WO2018135132A1 - Surface decoration structure provided with silver mirror film layer and method for forming same - Google Patents

Abstract

A surface decoration structure 10 according to one embodiment of the present invention is obtained by forming a primer coating film 12, a silver mirror film layer 13 and a top coating film 14 on the surface of a substrate. The silver mirror film layer 13 is formed by laminating nanometer-sized silver particles, the surfaces of which are covered with a polymer dispersant; the top coating film 14 is formed using a coating material that contains, as a solvent, at least one substance selected from among aliphatic hydrocarbon compounds, aliphatic hydrocarbon compound solutions containing 10% by mass or less of an aromatic compound, and diisobutyl ketone. At least one of the primer coating film 12 and the top coating film 14 may contain a rust inhibitor; and the silver mirror film layer 13 may also contain a rust inhibitor. According to this embodiment, a surface decoration structure which has good luster, while being provided with a silver mirror film layer having good corrosion resistance is able to be achieved.

Description

Surface decoration structure with silver mirror film layer and method for forming the same

The present invention relates to a surface decoration structure provided with a silver mirror film layer having a good specular gloss and a method for forming the surface decoration structure, and in particular, a surface provided with a silver mirror film layer in which discoloration or peeling of the silver mirror film layer produced by a coating method is difficult The present invention relates to a decorative structure and a method for forming the same.

Silver (Ag) has a high light reflectance in the visible region and a beautiful metallic luster. When a silver mirror film layer is formed on a substrate such as resin or metal, it exhibits a beautiful metallic luster, so the silver mirror film layer should be applied to automobile interior parts and exterior parts, bicycles, fishing gear, mobile phones, laptop computers, cosmetic containers, etc. There is expected. For example, automobiles are painted for the purpose of protecting the main materials of automobiles (in most cases, steel plates and plastic plates) and improving the aesthetics of automobiles. Compared to cars with the same shape and performance, a beautifully painted car looks better and increases its value as a product. Metallic paint has a high-class metallic texture, and when you look at the exterior of the car, the color looks different depending on the angle at which you look at the car, and it can give a sharp shape to the shape of the car. popular. Aluminum flakes are often used as metallic luster for car metallic paint. Such metallic coating is also used in other products, and the use of silver as a bright material or a mirror surface forming film is being studied in high-grade products.

Conventionally, silver mirror plating by a silver mirror reaction using an ammoniacal silver nitrate solution is well known as a method for forming a silver mirror film layer on a substrate. Silver mirror plating using this ammoniacal silver nitrate solution causes plating-specific chalking (also known as whitening or skinning), cracks, film thickness does not become uniform, and silver nanoplating that forms silver mirror plating. There may be unevenness in color development (metallic luster) on the silver mirror plating surface due to variations in particle aggregation. Furthermore, this silver mirror plating may cause the part that does not need to be silver mirror plated to be silver mirror plated, which has a high defect rate and that the formed silver mirror plating surface is easily peeled off from the surface of the substrate or the like. There is also a problem.

In order to solve the problem of silver mirror plating using such an ammoniacal silver nitrate solution, it is known to use a silver compound complex in which an amine compound or an ammonium carbamate compound is coordinated instead of ammonium as a silver compound complex. Yes. For example, Patent Document 1 (Japanese Patent No. 5610359) discloses a first complex in which an ammonium carbamate compound is coordinated to a silver atom of a silver compound in an alcohol solvent, and an amine compound to the silver atom of the silver compound. And a reducing agent, and the mixing ratio of the first complex to the second complex is 6: 4 to 8: 2 in terms of the molar ratio of silver atoms. The invention of a silver mirror film layer forming composition liquid, a method of producing a silver mirror film layer forming composition liquid, and a method of forming a silver mirror film coating surface is disclosed.

Also known is a method of once forming silver nanoparticles and then forming a silver mirror film layer as a coating film. For example, in the following Patent Document 2 (Japanese Patent Laid-Open No. 2012-144796), a silver compound, an organic amine compound, or an organic stabilizer containing an organic amine compound and an organic carboxylic acid compound, and an organic solvent are mixed, Obtaining a mixture, an acyl monohydrazide compound as a reducing agent is added to the mixture in a powder state, and in a heterogeneous system, the silver compound is reacted with the acyl monohydrazide compound to form silver nanoparticles. The silver nanoparticles obtained are separated, washed and dried, and then dispersed in a suitable organic solvent to prepare a silver ink, which is coated on a substrate using the silver ink and baked at 100 to 180 ° C. To obtain a silver conductive layer.

Similarly, the following Patent Document 3 (Patent No. 5950427) has a styrene-maleic anhydride resin structure in an alcohol solvent, and a part of the maleic anhydride is a polyalkylene glycol having a terminal hydroxyl group or a polyamino glycol having a terminal amino group. Using an alcohol solution in which at least one silver compound selected from silver oxide and silver carbonate is dispersed while dissolving a polymer dispersant having an acid value of 150 or less, which is modified with alkylene glycol, A composition solution for forming a silver mirror film layer comprising an alcohol solution in which silver nanoparticles are dispersed is prepared by irradiating ultrasonic waves in an alcohol solution, and this silver mirror film layer forming composition liquid is spray-coated on the surface of the substrate. A method for forming a silver mirror film layer by drying at room temperature is shown.

Japanese Patent No. 5610359 Japanese Patent Application Laid-Open No. 2012-144796 Japanese Patent No. 5950427

According to the silver mirror film layer forming method disclosed in Patent Document 1, a silver mirror film layer can be formed on the surface of a substrate by heating the silver mirror film layer forming composition solution to 77 to 90 ° C. after coating. . In addition, according to the method for forming a silver conductive layer disclosed in Patent Document 2, a nano-sized silver dispersion is used, and good conductivity is obtained by firing at a relatively low temperature of 100 to 180 ° C. A silver conductive layer can be formed. Furthermore, according to the method for forming a silver mirror film layer disclosed in Patent Document 3, a coating liquid for forming a silver mirror film layer comprising an alcohol solution in which silver nanoparticles are dispersed is spray-coated on the surface of the substrate and dried at room temperature. Thus, a silver mirror film layer can be formed on the surface of the substrate.

By the way, in the silver mirror film layer forming method disclosed in Patent Document 1, heating is performed at 77 to 90 ° C., and in the silver conductive layer forming method disclosed in Patent Document 2, 100 to 180. By baking at ° C, a silver mirror film layer or a silver conductive layer can be formed, respectively. However, in the method for forming a silver mirror film layer disclosed in Patent Document 3, a silver mirror film layer can be formed simply by spray coating the surface of the substrate with a composition liquid for forming a silver mirror film layer and drying at room temperature. Therefore, it has a great advantage at least with respect to the processing temperature as compared with those described in the cited references 1 and 2.

Among these, the silver mirror film layer forming method disclosed in Patent Document 1 includes an amine compound or an ammonium carbamate compound liberated from silver atoms in the silver mirror film layer forming composition liquid, and further a reducing agent. Since these compounds or by-products are contained in the formed silver mirror film layer, even if these compounds or by-products are non-corrosive, the properties of the formed silver mirror film layer are affected. There is a possibility to give.

On the other hand, in the silver mirror film layer forming methods disclosed in Patent Documents 2 to 3, the silver mirror film layer forming composition liquid contains components other than the solvent, nanometer-sized silver particles, and the polymer dispersant. Therefore, the formed silver mirror film layer does not contain corrosive components, and there is no need to remove harmful by-products after the silver mirror film layer is formed. There is an excellent effect that a film layer can be formed. In particular, the method for forming a silver conductive layer disclosed in Patent Document 3 was obtained after producing nano-sized silver particles as in the method for forming a silver mirror film layer described in Patent Document 2. Since silver nanoparticles are separated, washed, dried, and then dispersed in an organic solvent, a great advantage is obtained.

