JP5927688B2 - Mirror and manufacturing method thereof - Google Patents

Description

  The present invention relates to a mirror that is remarkably excellent in chemical resistance and corrosion resistance, particularly in a cass test, is excellent in workability such as cutting and chamfering, and has cleared environmental problems during manufacturing, and a manufacturing method thereof.

  Conventionally, for a mirror with a silver mirror film plated on the back surface of a glass substrate, discoloration and peeling of the silver mirror film caused by water vapor, various corrosion-resistant gases, various chemicals, etc. in an environment where this mirror is used, In addition, in order to prevent mechanical damage to the silver mirror film, a metal protective film is formed on the silver mirror film, and on top of that, a light alum, petal, lead cyanamide, calcium carbonate or alkyd resin coating is applied. A back coating film was formed. However, in a mirror having such a backing coating film, satisfactory performance in terms of chemical resistance, corrosion resistance, etc. has not necessarily been obtained depending on the environment in which the mirror is used.

  In order to solve this problem, some proposals have been made in the past. For example, Patent Document 1 discloses that a weight ratio (P / B) of a vehicle (B) and a pigment (P) mainly composed of a bisphenol type epoxy ester resin obtained by esterifying a backing coating film with a dibasic acid is 0. It is proposed to form with a coating composition containing in a proportion of .5 to 4.2, thereby improving the corrosion resistance, durability and processability of the mirror.

  Further, in Patent Document 2, drying for covering the edge of the mirror where the metal protective film is exposed is completed in a short time, and a glass protective film made of glass at the edge of the glass substrate, a silver mirror film, a metal protective film made of copper or the like, a back surface protective film Thus, there is provided a mirror rim coating liquid that adheres firmly to the surface and has excellent corrosion resistance and an excellent anticorrosive effect over a long period of time.

  In Patent Document 3, a coating formed by applying benzotriazole and / or a derivative thereof is provided between the copper protective film and the backing coating, and chemical durability such as alkali resistance and acid resistance is provided. In addition, a mirror has been proposed that is excellent in durability even under severe use conditions and excellent in workability such as cutting and chamfering.

  Further, Patent Document 4 discloses that silver plating is performed on a glass sheet to form a silver reflection layer (silver mirror film), and an acidic solution of tin chloride is sprayed on the reflection layer, and further 0.1 volume% -γ. -It is disclosed that after spraying an aminopropyltriethoxysilane solution, a thermosetting powder coating of an epoxy polyester resin is applied by electrostatic projection and then cured by heating to form a protective layer of a reflective layer. The protective layer of the reflective layer is for avoiding the use of a copper protective film used to protect the silver mirror film and a lead pigment blended in the paint to protect the copper protective film. In addition, in Patent Document 3, for the mirror having a copper protective layer on the silver reflective layer, the presence of copper reduces the adhesion of the coating powder. It is stated that it is not applicable.

  Patent Document 5 discloses a composition for a back coating film in which the content of a lead-based pigment is reduced, and Patent Document 6 discloses molybdenum as a lead-free rust preventive pigment instead of a lead-based pigment. A composition for a backing film using calcium acid is disclosed, and all of them are proposed as a composition for a backing film with reduced use of environmentally hazardous substances.

JP 05-161,531 JP 2005-307,179 A Japanese Patent Laid-Open No. 07-234,306 Japanese Patent Laid-Open No. 09-150,110 JP 2006-028,462 JP 2007-041,479

  However, in the conventional mirror as described above, although the effect based on the backing coating film is achieved, many use conditions of the mirror used in various environments while maintaining excellent processability. Under the adverse conditions existing below, satisfactory performance is not always obtained, and the coating composition for a back coating film described in other patent documents other than patent document 3 is environmental It is a solvent-based paint that uses an organic solvent such as xylene, which is a load substance, and it goes against self-restriction for the purpose of reducing environmental pollution and improving the work environment. It was.

Therefore, as a result of intensive studies on solving the conventional problems in mirrors having such a backing coating film, the present inventors surprisingly found that as an epoxy resin blended in a powder coating composition. By using a specific epoxy resin and a specific curing agent as the curing agent, even if a copper protective film is used as the protective layer of the silver mirror film, the adhesion of the powder coating is not lowered, and this type of conventional It can solve the problems of mirrors with a back coating film, and the back coating film can be used under various usage conditions under normal circumstances while maintaining excellent processability in cutting, chamfering, etc. Seeing that it is possible to provide chemical mirrors and corrosion resistances that should be possessed, and in particular, performances that can be satisfactorily satisfied in cast tests, and that can provide mirrors that do not contain organic solvents, and methods for manufacturing such mirrors. And, to complete the present invention.

