and a vivid hue may not be obtained. If the added amount exceeds 10 parts by mass, a vivid hue may not be obtained due to the dark color and the coating film may be obtained. The smoothness of the may deteriorate.

  Addition of fine particles to the topcoat layer is preferable from the viewpoint of adhesion to the silver thin film layer because the reaction heat during curing can be suppressed and the amount of cure shrinkage of the cured film can be reduced. The surface hardness can also be increased. As the fine particles, any of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be used.

  Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. However, since the fine particles generally tend to lower the transparency, it is necessary to adjust the filling method with a balance of various necessary characteristics.

  Generally, inorganic fine particles have low affinity with organic components such as the ultraviolet curable resin used in the present invention, so that they may form aggregates or the cracked top coat layer may be easily cracked by simply mixing them. In the present invention, in order to increase the affinity between the inorganic fine particles and the organic component, the surface of the inorganic fine particles can be treated with a surface modifier containing an organic component. The surface modifier preferably has a functional group capable of forming a bond with or adsorbing to the inorganic fine particles and a functional group having high affinity with the organic component in the same molecule.

  Examples of the surface modifier having a functional group capable of binding or adsorbing to the inorganic fine particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, phosphate groups, sulfate groups, sulfonate groups, carboxylic acid groups, and the like. A surface modifier having an anionic group is preferred.

  Furthermore, the functional group having high affinity with the organic component may be a group having only the organic component and hydrophilicity / hydrophobicity combined, but a functional group that can be chemically bonded to the organic component is preferable, such as an isocyanate compound or an amine compound. , Vinyl compounds, epoxy compounds, methacryloxy compounds, acrylic compounds, imide compounds, compounds having an alkyl group, and compounds having an aryl group.

  The surface modification of these inorganic fine particles is preferably performed in a solution. When inorganic fine particles are mechanically finely dispersed, the surface modifier is present together, or after finely dispersing the inorganic fine particles, the surface modifier is added and stirred, or before the fine particles are finely dispersed. A method may be used in which surface modification is performed and then fine dispersion is performed. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.

  Although there is no restriction | limiting in particular as organic fine particle, The polymer particle which consists of a monomer which has an ethylenically unsaturated group is used preferably. Examples thereof include polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyethylene, polypropylene, and polystyrene. Other examples include resin particles such as polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate, nylon, polyvinyl alcohol, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, acetylcellulose, nitrocellulose, and gelatin. . These particles are preferably crosslinked.

  For example, a general dyno mill, paint shaker, sand mill, ball mill, kneader, dissolver, homogenizer, ultrasonic vibration, stirrer or the like is preferably used as a disperser for refining fine particles. Further, as the dispersion medium, the above-mentioned solvent for surface modification is preferable, and it is possible to use a dispersant, a dispersion aid, a thickener, a coupling agent, and the like at the time of dispersion.

  The average particle size of the fine particles that can be used in the present invention is 1 to 20000 nm, more preferably 2 to 1000 nm, still more preferably 5 to 500 nm, and most preferably 10 to 200 nm. The shape of the crosslinked fine particles can be used without particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape. The filling amount of the fine particles is preferably 2 to 70% by volume, more preferably 10 to 60% by volume with respect to the volume of the film cured after filling.

  As a method for providing the topcoat layer, there is a method of applying and curing as a solvent-free type using a monomer of a low-viscosity ultraviolet curable resin, but a coating composition such as an ultraviolet curable resin is dissolved in an organic solvent. In general, it is applied as a paint. As a coating method, a conventionally known coating method may be used. For example, gravure roll method, reverse roll method, dip roll method, bar coater method, knife coater method, air spray method, airless spray method, dip method, etc. Can be used.

  Examples of the organic solvent include hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol, isopropyl alcohol, butyl alcohol, and cyclohexanol, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Esters such as methyl ethoxy acetate and ethyl ethoxy acetate, tetrahydrofuran, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol Cole monobutyl ether (butyl cellosolve), methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether (diethyl carbitol), propylene glycol monomethyl ether, propylene Examples include ethers such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Not intended to be. These organic solvents are selected depending on the solubility of the topcoat composition, but are also selected from the viewpoint of improving the coated surface state. Although it can be used alone, it is generally used in combination of two or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In addition, a part and% show a mass part and the mass%.

Example 1
The surface of the polycarbonate plate was degreased, washed with water and dried. A commercially available undercoat paint (Under Clear No. 0128, manufactured by Ohashi Chemical Co., Ltd.) is mixed with an organic solvent (methyl ethyl ketone and butyl cellosolve in a ratio of 1: 1) together with a curing agent (Cure Agent for Under Clear made by Ohashi Chemical Co., Ltd.). ) And the paint obtained by mixing at a ratio of 10: 2: 4, respectively, was applied by spraying using a spray gun. An undercoat layer having a thickness of 20 μm was formed by heating and drying at 80 ° C. for 2 hours to obtain a silver thin film layer forming surface.