The inventors have repeated experiments on forming silver mirror film layers on the surfaces of various substrates, in particular, in order to take advantage of the silver mirror film layer forming method disclosed in Patent Document 3. As a result, the gloss of the silver mirror film layer may be lowered when the top coat film is formed on the surface of the silver mirror film layer or after the top coat film is formed, depending on the type of solvent used at the time of top coat formation, or after the top coat film is formed. It has been found that there are problems such as discoloration or peeling of the silver mirror film layer when various corrosion resistance tests are performed. Such problems are particularly severe for products used outdoors, such as fishing rods and bicycle parts, because the use conditions are harsh compared to products used indoors. There is a possibility to give.

The present invention has been made to solve the above-described problems of the prior art. That is, the present invention is a surface decoration structure having an undercoat coating film, a silver mirror film layer and a top coating film formed on the surfaces of various substrates, and particularly has a good gloss by reexamining the composition of the top coating. And it aims at providing the surface decoration structure provided with the silver mirror film layer with favorable corrosion resistance, and its formation method.

The surface decoration structure according to the first aspect of the present invention comprises:
In the surface decoration structure in which a base coat film, a silver mirror film layer and a top coat film are formed on the substrate surface,
The silver mirror film layer forms a film in a state where nanometer-sized silver particles are laminated,
The top coat film was formed using a solvent containing at least one selected from an aliphatic hydrocarbon compound solution containing 10% by mass or less of an aromatic compound and diisobutyl ketone as a solvent. It consists of things.

According to the surface decoration structure of this aspect, the surface coating structure having good glitter can be obtained without any unevenness in the glitter of the silver mirror film layer due to the top coating film. Although diisobutylketone is not an aliphatic hydrocarbon compound, since four methyl groups are located sterically around the ketone group, the polarity of the ketone group on the surface of nano-sized silver is caused by steric hindrance. Since it has no effect, it has substantially the same function as an aliphatic hydrocarbon compound. In addition, the aromatic hydrocarbon compound adversely affects the glitter of the silver mirror film layer, but the effect does not appear as long as it is 10% by mass or less in the aliphatic hydrocarbon compound.

The surface decoration structure according to the second aspect of the present invention is the surface decoration structure according to the first aspect, wherein the aliphatic hydrocarbon compound is selected from n-hexane, n-heptane, cyclohexane, and ethylcyclohexane. And at least one kind.

According to the surface decoration structure of this aspect, the operational effects exhibited by the first aspect can be exhibited particularly well.

Further, the surface decoration structure of the third aspect of the present invention is characterized in that, in the surface decoration structure of the first aspect, the undercoat film is the same type as the topcoat film.

According to the surface decoration structure of this aspect, since the undercoat film and the topcoat film are of the same type, the effect produced between the above-described topcoat film and the silver mirror film layer is the same as that of the undercoat film and the silver mirror. This also occurs between the film layers, and the above-described effect is more satisfactorily achieved.

The surface decoration structure of the fourth aspect of the present invention is the surface decoration structure of the first aspect, wherein at least one of the top coat film and the undercoat film is any of the following (1) to (3): It contains the ultraviolet absorber and light stabilizer of these combinations.
(1) A benzotriazole compound and a benzoate compound.
(2) A benzotriazole compound and a hindered amine compound.
(3) Triazine compounds and hindered amine compounds.

According to the surface decoration structure of this aspect, since at least the top coating film contains the ultraviolet absorber and the light stabilizer in any combination of (1) to (3), the corrosion resistance, weather resistance, and adhesion are high. A good surface decoration structure is obtained.

The surface decoration structure according to the fifth aspect of the present invention is the surface decoration structure according to any one of the first to fourth aspects, wherein at least one of the top coat film, the undercoat film, and the silver mirror film layer is: As a rust preventive agent, it contains at least one selected from a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester, and a phosphite compound. .

According to the surface decoration structure of this aspect, the influence on the glitter of the silver mirror film layer is reduced, and the glitter can be maintained for a long time. In addition, these rust preventive agents can also be used as an ultraviolet absorber, and can also be used in combination with an ultraviolet absorber and a light stabilizer. In addition, since the rust preventive agent exhibits a good rust preventive effect because the molecules constituting the rust preventive agent are in contact with or in the vicinity of the silver particles, the top coat film and the undercoat film If at least one of the silver mirror film layers contains a rust inhibitor, a good rust preventive effect can be obtained. In addition, since the thickness of the silver mirror film layer is thinner than the thickness of the top coat film or the undercoat film, the content of the rust inhibitor in the silver mirror film layer is the content of the rust inhibitor in the top coat film or the undercoat film. Even if it is less, it has a good rust prevention effect. Furthermore, when adding a rust preventive agent also in a silver mirror film layer, when the interaction between rust preventive agents is considered, the same thing as the rust preventive agent in top coat film or undercoat film is preferable.

Furthermore, the surface decoration structure of the sixth aspect of the present invention is:
In the surface decoration structure in which a base coat film, a silver mirror film layer and a top coat film are formed on the substrate surface,
The silver mirror film layer forms a film in a state where nanometer-sized silver particles are laminated,
The top coat film comprises a resin film having a polar group.

According to the surface decoration structure of this aspect, when the top coat film is made of a resin film having a polar group, the bond strength between the top coat film and the silver mirror film layer is increased, so that the top coat film and the silver mirror film layer are peeled off. A difficult surface decoration structure is obtained.

The surface decoration structure according to a seventh aspect of the present invention is the surface decoration structure according to the sixth aspect, wherein the polar group is an OH group or an NH ₂ group.

According to the surface decoration structure of this aspect, the effect exhibited by the surface decoration structure of the sixth aspect appears more favorably.

Further, the surface decoration structure of the eighth aspect of the present invention is the surface decoration structure of the sixth aspect, wherein the top coating film is an acrylic urethane resin coating film, a polyurethane resin coating film, a silicon resin coating film, or acrylic silicon. It consists of a resin coating film or an acrylic melamine resin coating film.

According to the surface decoration structure of this embodiment, the acrylic urethane resin coating film, polyurethane resin coating film, silicon resin coating film, acrylic silicon resin coating film, and acrylic melamine resin coating film each have an OH group or NH ₂ group as a polar group. Since it has, the effect which the surface decoration structure of the said 6th aspect show | plays appears more favorable.

The surface decoration structure according to the ninth aspect of the present invention is the surface decoration structure according to the sixth aspect, characterized in that the undercoat coating film is the same type as the top coating film.

According to the surface decoration structure of this aspect, since the undercoat film and the topcoat film are of the same type, the effect produced between the above-described topcoat film and the silver mirror film layer is the same as that of the undercoat film and the silver mirror. Since it also occurs between the film layers, the above-described effect can be achieved better.

The surface decoration structure according to the tenth aspect of the present invention is the surface decoration structure according to the sixth aspect, wherein at least one of the top coating film and the undercoating film is any of the following (1) to (3): It contains the ultraviolet absorber and light stabilizer of these combinations.
(1) A benzotriazole compound and a benzoate compound.
(2) A benzotriazole compound and a hindered amine compound.
(3) Triazine compounds and hindered amine compounds.

According to the surface decoration structure of this aspect, since at least the top coating film contains the ultraviolet absorber and the light stabilizer in any combination of (1) to (3), the corrosion resistance, weather resistance, and adhesion are high. A good surface decoration structure is obtained.

The surface decoration structure according to the eleventh aspect of the present invention is the surface decoration structure according to any one of the sixth to tenth aspects, wherein at least one of the top coat film, the undercoat film and the silver mirror film layer is: As a rust preventive agent, it contains at least one selected from a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester, and a phosphite compound. .