  Therefore, the object of the present invention is to have excellent workability in cutting, chamfering, etc., as well as excellent chemical resistance and corrosion resistance under various usage conditions considered under normal circumstances, particularly in a cast test. Another object of the present invention is to provide a mirror that can solve the environmental problem in which the coating composition for forming a backing coating film does not contain an organic solvent.

  Another object of the present invention is to provide a mirror manufacturing method capable of solving various problems of such a conventional mirror having such a back coating film.

That is, the present invention provides a mirror in which a silver mirror film, a copper protective film, and a back coating film are sequentially formed on a glass substrate, and the back coating film has an epoxy equivalent in the range of 706 to 1550. Powder coating containing one or more epoxy resins selected from a certain bisphenol A type epoxy resin, bisphenol F type epoxy resin, and cresol novolac epoxy resin, and a curing agent comprising adipic acid hydrazide and / or dicyandiamide the powder coating coating der Rukoto composition is a mirror, characterized.

Moreover, this invention is a manufacturing method of the mirror which forms a silver mirror surface film | membrane, a copper protective film, and a back coating film in order on a glass substrate, The epoxy equivalent is the range of 706-1550 on the said copper protective film. bisphenol a type epoxy resin is an internal, bisphenol F type epoxy resin, and cresol novolac epoxy and one or more epoxy resins selected from resins, flour and a curing agent comprising a hydrazide adipic acid and / or dicyandiamide A mirror manufacturing method characterized in that a back coating film is formed by powder coating using a body coating composition.

In the present invention, the silver mirror film formed on the glass substrate is usually a silver film formed by being deposited on the glass substrate surface by an electroless plating method, but is not necessarily limited thereto. In addition, a silver film formed by a vacuum deposition method, a sputtering method, or other various film forming methods can also be used as the mirror surface film. Such a silver mirror surface film usually has a film thickness of 0.5 g / m ² or more and 2 g / m ² or less so that a sufficient mirror reflectance can be obtained and a silver mirror film excellent in durability can be obtained. Preferably, it is formed in a range of 0.7 g / m ² or more and 1.2 g / m ² or less.

In the present invention, the copper protective film formed on the silver mirror film is formed for the purpose of enhancing the chemical durability of the silver mirror film that is easily chemically altered, and is in close contact with the silver mirror film. It has excellent properties, has high chemical stability, and can be easily formed by a film formation method similar to that of a silver mirror film, such as an electroless plating method. As for the film thickness of the copper protective film, it is usually 0.1 g / m ² or more and 1 g / m so that a sufficient chemical durability improving effect on the silver mirror film can be obtained and the adhesion to the silver mirror film is not impaired. m ² or less, preferably 0.2 g / m ² or more and 0.6 g / m ² or less.

Further, in the present invention, the back stop coating film formed on the copper protective film is for imparting corrosion resistance and mechanical durability of silver mirror film and a copper protective film of the epoxy Powder containing an epoxy resin selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and cresol novolac epoxy resin having an equivalent weight in the range of 706 to 1550 , and a curing agent made of adipic acid hydrazide and / or dicyandiamide. Ru is formed by powder coating with body paint composition. And as an epoxy resin, only 1 type can be used, and 2 or more types can also be used if necessary. By using such an epoxy resin, even if a copper protective film is present on the silver mirror film, the adhesion of the coating powder is not reduced, and the backing coating film has good adhesion on the copper protective film. Can be formed.

In the present invention, in addition to the epoxy resin and the curing agent , a pigment is usually blended in the powder coating composition, and, if necessary, a surface conditioner and a cup used in a normal powder coating composition. Additives such as a ring agent and a curing accelerator are blended.

Here, the curing agent blended in the powder coating composition of the present invention is adipic acid hydrazide and / or dicyandiamide, and these curing agents are 0.5 or more in an equivalent ratio with respect to the epoxy group of the epoxy resin. It is used in the range of 1.5 or less, preferably 0.6 or more and 1.2 or less. The blending ratio of this curing agent affects the coating performance and the machinability of the backing coating film formed using this powder coating composition, and when the equivalent ratio is more than 1.5, the workability at the time of production is poor. On the contrary, if the equivalent ratio is less than 0.5, sufficient performance as a backing coating film cannot be obtained.