  This silver thin film layer forming surface is subjected to an activation treatment by spraying an activation treatment liquid containing 0.15 mol of hydrochloric acid and 0.06 mol of stannous chloride as hydrogen chloride per 1000 parts of water with a spray gun, Washed with purified water. Subsequently, an activation treatment was performed by spraying a silver nitrate aqueous solution in which 10 parts of silver nitrate was dissolved in 1000 parts of deionized water with a spray gun. Thereafter, silver mirror plating was performed by a chemical plating method using a silver mirror reaction.

  The silver mirror plating solution was prepared as follows. Separately from a silver nitrate solution obtained by dissolving 20 parts of silver nitrate in 1000 parts of deionized water, 100 parts of 28% aqueous ammonia solution and 5 parts of monoethanolamine were dissolved in 1000 parts of deionized water to prepare an ammonia solution. Prior to use, the silver nitrate solution and the ammonia solution were mixed one-to-one to obtain an ammoniacal silver nitrate solution. Next, 10 parts of hydrazine sulfate, 5 parts of monoethanolamine and 10 parts of sodium hydroxide were dissolved in 1000 parts of deionized water to prepare a reducing agent solution.

  The obtained ammoniacal silver nitrate solution and the reducing agent solution were simultaneously sprayed onto the surface subjected to the activation treatment using a double-head spray gun to form a silver thin film layer, and washed with purified water. It was dried in a dryer at 70 ° C. for 30 minutes.

Next, a top coat layer was provided on the silver thin film layer. 100 parts of acrylic silicon oligomer, 3 parts of photopolymerization initiator (Irgacure 184), 1.5 parts of pentaerythritol tetrakisthiopropionate, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl]- 0.8 part of 2H-benzotriazole was sufficiently dissolved in 280 parts of an organic solvent (mixing methyl ethyl ketone and butyl cellosolve in a ratio of 1: 1) to form a top coat paint, and spray-coated on the silver thin film layer with a spray gun. The topcoat paint was cured by irradiating with ultraviolet rays having an irradiation energy of about 800 mJ / cm ² with an ultraviolet irradiation device using a xenon lamp after being heated and dried at 80 ° C. for 15 minutes to form a topcoat layer having a thickness of 7 μm. Thus, the coating body which formed the silver thin film layer on the polycarbonate plate surface was obtained.

(Example 2)
Except that the addition amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 1.5 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Example 3)
Except that the addition amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 3.0 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

Example 4
Except that the addition amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 5.0 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Example 5)
Except that the addition amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 8.0 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Example 6)
Except that the added amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 10.0 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Example 7)
Except that the addition amount of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 1 was changed to 15.0 parts. A top coat paint was prepared in the same manner as in Example 1 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Example 8)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to 2- [2'-hydroxy-3 '-T-butyl-5'-2- (2-methacryloyloxyethoxycarbonyl) ethylphenyl] -2H-benzotriazole was prepared in the same manner as in Example 2 except that it was changed to 1.5 parts. A coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

Example 9
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to 2- [2'-hydroxy-5 '-(Β-Methacryloyloxyethoxy) -3'-t-butylphenyl] -5-t-butyl-2H-benzotriazole was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts. Thus, a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

(Comparative Example 1)
A top coat paint was prepared in the same manner as in Example 1 except that 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the top coat formulation of Example 1 was omitted. Thus, a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

(Comparative Example 2)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was 2- (2H-benzotriazol-2-yl). A top coat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts of -4-tert-octylphenol, to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Comparative Example 3)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 is 2- (2H-benzotriazol-2-yl) A topcoat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts of -6-dodecyl-4-methylphenol, to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Comparative Example 4)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was 2- (2H-benzotriazol-2-yl) A coated body in which a top coat paint was prepared in the same manner as in Example 2 except that 1.5 parts of -4,6-bis (α, α-dimethylbenzyl) phenol was changed, and a silver thin film layer was formed on the polycarbonate plate surface. Got.

(Comparative Example 5)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 is 3,5-di-tert-butyl-4- A coated body in which a top coat paint was prepared in the same manner as in Example 2 except that the hydroxybenzoic acid-2,4-di-tert-butylphenyl ester was changed to 1.5 parts, and a silver thin film layer was formed on the polycarbonate plate surface. Got.

(Comparative Example 6)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was converted to 2-hydroxy-4- (octyloxy) benzophenone 1 The top coat paint was adjusted in the same manner as in Example 2 except that the content was changed to 5 parts, thereby obtaining a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Comparative Example 7)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was 2- (4,6-diphenyl-1,3 , 5-triazin-2-yl) -5-hydroxyphenol Except for changing to 1.5 parts, a top coat paint was prepared in the same manner as in Example 2, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained. Obtained.

(Comparative Example 8)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to (2- [4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropyloxy] phenol Same as Example 2 except for changing to 1.5 parts Thus, a top coat paint was prepared to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Comparative Example 9)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to 2,4-bis (2-hydroxy-4- Butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine was changed to 1.5 parts, and the topcoat paint was prepared in the same manner as in Example 2 to obtain a polycarbonate plate surface. A coated body on which a silver thin film layer was formed was obtained.

(Comparative Example 10)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to 2-butyl-2- (4-hydroxy-3 , 5-di-tert-butylbenzyl) malonate bis (1,2,2,6,6-pentamethylpiperidin-4-yl) The coating material which adjusted the coating material and formed the silver thin film layer on the polycarbonate plate surface was obtained.