According to the surface decoration structure of this aspect, the influence on the glitter of the silver mirror film layer is reduced, and the glitter can be maintained for a long time. In addition, these rust preventive agents can also be used as an ultraviolet absorber, and can also be used in combination with an ultraviolet absorber and a light stabilizer. In addition, since the rust preventive agent exhibits a good rust preventive effect because the molecules constituting the rust preventive agent are in contact with or in the vicinity of the silver particles, the top coat film and the undercoat film If at least one of the silver mirror film layers contains a rust inhibitor, a good rust preventive effect can be obtained. In addition, since the thickness of the silver mirror film layer is thinner than the thickness of the top coat film or the undercoat film, the content of the rust inhibitor in the silver mirror film layer is the content of the rust inhibitor in the top coat film or the undercoat film. Even if it is less, it has a good rust prevention effect. Furthermore, when adding a rust preventive agent also in a silver mirror film layer, when the interaction between rust preventive agents is considered, the same thing as the rust preventive agent in top coat film or undercoat film is preferable.

Furthermore, the method for forming the surface decoration structure according to the twelfth aspect of the present invention includes:
In the method for forming a surface decoration structure comprising sequentially forming an undercoat coating film, a silver mirror film layer, and a top coating film on the substrate surface,
Spray coating an undercoating paint on the surface of the substrate, and forming the undercoating film by drying,
The silver mirror film layer is spray-coated on a substrate on which the undercoat film is formed with a composition solution for forming a silver mirror film layer in which nanometer-sized silver particles are dispersed in an organic solvent in which a polymer dispersant is dissolved. And then formed by drying at room temperature or under heating,
A top coating material containing at least one selected from aliphatic hydrocarbon compounds containing 10% by mass or less of aromatic compounds and dimethyl isobutyl ketone as a solvent is sprayed on the surface of the silver mirror film layer. The top coat film is formed by painting and drying.

The surface decoration structure forming method of the thirteenth aspect of the present invention is the method of forming the surface decoration structure of the twelfth aspect, wherein the aliphatic hydrocarbon compound is n-hexane, n-heptane, cyclohexane. And at least one selected from ethylcyclohexane.

The surface decoration structure forming method according to the fourteenth aspect of the present invention is the same as the top coating film forming paint as the primer coating forming paint in the surface decoration structure forming method according to the twelfth aspect. It is characterized by using.

The surface decoration structure forming method of the fifteenth aspect of the present invention is the surface decoration structure forming method of the twelfth aspect, wherein at least one of the top coating and the undercoating amount includes the following (1) to (3) A combination containing an ultraviolet absorber and a light stabilizer in any combination is used.
(1) A benzotriazole compound and a benzoate compound.
(2) A benzotriazole compound and a hindered amine compound.
(3) Triazine compounds and hindered amine compounds.

The surface decoration structure forming method according to the sixteenth aspect of the present invention is the surface decoration structure forming method according to any one of the twelfth to fifteenth aspects, wherein the top coating material, the undercoating material, and the silver mirror film layer are formed. At least one selected from a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester and a phosphite compound as at least one of the composition liquids It is characterized by using a seed-containing material.

Furthermore, the surface decoration structure forming method of the seventeenth aspect of the present invention is
In the method for forming a surface decoration structure comprising sequentially forming an undercoat coating film, a silver mirror film layer, and a top coating film on the substrate surface,
Spray coating an undercoating paint on the surface of the substrate, and forming the undercoating film by drying,
The silver mirror film layer is spray-coated on a substrate on which the undercoat film is formed with a composition solution for forming a silver mirror film layer in which nanometer-sized silver particles are dispersed in an organic solvent in which a polymer dispersant is dissolved. And then formed by drying at room temperature or under heating,
The surface of the silver mirror film layer is spray-coated with a paint containing a resin having a polar group as a top coat and dried to form the top coat.

The surface decoration structure forming method of the eighteenth aspect of the present invention is characterized in that in the seventeenth aspect surface decoration structure forming method, the polar group is an OH group or an NH ₂ group. To do.

The surface decoration structure forming method of the nineteenth aspect of the present invention is the surface decoration structure forming method of the seventeenth aspect, wherein the paint for forming the top coat film is an acrylic urethane resin paint, a polyurethane resin paint, Silicone resin paint, acrylic silicon resin paint, or acrylic melamine resin paint is used.

The surface decoration structure forming method of the twentieth aspect of the present invention is the same as the top coating film forming paint as the primer coating forming paint in the surface decoration structure forming method of the seventeenth aspect. It is characterized by using.

A surface decoration structure forming method according to a twenty-first aspect of the present invention is the surface decoration structure forming method according to the seventeenth aspect, wherein the paint for forming a top coat film is the following (1) to (3): A combination containing any combination of an ultraviolet absorber and a light stabilizer is used.
(1) A benzotriazole compound and a benzoate compound.
(2) A benzotriazole compound and a hindered amine compound.
(3) Triazine compounds and hindered amine compounds.

A surface decoration structure forming method according to a twenty-second aspect of the present invention is the surface decoration structure forming method according to any one of the seventeenth to twenty-first aspects, wherein the top coating material, the undercoating material, and the silver mirror film layer are formed. At least one selected from a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester and a phosphite compound as at least one of the composition liquids It is characterized by using a seed-containing material.

According to the surface decoration structure forming method of any one of the twelfth to sixteenth to seventeenth to twenty-second aspects, the surface decoration structure of any one of the first to fifth to sixth to eleventh aspects can be easily obtained. Can be formed.

As described above, according to the present invention, a surface decoration structure provided with a silver mirror film layer excellent in specular appearance, corrosion resistance, light resistance, adhesion, and the like, and a method for forming the surface decoration structure can be obtained.

It is a schematic cross section of the surface decoration structure provided with the silver mirror film layer created by each experiment example or preliminary experiment. It is a photograph which shows the result of having performed the salt spray test about the preliminary experiment sample. It is a photograph which shows the result of having performed the adhesion test about the preliminary experiment sample. FIG. 4A is an enlarged photograph with a magnification of 100,000 times by TEM of a cross section of the preliminary experimental sample, and FIG. 4B is an enlarged photograph with a magnification of 500,000 times. FIG. 5A to FIG. 5C are schematic diagrams for explaining the silver mirror film layer forming process in each experimental example or preliminary experiment step by step.

Hereinafter, the surface decoration structure provided with the silver mirror film layer according to the present invention and the forming method thereof will be described in detail using various experimental examples. However, the following various experimental examples show examples for embodying the technical idea of the present invention, and are not intended to specify the present invention to those shown in these experimental examples. . The invention is equally applicable to other embodiments within the scope of the claims.

FIG. 1 shows a schematic cross-sectional view of a surface decoration structure provided with a silver mirror film layer prepared in each experimental example or preliminary experiment of the present invention. The surface decoration structure 10 provided with the silver mirror film layer includes a base body 11, an undercoat film 12 formed on the surface of the base body 11, a silver mirror film layer 13 formed on the surface of the undercoat film 12, and a silver mirror film. And an overcoating film 14 formed on the surface of the layer 13. In the following, each of the experimental examples and preliminary experiments will be specifically described mainly with respect to the forming method with respect to the substrate 11, the undercoat film 12, the silver mirror film layer 13, and the top coat film 14.

The substrate that can be used in this embodiment includes various metals such as Al, Fe, Mg, and Ti, alloys thereof, those in which an anodized film is formed on the surface of these metals or alloys, and nonmetallic materials. , For example, synthetic resins such as epoxy resin, phenol resin, polyester resin, polyethylene, ABS resin, nylon, composite materials of these synthetic resins and reinforcing fibers (glass fiber, carbon fiber, aramid fiber, alumina fiber, etc.) Can be appropriately selected and used.