  Further, the pigment blended in the powder coating composition of the present invention is not particularly limited, and representative examples include titanium dioxide, bengara, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, and quinacridone. And pigments such as pigments and azo pigments, and extender pigments such as silica, talc, precipitated barium sulfate and calcium carbonate. The blending ratio of such a pigment is usually 20% by weight or more and 50% by weight or less, preferably 30% by weight or more and 40% by weight or less, based on the total weight of the powder coating composition. If the amount is too small, the flexibility of the resulting backing coating film will be too good, and when the final shape is made by cutting, the cut-off property of the cut ends will worsen. On the other hand, if it exceeds 50% weight, the finished appearance will be Deteriorate.

  Furthermore, as for the additives to be blended as necessary in the powder coating composition of the present invention, examples of the surface conditioner include acrylic oligomers such as Regiflow P67, Acronal 4F, Modaflow Powder, Polyflow 95, etc. Examples of the ring agent include silane coupling agents, and further examples of the curing accelerator include imidazole compounds, tertiary amines such as triphenylphosphine and N, N-dimethylbenzylamine, and tetrabutylammonium bromide. Examples include quaternary ammonium salts.

  The powder coating composition of the present invention should be prepared by mixing and kneading the blending components according to a conventional method that has been conventionally employed, and uniformly dispersing the whole, followed by pulverization. Can do.

  Moreover, the powder coating composition of this invention can be apply | coated on a copper protective film by the method similar to a normal powder coating composition. The most preferred coating method is an electrostatic powder spray method. Further, the baking conditions after coating are such that the baking temperature is usually 140 ° C. or more and 200 ° C. or less, preferably 140 ° C. or more and 160 ° C. or less, and the baking time is usually 3 minutes or more and 20 minutes or less depending on the temperature and equipment. It is.

  In the present invention, as a method for manufacturing the above-mentioned mirror, a method that has been employed in the manufacture of this type of mirror can be applied. Typically, first, the surface is first smooth and the surface Prepare a glass substrate with as few defects as possible, thoroughly wash the glass substrate with, for example, cerium oxide, and then contact the surface on which the silver mirror film is formed with a sensitizing solution containing, for example, tin (II) chloride. Bismuth (III), chromium (II), gold (III), indium (III), nickel (II), palladium (II), platinum (II), rhodium (III), ruthenium (III), titanium ( III), silver plating that activates with an activation solution containing at least one ion of vanadium (III) and zinc (II), and deposits silver on the surface, for example, by electroless plating (so-called silver mirror reaction) Liquid on glass substrate The silver mirror surface film is formed by a method of playing), and then a copper plating solution for depositing copper or copper alloy is sprayed on the formed silver mirror surface film by an electroless plating method to form a copper protective film, followed by washing. A mirror substrate having a silver mirror film and a metal protective film formed on a glass substrate by drying, and the corrosion resistance and mechanical durability of the silver mirror film and the metal protective film on the copper protective film of the mirror substrate In order to enhance the properties, the above-mentioned powder coating composition is applied and cured to form a backing coating film.

  In the mirror of the present invention, the backing coating film is formed by powder coating of a powder coating composition containing a specific epoxy resin, and excellent adhesion is ensured even if a copper protective film is used for the silver mirror film. In addition to being excellent in workability such as cutting and chamfering, it exhibits excellent chemical resistance and corrosion resistance under various usage conditions that can be considered under normal circumstances, especially in cast tests. Moreover, there are no environmental problems due to organic solvents.

FIG. 1 is a partial cross-sectional explanatory view showing a mirror according to an embodiment of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples.

First, FIG. 1 shows a specific example of a mirror according to an embodiment of the present invention.
In the mirror of this embodiment, a silver mirror film 2 is formed on a glass substrate 1, and the chemical durability of the silver mirror film 2 is enhanced on the silver mirror film 2 to protect the silver mirror film 2. The copper protective film 3 is formed on the copper protective film 3. Further, the silver mirror surface film 2 and the copper protective film 3 are protected on the copper protective film 3 to improve the corrosion resistance and durability as a mirror. A film 4 is formed.