(Comparative Example 11)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to bis (1,2,2,6, sebacate). The topcoat paint was prepared in the same manner as in Example 2 except that the amount of 6-pentamethyl-4-piperidyl) ester was changed to 1.5 parts, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

(Comparative Example 12)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to bis (2,2,6,6-sebacate). Tetramethylpiperidin-4-yl) A topcoat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

(Comparative Example 13)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was 2- (2-hydroxy-3-tert-butyl). -5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate Except for changing to 1.5 parts, the topcoat paint was prepared in the same manner as in Example 2 to form a silver thin film layer on the polycarbonate plate surface. A painted body was obtained.

(Comparative Example 14)
1.5 parts of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was replaced with 2- [1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, except that the amount was changed to 1.5 parts. A coated body on which a silver thin film layer was formed was obtained.

(Comparative Example 15)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was replaced with 4,6-bis (octylthiomethyl) o- A top coat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts of cresol, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained.

(Comparative Example 16)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to pentaerythritol tetrakis [3- (3,5-di -Tert-butyl-4-hydroxy) phenyl) propionate] Except for changing to 1.5 parts, the topcoat paint was prepared in the same manner as in Example 2 to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface. It was.

(Comparative Example 17)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to thioethylenebis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate] A topcoat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained. .

(Comparative Example 18)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to octadecyl-3- (3,5-di-tert. A top coat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts of (butyl-4-hydroxyphenyl) propionate to obtain a coated body having a silver thin film layer formed on the polycarbonate plate surface.

(Comparative Example 19)
1.5 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole used in the topcoat formulation of Example 2 was added to hexamethylenebis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate] A topcoat paint was prepared in the same manner as in Example 2 except that the amount was changed to 1.5 parts, and a coated body having a silver thin film layer formed on the polycarbonate plate surface was obtained. .

<Evaluation test method>
The following evaluation test was done about the silver thin film coating body obtained in Examples 1-9 and Comparative Examples 1-19. The results are shown in Table 1.

1) Evaluation A (Adhesion)
A cross-cut was made on the surface of the coated body before the evaluation test so as to reach the base material with a cutter, the cellophane tape was strongly pressed, the cellophane tape was peeled off, and the determination was made based on the following criteria.
◯: Good with no peeling of the paint film.
(Triangle | delta): The coating film peeled off a little.
X: The coating film was all peeled off.

2) Evaluation B (heat resistance test)
The sample was left for 15 days in a hot air circulating dryer maintained at 80 ° C. A cross-cut was made on the surface of the coated body after the test so as to reach the base material with a cutter, and the cellophane tape was strongly pressed, and then the cellophane tape was peeled off and judged in the same manner as in the evaluation A standard.

3) Evaluation C (moisture and heat resistance test)
The sample was left for 10 days in a thermo-hygrostat maintained at 60 ° C. and a relative humidity of 95%. A cross-cut was made on the surface of the coated body after the test so as to reach the base material with a cutter, and the cellophane tape was strongly pressed, and then the cellophane tape was peeled off and judged in the same manner as in the evaluation A standard.

4) Evaluation D (light resistance test)
Using a xenon fade meter, xenon light was irradiated for 10 days in an environment of a bath temperature of 42 ° C. and a relative humidity of 50%. A cross-cut was made on the surface of the coated body after the test so as to reach the base material with a cutter, and the cellophane tape was strongly pressed, and then the cellophane tape was peeled off and judged in the same manner as in the evaluation A standard.

5) Evaluation E (scratch resistance test)
Using a xenon fade meter, irradiation with xenon light and intermittent pure water spraying were performed for 10 days in an environment where the temperature in the tank was 42 ° C. and the relative humidity was 50%. A cross-cut was made on the surface of the coated body after the test so as to reach the base material with a cutter, and the cellophane tape was strongly pressed, and then the cellophane tape was peeled off and judged in the same manner as in the evaluation A standard.

  As is clear from the evaluation results, a coated body having a silver thin film layer that is stable with respect to long-term weather resistance and light resistance tests can be obtained by the present invention, and it can be used without limitation even outdoors exposed to light and humidity. I was able to do that. Thereby, it can be widely used indoors and outdoors as a metal base material, a material having excellent metallic luster on the surface of a plastic base material, an excellent design property, a reflective material, an electromagnetic shielding material, or the like.

Claims (4)

  In a coated body in which a silver thin film layer and a topcoat layer are sequentially provided directly on the surface of the substrate or on an undercoat layer provided on the substrate, the topcoat layer is formed from a photopolymerization initiator and an ultraviolet curable resin. And a coated body comprising a (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound.   The coated body according to claim 1, wherein the silver thin film layer is a silver thin film layer formed by a silver mirror reaction.   The coated body according to claim 1 or 2, wherein the (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound is 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole. .   The content of the (meth) acryloyl group-containing benzotriazole type ultraviolet absorbing compound in the top coat layer is 1 to 10% by mass with respect to the ultraviolet curable resin. The coated body according to item 1.