In addition, paints that can be used as undercoat or topcoat
(1) a two-component acrylic urethane resin paint formed by a urethane reaction between an isocyanate group and a hydroxyl group;
(2) A two-component acrylic silicone resin paint formed by dehydration and dealcoholization condensation reaction between an acrylic resin having an amino group and a silicone compound having an epoxy group,
(3) Two-component or three-component urethane-modified acrylic silicone resin paint in which urethane reaction and dehydration and dealcohol condensation reaction occur simultaneously,
However, the present invention is not limited to this, and fluororesin-based paints, polyethylene-based paints, polypropylene-based paints, and the like can also be used.

In addition, as the composition liquid for forming the silver mirror film layer, a commercially available liquid prepared by the method described in Patent Document 3 was appropriately selected and used. In addition, spray coating in each experimental example was unified so that all the conditions were the same, so that the coating thickness was substantially the same.

[Preliminary experiment]
(Undercoat)
First, a preliminary experiment was conducted to confirm the problem of the surface decoration structure provided with a silver mirror film layer. Acrylic urethane paint based on acrylic polyol (AT62-2 (trade name), Dainippon Paint Co., Ltd.) 6 parts by weight, toluene 7 parts by weight as a solvent, polyisocyanate curing agent (acrylane (trade name) The undercoat paint was prepared by uniformly stirring and mixing the hardener, Dainippon Paint Co., Ltd.) at a ratio of 1 part by mass, and spray-coating the undercoat paint onto the surface of a standard test piece as a base material. The sample was forcibly dried at 100 ° C. for 30 minutes to obtain a plurality of standard test piece preliminary experimental samples on which an undercoat film was formed.

(Silver mirror film layer)
A silver mirror film layer forming composition liquid and a thinner prepared using the commercially available liquid composition (GLANTZCOAT Type RT Silver (trade name), Perfect Co., Ltd.) based on Patent Document 3 as a silver mirror film layer forming composition liquid. (GLANTZCOAT TypeRT Silver Thinner T2 (trade name), Perfect Co., Ltd.) diluted twice and spray-coated, dried at 95 ° C for 45 minutes to form a silver mirror film layer on multiple undercoat films Standard test specimen preliminary experimental samples were obtained. In addition, this composition liquid for silver mirror film layer formation is a dispersion liquid which contains a silver nanoparticle as a main component in an organic solvent, and also contains a polymer dispersing agent. After the spray coating of the silver mirror film layer forming composition liquid, the silver mirror film layer is formed simply by drying. Here, each of the silver mirror film layers is formed by forced drying at 90 ° C. for 45 minutes. The drying conditions of the silver mirror film layer were made constant so that the effect of room temperature, humidity, etc. did not appear on the formed silver mirror film layer.

(Top coat)
Uniform stirring and mixing at a ratio of 6 parts by weight of acrylic urethane paint (AT62-2) based on acrylic polyol, 7 parts by weight of ethanol as solvent, and 1 part by weight of polyisocyanate curing agent (acrylane curing agent) A top coat was prepared. This top coat paint is spray-coated on the surface of the silver mirror film layer, and then forcibly dried at 100 ° C. for 30 minutes, and a preliminary test consisting of a standard test piece on which a plurality of base coat films, silver mirror film layers and top coat films are formed. Experimental samples were obtained.

When the preliminary test sample prepared in this way was confirmed by visual observation, when the top coat was applied to the surface of the silver mirror film layer or after the top coat was applied, there was a part where the specular gloss was partially reduced. Admitted.

Furthermore, using this standard specimen preliminary experiment sample,
(1) As a result of performing a salt spray test on the surface on which a crosscut conforming to JIS K5600-7-1 was formed, discoloration or peeling was observed in the crosscut portion (see FIG. 2).
(2) When a weather resistance promotion test using a xenon arc lamp according to JIS K5600-7-7 was conducted, yellowing was observed in the color tone.
(3) When an adhesion test was performed on the surface on which a crosscut conforming to JIS K5600-5-6 was formed, it was found between the silver mirror film layer and the undercoat film or between the silver mirror film layer and the top coat film. Was peeled off (see FIG. 3).

From the above preliminary experiment results, the silver mirror film layer prepared using the silver mirror film layer forming composition liquid containing silver nanoparticles and polymer dispersant shown in Patent Document 3 also contains silver nanoparticles. It is presumed that the structure is different from that of the silver conductive layer shown in Patent Document 2 that is prepared using ink but baked at 100 to 180 ° C. Therefore, in order to confirm the cross-sectional structure of the silver mirror film layer, a cross-sectional sample was taken out from the standard test piece preliminary experimental sample described above by the microtome method, and the cross-section was observed using a transmission electron microscope (TEM). The results are shown in FIG. 4A is a magnified photograph at a magnification of 100,000 times by TEM of a cross section, and FIG. 4B is a magnified photograph at a magnification of 500,000 times, and L = 120 nm in FIG. 4B.

4A and 4B, the silver mirror film layer prepared using the silver mirror film layer-forming composition liquid containing silver nanoparticles and the polymer dispersant is not sintered with silver nanoparticles. It can be confirmed that silver nanoparticles are deposited and formed. Furthermore, especially from the photograph of FIG. 4B, it can be confirmed that the individual silver nanoparticles are almost uniform in size and have a diameter of several tens of nanometers.

This is because the silver mirror film layer forming composition liquid used in the preliminary experiment is a volatile solvent other than the silver nanoparticles and the polymer dispersant, so that the silver mirror film layer forming composition liquid is used. The image of layer formation is presumed to be as shown in FIG. That is, in the silver mirror film forming solution, the silver nanoparticles are uniformly dispersed in the solution with the polymer dispersant adhering to the surroundings (FIG. 5A). When this silver mirror film layer forming solution is applied to the surface of the substrate in a film form, the solvent gradually evaporates (FIG. 5B). When the solvent is completely evaporated, a silver mirror film layer is formed in a state where silver nanoparticles having a polymer dispersant adhering to the periphery are laminated, and the polymer dispersant is formed between the silver nanoparticles constituting the silver mirror film layer. A silver mirror film layer in a three-dimensional network form is obtained (FIG. 5C). Thereby, even if a drying process is normal temperature, even if it is mild heating conditions of 100 degrees C or less, a homogeneous silver mirror film layer will be obtained.

Therefore, an approach different from the prior art is required to overcome the weaknesses while taking advantage of the silver mirror film layer formation using the silver mirror film layer forming composition liquid containing silver nanoparticles and polymer dispersant. It is. Hereinafter, the technical significance of the surface decoration structure provided with the silver mirror film layer of the present invention and the method for forming the surface decoration structure will be described in detail using various experimental examples.

[Influence on the silver mirror film layer by the type of solvent]
First, according to Experimental Examples 1 to 21, the silver mirror film layer previously formed on the base coat was spray-coated with various solvents for the top coat film forming paint, and after drying, the degree of discoloration of the silver mirror film layer was visually observed. Confirmed by

[Experimental Example 1]
(Undercoat)
6 parts by mass of silicon oligomer (GLANZCOAT Type RT Primer Black G, Co., Ltd.) containing alkoxyl group as the main component of the undercoat paint, 7 parts by mass of ethanol as a solvent, curing agent (GLANZCOAT type RT primer curing agent U, Undercoat paint was prepared by uniformly stirring and mixing at a ratio of 1 part by mass of “Ffect”. This undercoat paint was spray-coated on the surface of a standard test piece as a base material, and then forcedly dried at 100 ° C. for 30 minutes to obtain a standard test piece sample on which an undercoat coating film was formed.

(Silver mirror film layer)
A silver mirror film layer forming composition liquid prepared on the basis of Patent Document 3 and commercially available (GLANTZCOAT Type RT Silver) is used. The sample was spray-coated and dried at 100 ° C. for 30 minutes to obtain a standard test piece having a silver mirror film layer formed on the undercoat film. The silver mirror film layer forming composition liquid is also a dispersion liquid containing silver nanoparticles as a main component in an organic solvent, and additionally contains a polymer dispersant. After spray coating of the silver mirror film layer forming solution, a silver mirror film layer is formed simply by drying. In all of the experimental examples, by drying at 100 ° C. for 30 minutes, The drying condition of the silver mirror film layer was made constant so that the effect of room temperature, humidity, etc. did not appear on the formed silver mirror film layer.

(Top coat)
10 parts by mass of an alkoxyl group-containing silicon oligomer (GLANZCOAT Type RT Primer Top, Co., Ltd.) as the main component of the top coating, 7 parts by mass of ethanol as a solvent, a curing agent (GLANZCOAT type RT top curing agent G, The top coating composition was prepared by uniformly stirring and mixing so that “fect” was 1 part by mass. This top coat paint was spray-coated on the surface of the silver mirror film layer, and then forced-dried at 100 ° C. for 30 minutes, whereby an undercoat film, a silver mirror film layer, and a top coat film were formed on the surface of the standard test piece. A silver mirror film layer-forming sample was obtained. The top coating used here is a transparent coating.

[Experiment 2]
The undercoat, silver mirror film and top coat are formed on the surface of the standard test piece in the same manner as in Experimental Example 1 except that isopropyl alcohol is used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer-forming sample of Experimental Example 2 was obtained.

[Experiment 3]
The undercoat, silver mirror film and topcoat were formed on the surface of the standard test piece in the same manner as in Experimental Example 1 except that butanol was used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer formation sample of Experimental Example 3 was obtained.

[Experimental Example 4]
The undercoat, silver mirror film and topcoat are formed on the surface of the standard test piece in the same manner as in Experimental Example 1 except that ethyl acetate is used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer-forming sample of Experimental Example 4 was obtained.

[Experimental Example 5]
The undercoat, silver mirror film and top coat are formed on the surface of the standard test piece in the same manner as in Experiment 1 except that butyl acetate is used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer-forming sample of Experimental Example 5 was obtained.

[Experimental Example 6]
As in the case of Experimental Example 1 except that propylene glycol monomethyl ether acetate was used in place of ethanol as the solvent for the undercoat and topcoat, undercoat, silver mirror film and topcoat on the surface of the standard test piece A silver mirror film layer-forming sample of Experimental Example 6 was obtained.

[Experimental Example 7]
As in the case of Experimental Example 1 except that methyl ethyl ketone was used instead of ethanol as the solvent for the undercoat and topcoat, an undercoat film, a silver mirror film layer and an overcoat film were formed on the surface of the standard test piece. A silver mirror film layer-forming sample of Experimental Example 7 was obtained.

[Experimental Example 8]
As in the case of Experimental Example 1 except that diisobutylketone was used instead of ethanol as the solvent for the undercoat and topcoat, an undercoat film, a silver mirror film layer and an overcoat film were formed on the surface of the standard test piece. A silver mirror film layer-forming sample of Experimental Example 8 was obtained.

[Experimental Example 9]
As in the case of Experimental Example 1 except that methyl isobutyl ketone was used instead of ethanol as the solvent for the undercoat and topcoat, an undercoat film, a silver mirror film layer and an overcoat film were formed on the surface of the standard test piece. Thus, a silver mirror film layer formation sample of Experimental Example 9 was obtained.

[Experimental Example 10]
As the solvent for the undercoat and topcoat, cyclohexanone was used instead of ethanol, and the undercoat, silver mirror film and topcoat were formed on the surface of the standard test piece in the same manner as in Experimental Example 1. A silver mirror film layer formation sample of Experimental Example 10 was obtained.

[Experimental Example 11]
As in the case of Experimental Example 1 except that ethylene glycol monomethyl ether was used instead of ethanol as the solvent for the undercoat and topcoat, an undercoat, a silver mirror film and an overcoat were formed on the surface of the standard test piece. A silver mirror film layer-formed sample of Experimental Example 11 was obtained.

[Experimental example 12]
As in the case of Experimental Example 1, except that 3-methoxy-1-butanol was used instead of ethanol as the solvent for the undercoat and topcoat, the surface of the standard test piece was coated with the undercoat, silver mirror film and topcoat. The silver mirror film layer formation sample of Experimental example 12 in which the coating film was formed was obtained.

[Experimental Example 13]
The undercoat, silver mirror film and topcoat were formed on the surface of the standard test piece in the same manner as in Experimental Example 1 except that toluene was used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer-forming sample of Experimental Example 13 was obtained.

[Experimental Example 14]
The undercoat film, the silver mirror film layer and the top coat film were formed on the surface of the standard test piece in the same manner as in Experimental Example 1 except that xylene was used instead of ethanol as the solvent for the undercoat paint and the topcoat paint. A silver mirror film layer-forming sample of Experimental Example 13 was obtained.

[Experimental Example 15]
Standard test piece as in Experimental Example 1 except that solvent naphtha solvent (Solvesso 200 (trade name), TonenGeneral Sekiyu KK) was used instead of ethanol as the solvent for the undercoat and topcoat. A silver mirror film layer-forming sample of Experimental Example 15 was obtained in which an undercoat coating film, a silver mirror film layer and a top coating film were formed on the surface.

[Experimental Example 16]
The undercoat, silver mirror film and topcoat are formed on the surface of the standard test piece in the same manner as in Example 1 except that n-hexane is used instead of ethanol as the solvent for the undercoat and topcoat. Thus, a silver mirror film layer formation sample of Experimental Example 16 was obtained.

[Experimental Example 17]
In the same manner as in Experimental Example 1, except that n-heptane was used instead of ethanol as the solvent for the undercoat and topcoat, an undercoat, a silver mirror film and an overcoat were formed on the surface of the standard test piece. A silver mirror film layer-formed sample of Experimental Example 17 was obtained.

[Experiment 18]
The undercoat, silver mirror film and top coat were formed on the surface of the standard test piece in the same manner as in Example 1 except that cyclohexane was used instead of ethanol as the solvent for the undercoat and the topcoat. A silver mirror film layer formation sample of Experimental Example 18 was obtained.

[Experimental Example 19]
The undercoat, silver mirror film and top coat are formed on the surface of the standard test piece in the same manner as in Example 1 except that ethylcyclohexane is used instead of ethanol as the solvent for the undercoat and topcoat. Thus, a silver mirror film layer-forming sample of Experimental Example 19 was obtained.

[Experiment 20]
In the same manner as in Experimental Example 1 except that mineral spirit (aromatic hydrocarbon ≦ 10% by mass) was used instead of ethanol as a solvent for the undercoat and topcoat, The silver mirror film layer formation sample of Experimental Example 20 in which the silver mirror film layer and the top coat film were formed was obtained.

[Experimental example 21]
In the same manner as in Experimental Example 1 except that mineral spirit (aromatic hydrocarbon> 10 vol) was used instead of ethanol as a solvent for the undercoat and topcoat, an undercoat film and a silver mirror film were formed on the surface of the standard test piece. The silver mirror film layer formation sample of Experimental example 21 in which the layer and the top coat film were formed was obtained.

[Measurement results of Experimental Examples 1 to 21]
About each silver mirror film layer formation sample of Experimental Examples 1 to 21 formed as described above, the degree of discoloration was measured visually. The result is the degree of discoloration
(1) A substantially uniform silver mirror film layer was obtained.
(2) “△” indicates that a slight unevenness in the brightness was partially observed.
(3) “x” indicates that the brightness is clearly markedly uneven.
Expressed in The results are summarized in Table 1.

From the results shown in Table 1, the following can be understood. In other words, the sample with the silver mirror film layer formed with large unevenness in glitter was in the case of alcohol compounds in which the solvent was ethanol (Experimental Example 1), isopropyl alcohol (Experimental Example 2), and butanol (Experimental Example 3). there were. In addition, samples with silver mirror film layer formation with slightly uneven brightness were ethyl acetate (Experimental Example 4), butyl acetate (Experimental Example 5), propylene glycol monomethyl ether acetate (Experimental Example 6), methyl ethyl ketone ( Experimental example 7), methyl isobutyl ketone (experimental example 9), cyclohexanone (experimental example 10), ethylene glycol monomethyl ether (experimental example 11), 3-methoxy-1-butanol (experimental example 12), toluene (experimental example 13) And xylene (Experimental Example 14), Solvesso 200 (Experimental Example 15), which is a solvent naphtha solvent, and mineral spirits (aromatic hydrocarbon> 10% by mass) (Experimental Example 21). In contrast, diisobutyl ketone (Experimental Example 8), n-hexane (Experimental Example 16), n-heptane (Experimental Example 17), cyclohexane (Experimental Example 18), ethylcyclohexane (Experimental Example 19) and mineral spirit (aromatic carbonization). In the case of (hydrogen ≦ 10% by mass) (Experimental Example 20), the brightness of the silver mirror film layer-formed sample was not substantially uneven, and good brightness was maintained.

From the above results, it can be seen that alcohol compounds most adversely affect the glitter of the silver mirror film layer. Next, it is found that ester compounds, ketone compounds, ether compounds and aromatic compounds have an adverse effect on the glitter of the silver mirror film layer. When aliphatic hydrocarbon compounds are used, the glitter of the silver mirror film layer is affected. It can be seen that the best results are obtained.

However, among the ketone-based compounds, diisobutyl ketone (Experimental Example 8) has good results in the glitter of the silver mirror film layer, but in methyl ethyl ketone (Experimental Example 7) and methylisobutylketone (Experimental Example 9). The result is inferior luster of the silver mirror film layer. This is because diisobutyl ketone has a chemical structural formula represented by the following chemical formula I, and the three-dimensional structure is a structure in which four methyl groups are arranged equidistantly on the outer peripheral side of the oxygen atom constituting the ketone group. Therefore, it is considered that the oxygen atom constituting the ketone group substantially acts as a nonpolar group due to the steric hindrance caused by these four methyl groups.

Therefore, when the results shown in Table 1 are summarized, since cyclohexane is classified as a kind of cycloaliphatic hydrocarbon compound, at least one kind selected from an aliphatic hydrocarbon compound or diisobutylketone as a solvent for the top coat is used. It can be seen that a silver mirror film layer with good luster can be obtained if used. Mineral spirit is an oil-based solvent that is classified into industrial gasoline containing an aliphatic hydrocarbon as a main component and containing an aromatic hydrocarbon, but the content of the aromatic hydrocarbon exceeds 10% by mass. (Experimental example 21) and the glitter of the silver mirror film layer are adversely affected. However, if the aromatic hydrocarbon content is 10% by mass or less (Experimental example 20), a silver mirror film layer with good glitter is obtained. It has been. Therefore, it can be said that the solvent for the top coat is acceptable even if the aliphatic hydrocarbon compound and diisobutyl ketone contain 10% by mass or less of an aromatic compound.

[Experimental Examples 22 to 26]
In Experimental Examples 22 to 26, a commercially available thinner (35% by mass of toluene, 65% by mass of ethyl acetate) as a solvent and 10% by mass of mineral spirit (having an aromatic hydrocarbon content of less than 10% by mass) each ( Experimental Example 22), 30% by mass (Experimental Example 23), 50% by mass (Experimental Example 24), 80% by mass (Experimental Example 25) and 90% by mass (Experimental Example 26) The effect of silver on the glitter of silver mirror film layer was investigated. That is, as the solvent for undercoating and topcoating, except that the thinner was added with mineral spirit, the same as in Experimental Example 1, the surface of the standard test piece was coated with an undercoating film, a silver mirror film layer, and The silver mirror film layer formation samples of Experimental Examples 22 to 26 in which the top coat film was formed were prepared, and the degree of glitter of the silver mirror film layer was visually confirmed. The results are summarized in Table 2.

According to the results of Experimental Examples 22 to 26, when thinner is used as the solvent for at least the top coat, it has good glitter when used so that the addition ratio of mineral spirit is 30 to 80% by mass. It can be seen that a silver mirror film layer is obtained. This result probably suggests that a silver mirror film layer with good luster can be obtained when the content ratio of the aromatic compound component in the solvent mixture of thinner and mineral spirit is within an appropriate range. It is.

[Experimental examples 27 to 34]
In Experimental Examples 27 to 34, an ultraviolet absorber and a light stabilizer were added to the top coat film to prepare a silver mirror film layer formation sample, and the degree of discoloration when a weather resistance promotion test using a xenon arc lamp was performed. Was visually observed to perform a discoloration resistance test by adding an ultraviolet absorber and a light stabilizer.

First, commercially available benzotriazole compounds (Experimental Examples 27 and 31), triazine compounds (Experimental Examples) as UV absorbers in the top coat of Experimental Example 16 in which a sample for forming a mirror film layer having good glitter was obtained. 28, 32), a benzophenone compound (Experimental Examples 29 and 33) and a cyclonoacrylate compound (Experimental Examples 30 and 34) were added at a ratio of 5% by mass with respect to the total mass of the top coating material, respectively. A commercially available benzoate compound (Experimental Examples 27 to 30) or a hindered amine compound (Experimental Examples 31 to 34) was added so as to be 2% by mass in the same manner. Silver mirror film layer formation samples of Experimental Examples 27 to 34 in which an undercoat film, a silver mirror film layer, and a top coat film were formed on the surface of the test piece were obtained. The undercoating film was prepared using the same material as the top coating except that no UV absorber and light stabilizer were added.

For each of the prepared silver mirror film layer formation samples of Experimental Examples 27 to 34, a weather resistance promotion test using a xenon arc lamp was performed by a method in accordance with JIS K5600-7-7. As a result, the degree of yellowing on the surface of each silver mirror film layer-formed sample was evaluated as “◎” when no yellowing was observed, and “○” when slightly yellowing was observed. Those in which yellowing was observed were represented by “Δ”, and those in which yellowing was clearly recognized were represented by “x”, and are summarized in Table 3.

[Experimental Example 35]
From the results shown in Table 3, it was found that good discoloration resistance was obtained when a benzotriazole-based compound was used as the ultraviolet absorber and a hindered amine-based compound was used as the light stabilizer. Therefore, as Experimental Example 35, the addition ratio of the benzotriazole-based compound as the ultraviolet absorber is from 0.5% by mass to 15.0% by mass, and the hindered amine-based compound as the light stabilizer is from 0.5% by mass to 5%. 0.0 mass%, each was changed into a matrix, and the others were the same as in Experimental Examples 27 to 34, and a plurality of samples having an undercoat film, a silver mirror film layer, and an overcoat film formed on the surface of the standard test piece. A silver mirror film layer-formed sample of Experimental Example 35 was prepared, and a weather resistance promotion test was performed in the same manner as in Experimental Examples 27 to 34. The results are summarized in Table 4.

From the results shown in Table 4, the addition ratio of the UV absorber composed of the benzotriazole compound is 1.0 to 10% by mass and the addition ratio of the hindered amine light stabilizer is 0 with respect to the total volume of the main component of the top coat. It can be seen that 0.5 to 4.0 mass% is preferable. The most preferable addition ratio is 4.0 to 6.0% by mass of the UV absorber made of a benzotriazole compound and 1.0 to 2.0 of the hindered amine light stabilizer with respect to the total volume of the main component of the top coating. % By mass.

In Experimental Examples 27 to 35, an example was shown in which a sample for forming a silver mirror film layer was prepared by adding an ultraviolet absorber and a light stabilizer only in the top coat film. A light stabilizer may be added, and an ultraviolet absorber and a light stabilizer may be added only to the undercoat film. In particular, when a configuration in which an ultraviolet absorber and a light stabilizer are added to the topcoat and the undercoat, it is not necessary to prepare different compositions for the undercoat and the topcoat, so the topcoat and the undercoat The forming operation is simplified.

[Experimental examples 36 to 41]
In Experimental Examples 36 to 41, a sample for forming a silver mirror film layer was prepared by adding a rust preventive agent to the top coat film and the undercoat film, and the degree of discoloration of the silver mirror film layer after forming the top coat film was investigated. That is, commercially available triazole compounds (Experimental Example 36), triazine compounds (Experimental Example 37), benzothiazole compounds (Experimental Example 38), fatty acid amide compounds (Experimental Example 39), and phosphate esters as rust inhibitors. An amine salt (Experimental Example 40) and a phosphite compound (Experimental Example 41) were respectively added at a ratio of 5% by mass with respect to the total volume of the top coat, and the others were the same as in Experimental Example 16. The silver mirror film layer-formed samples of Experimental Examples 36 to 41 in which the undercoat film, the silver mirror film layer, and the top coat film were formed on the surface of the standard test piece were obtained.

Each of the silver mirror film layer-formed samples of Experimental Examples 36 to 41 prepared as described above was subjected to a salt spray test in accordance with JIS K5600-7-1, and the degree of discoloration of the silver mirror film layer was visually confirmed. did. The result is “◎” when no discoloration was observed, “○” when slight discoloration was observed, and “△” when light discoloration was observed. These items are represented by “x” and are summarized in Table 5.

In Experimental Examples 27 to 35, an example in which an ultraviolet absorber and a light stabilizer are added to the top coat film or the undercoat film is shown. In Experimental Examples 36 to 41, a rust inhibitor is added to the top coat film or the undercoat film. Although the example which added was shown, you may add not only a ultraviolet absorber and a light stabilizer but a rust preventive agent simultaneously in top coat film or undercoat film. Furthermore, not only the top coat film or the undercoat film contains a rust preventive agent, but also a rust preventive agent is added to the silver mirror film layer forming composition liquid so that the silver mirror film layer contains the rust preventive agent. Also good. Furthermore, a rust inhibitor may be added only to the silver mirror film layer without adding a rust inhibitor to the top coat film or the undercoat film. That is, the rust preventive agent exhibits a good rust preventive effect because the molecules constituting the rust preventive agent are present in contact with or in the vicinity of the silver particles. If at least one of the silver mirror film layers contains a rust inhibitor, a good rust preventive effect can be obtained.

On the other hand, since the thickness of the silver mirror film layer is much thinner than the thickness of the top coat film or the undercoat film, the content of the rust inhibitor in the silver mirror film layer is the same as that in the top coat film or the undercoat film. Even if the content is less than the content of the rust inhibitor, a good rust preventive effect can be obtained. Therefore, when a rust inhibitor is added to the silver mirror film layer forming composition liquid, the content of the rust inhibitor is less than the content of the rust inhibitor in the top coat or undercoat. In addition, when a rust inhibitor is added to the top coat or the undercoat paint and further added to the silver mirror film layer forming composition liquid, the top coat paint or the The same rust preventive as that in the undercoat paint is preferred.

[Experimental examples 42 to 46]
From the results shown in Table 5, it was found that triazole type rust preventives are preferable. Therefore, in Experimental Examples 42 to 46, the content of the commercially available triazole rust preventive agent is set to the total volume of the top coat and undercoat paints. 1% by mass (Experimental example 42), 2% by mass (Experimental example 43), 5% by mass (Experimental example 44), 10% by mass (Experimental example 45) and 20% by mass (Experimental example 46) The degree of discoloration was prepared in the same manner as in Experimental Examples 36 to 41. The results are summarized in Table 6.

From the results shown in Table 6, if the content of the triazole compound as a rust preventive agent is 2 to 10% by mass with respect to the total volume of the top coat and the undercoat, a good antirust effect (discoloration resistance) However, when the result of Experimental Example 43 is extrapolated to the Experimental Example 42 side and the Experimental Example 44 side, it can be seen that a better effect is obtained if it is 4 to 7% by mass.

[Experimental examples 47 to 52]
In Experimental Examples 1 to 46, an example in which a silicon oligomer containing an alkoxyl group as a main agent was used as a top coat film and a base coat film forming paint was used. In Experimental Example 47, an acrylic urethane paint (Acridic A801P ( (Trade name), DIC Co., Ltd.), in Experimental Example 48, a silicon oligomer paint containing an alkoxyl group different from that used in Experimental Examples 1 to 46 (FOC100 (trade name), Ffect Co., Ltd.), Experimental Example 49 In the acrylic silicone paint (B1161 (trade name), DIC Corporation), acrylic melamine paint (ARBT100 (trade name), Takashi Kubo Paint Co., Ltd.), and in Experimental Example 50, the epoxy paint (GR clear (trade name), cashew) In Example 50, methacrylic acid lacquer (Acridic A-166 (trade name), DIC (Inc.) In the same manner as in Experimental Example 16, the silver mirror film layer-formed samples of Experimental Examples 47 to 52 in which the undercoat film, the silver mirror film layer, and the top coat film were formed on the surface of the standard test piece were used. I made several. However, the curing agent addition ratio and the drying conditions of each paint are adjusted so as to be optimum values according to each paint based on the catalog value of each paint.

Using the thus prepared silver mirror film layer formation samples of Experimental Examples 47 to 52, a peel test was conducted by a cross-cut method in accordance with JIS K5600-5-6 to examine the degree of adhesion. The degree of peeling was confirmed by visual inspection. When no peeling was observed on all of the samples, “◎”, and when some peeling was found on some samples, “○” "△" indicates that large peeling was observed in each sample, and "X" indicates that large peeling was observed in all samples, and the results are the addition ratio of the curing agent, drying conditions, and polarity of the paint. Table 7 summarizes the types of groups.

From the results shown in Table 7, as the main component of the top coat film and the undercoat film, those having a polar group such as OH or NH ₂ have better adhesion than the paint of Experimental Example 52 having no polar group. In particular, it was found that the best adhesion was obtained when the coating material mainly composed of the silicon oligomer having an alkoxyl group in Experimental Example 48 was used. Also, from the comparison of the results of Experimental Examples 47 to 49 and Experimental Examples 50 and 51, it was found that the adhesiveness was better when the polar group was OH group than when the polar group was NH ₂ group.

[Experimental Examples 53-55]
From the measurement results of Experimental Examples 47 to 52, it was found that those having an OH group as a polar group as the main agent of the top coat film and the undercoat film have good adhesion. Then, although it was the same kind of main ingredient, the adhesiveness of top coat film and undercoat film was investigated using the several coating material from which OH value differs, respectively. That is, as a main agent of the top coat film and the undercoat paint film, an acrylic urethane paint (Aclidick A801P (trade name), DIC Corporation) having an OH value of “50” in Experimental Example 53, and an OH value of “50” in Experimental Example 54 25 ”acrylic urethane paint (Acridic A837 (trade name), DIC Corporation) and in Experimental Example 55, acrylic urethane paint (Acridick 57-773 (trade name), DIC Corporation) with an OH value of“ 15 ” In the same manner as in Experimental Example 16, the silver mirror film layer-formed samples of Experimental Examples 53 to 55 in which an undercoat film, a silver mirror film layer, and a top coat film were formed on the surface of a standard test piece were used. A plurality of samples were prepared, and adhesion tests were conducted in the same manner as in Experimental Examples 47 to 52. However, the curing agent addition ratio and the drying conditions of each paint are adjusted so as to be optimum values according to each paint based on the catalog value of each paint. The results are summarized in Table 8.

From the results shown in Table 8, it was found that the adhesion was improved when a material having a large OH value, that is, containing a large amount of polar groups, was used as the main component of the top coat and the undercoat. Such a polar group in the main agent of the coating is considered to form hydrogen bonds with the polymer dispersant attached to the surface of the nano-sized silver particles. Moreover, as shown in FIG. 5C in the preliminary experiment, the silver mirror film layer formed in each of the embodiments described above has a three-dimensional network of polymer dispersants between the silver nanoparticles constituting the silver mirror film layer. Can be considered to exist. For this reason, when a polymer having a large OH number is used as the main agent of the topcoat and undercoat, the polymer dispersant traps silver nanoparticles while intermolecular forces such as hydrogen bonding with the topcoat or undercoat. It is thought that it forms and binds firmly.

Interpolating the results of Experimental Examples 53 and 54 shows that the OH value of the main component of the top coat and the undercoat is preferably 25 or more, and more preferably 40 or more. However, the upper limit of the OH value is not clearly defined as critical, but is considered to be about 200 in consideration of the general OH value range of commercially available paints.

DESCRIPTION OF SYMBOLS 10 ... Surface decoration structure provided with silver mirror film layer 11 ... Base | substrate 12 ... Undercoat film 13 ... Silver mirror film layer 14 ... Top coat film

Claims (22)

1. In the surface decoration structure in which a base coat film, a silver mirror film layer and a top coat film are formed on the substrate surface,
   The silver mirror film layer forms a film in a state where nanometer-sized silver particles are laminated,
   The top coat film was formed using a solvent containing at least one selected from an aliphatic hydrocarbon compound solution containing 10% by mass or less of an aromatic compound and diisobutyl ketone as a solvent. Surface decoration structure characterized by consisting of things.
2. 2. The surface decoration structure according to claim 1, wherein the aliphatic hydrocarbon compound is at least one selected from n-hexane, n-heptane, cyclohexane, and ethylcyclohexane.
3. The surface decoration structure according to claim 1, wherein the undercoat coating film is the same kind as the topcoat coating film.
4. 2. The surface according to claim 1, wherein at least one of the top coating film and the undercoating film contains an ultraviolet absorber and a light stabilizer in any combination of the following (1) to (3): Decorative structure.
   (1) A benzotriazole compound and a benzoate compound.
   (2) A benzotriazole compound and a hindered amine compound.
   (3) Triazine compounds and hindered amine compounds.
5. At least one of the top coating film, the undercoating film, and the silver mirror film layer is a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester, and a sub-layer as a rust inhibitor. The surface decoration structure according to any one of claims 1 to 4, comprising at least one selected from phosphate ester compounds.
6. In the surface decoration structure in which a base coat film, a silver mirror film layer and a top coat film are formed on the substrate surface,
   The silver mirror film layer forms a film in a state where nanometer-sized silver particles are laminated,
   The surface coating structure, wherein the top coat film comprises a resin film having a polar group.
7. The surface decoration structure according to claim 6, wherein the polar group is an OH group or an NH ₂ group.
8. The surface decoration structure according to claim 6, wherein the top coat film comprises an acrylic urethane resin film, a polyurethane resin film, a silicon resin film, an acrylic silicon resin film, or an acrylic melamine resin film. .
9. The surface decoration structure according to claim 6, wherein the undercoat film is the same kind as the topcoat film.
10. 7. The surface according to claim 6, wherein at least one of the top coat film and the undercoat film contains an ultraviolet absorber and a light stabilizer in any combination of the following (1) to (3): Decorative structure.
    (1) A benzotriazole compound and a benzoate compound.
    (2) A benzotriazole compound and a hindered amine compound.
    (3) Triazine compounds and hindered amine compounds.
11. At least one of the top coating film, the undercoating film, and the silver mirror film layer is a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester, and a sub-layer as a rust inhibitor. The surface decoration structure according to any one of claims 6 to 10, comprising at least one selected from phosphoric ester compounds.
12. In the method for forming a surface decoration structure comprising sequentially forming an undercoat coating film, a silver mirror film layer, and a top coating film on the substrate surface,
    Spray coating an undercoating paint on the surface of the substrate, and forming the undercoating film by drying,
    The silver mirror film layer is spray-coated on a substrate on which the undercoat film is formed with a composition solution for forming a silver mirror film layer in which nanometer-sized silver particles are dispersed in an organic solvent in which a polymer dispersant is dissolved. And then formed by drying at room temperature or under heating,
    On the surface of the silver mirror film layer, a top coating material containing at least one selected from an aliphatic hydrocarbon compound solution containing 10% by mass or less of an aromatic compound and diisobutyl ketone as a solvent is spray-coated. And forming the top coat film by drying, and forming a surface decoration structure.
13. The method for forming a surface decoration structure according to claim 12, wherein at least one selected from n-hexane, n-heptane, cyclohexane, and ethylcyclohexane is used as the aliphatic hydrocarbon compound of the solvent. .
14. The method for forming a surface decoration structure according to claim 12, wherein the undercoat paint is the same type as the top coat paint.
15. 13. The system according to claim 12, wherein at least one of the top coating and the undercoating amount includes a combination of an ultraviolet absorber and a light stabilizer in any one of the following (1) to (3). Method for forming the surface decoration structure.
    (1) A benzotriazole compound and a benzoate compound.
    (2) A benzotriazole compound and a hindered amine compound.
    (3) Triazine compounds and hindered amine compounds.
16. At least one of the top coating composition, the undercoating composition and the silver mirror film layer forming composition liquid, as a rust preventive agent, a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester The method for forming a surface decoration structure according to any one of claims 12 to 15, wherein a material containing at least one selected from phosphite compounds is used.
17. In the method for forming a surface decoration structure comprising sequentially forming an undercoat coating film, a silver mirror film layer, and a top coating film on the substrate surface,
    Spray coating an undercoating paint on the surface of the substrate, and forming the undercoating film by drying,
    The silver mirror film layer is spray-coated on a substrate on which the undercoat film is formed with a composition solution for forming a silver mirror film layer in which nanometer-sized silver particles are dispersed in an organic solvent in which a polymer dispersant is dissolved. And then formed by drying at room temperature or under heating,
    A method for forming a surface decoration structure, wherein the top coating film is formed by spray-coating a coating containing a resin having a polar group as a top coating on the surface of the silver mirror film layer and drying the coating.
18. The method for forming a surface decoration structure according to claim 17, wherein the polar group is an OH group or an NH ₂ group.
19. 18. The method for forming a surface decoration structure according to claim 17, wherein an acrylic urethane resin paint, a polyurethane resin paint, a silicon resin paint, an acrylic silicon resin paint, or an acrylic melamine resin paint is used as the top coating.
20. The method for forming a surface decoration structure according to claim 17, wherein the undercoat paint is the same as the top coat paint.
21. 18. The composition according to claim 17, wherein at least one of the top coating and the undercoating amount includes an ultraviolet absorber and a light stabilizer in any combination of the following (1) to (3). Method for forming the surface decoration structure.
    (1) A benzotriazole compound and a benzoate compound.
    (2) A benzotriazole compound and a hindered amine compound.
    (3) Triazine compounds and hindered amine compounds.
22. At least one of the top coating composition, the undercoating composition and the silver mirror film layer forming composition liquid, as a rust preventive agent, a triazole compound, a triazine compound, a benzothiazole compound, a fatty acid amide compound, an amine salt of a phosphate ester The method for forming a surface decoration structure according to any one of claims 17 to 21, wherein a material containing at least one selected from phosphite compounds is used.

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