[Examples 1, 2, 4, 5, and 7 to 9, and Reference Examples 3, 6, and 10]
First, according to a conventional method, on a sufficiently cleaned glass substrate (size: 72 mm × 36 mm × 5 mm), a silver plating solution of a solution containing silver nitrate that precipitates silver by a silver mirror reaction and a reducing solution that reduces silver is prepared. Spraying was performed to form a 1 g / m ² thick silver mirror film. Next, this silver mirror film is washed with water, and then a copper plating solution of a solution containing copper sulfate for depositing copper by an electroless plating method and a reducing solution for reducing copper is sprayed on the silver mirror film, and 0.30 g A copper protective film having a thickness of / m 2 was formed, then washed with water and dried to form a mirror base material in which a silver mirror film and a copper protective film were laminated on a glass substrate. About this mirror base material, it prepared for the number of the Example and the comparative example.

[Preparation of powder coating composition]
Epoxy resin A [trade name: Epicoat 1003; Epoxy equivalent: 706], epoxy resin B [Product name: Epicoat 1004AF; Epoxy equivalent: 950], Epoxy resin C [Japan] Epoxy resin product name: Epicoat 1005HL; Epoxy equivalent: 1278], Epoxy resin D [Japan Epoxy Resin product name: Epicoat 1001; Epoxy equivalent: 650], and Epoxy resin E [Japan Epoxy Resin product name: Epicoat 1007; epoxy equivalent: 1550], acrylic leveling agent (trade name: Polyflow # 95, manufactured by Kyoeisha Chemical Co., Ltd.) as the surface conditioner, and adipic acid hydrazide (manufactured by Nippon Hydrazine Kogyo Co., Ltd.) as the curing agent. Product name: ADH), Dicyandiamide (SKW product name: Dyhard 100S) , Phenolic hydroxyl group-containing epoxy resin (epoxy phenol 1; trade name: DEH81 manufactured by Dow) and phenolic hydroxyl group-containing epoxy resin (epoxy phenol 2; trade name: TH2000 manufactured by Tohto Kasei Co., Ltd.), and a curing accelerator As 2-heptadecylimidazole (trade name: Curezol C17Z, manufactured by Shikoku Chemicals Co., Ltd.) and 2-methylimidazole (trade name: Curezol 2MZ, manufactured by Shikoku Chemicals Co., Ltd.), and calcium carbonate (manufactured by Shimizu Kogyo Co., Ltd.) as a pigment. ) And carbon black (trade name: MA100 manufactured by Mitsubishi Chemical Co., Ltd.) and blended in the proportions shown in Table 1 below, and coarsely mixed using a Henschel mixer to obtain a coarse mixture of powder coating components.

Next, the coarse mixture of the powder coating components obtained as described above is melt-kneaded at 100 ° C. with a twin-screw extruder, and the obtained kneaded product is cooled with a cooling roll and then finely pulverized with a pulverizer. A powder coating composition of 150 mesh pass was prepared.

For each of the powder coating compositions of Examples 1 to 10 and Comparative Example 1 thus obtained, using an electrostatic powder spray coating machine, the copper protection of the mirror base of the mirror base prepared earlier was performed. Powder coating was performed on the film so that the film thickness after drying was about 60 μm, followed by baking at 160 ° C. for 20 minutes to form mirror test pieces of Examples 1 to 10 and Comparative Example 1.
The following performance test was done about the mirror test piece of each obtained Examples 1-10. The results are shown in Table 2.

[Cross-cut test]
This was performed in accordance with JIS K 5400 6.15. Judgment determined that the evaluation score was 10 points.

[Hot water immersion test]
The mirror test piece was immersed in pure water at 60 ° C. for 240 hours, and when taken out from the pure water, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Water vapor exposure test]
The mirror specimen was immersed in pure water, heated to a temperature of 60 ° C., exposed for 240 hours, and then visually observed whether any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Hydrogen sulfide gas exposure test]
Four sides of the mirror test piece were sealed with Eponics # 3100SM Clear (manufactured by Dainippon Paint Co., Ltd.), and the sealed mirror test piece was placed in a desiccator under a hydrogen sulfide gas atmosphere and exposed at 30 ° C. for 168 hours. When taking out from the desiccator, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Hydrochloric acid immersion test]
The four sides of the mirror specimen were sealed with Eponics # 3100SM Clear (Dainippon Paint Co., Ltd.), and the mirror specimen after sealing was immersed in 20wt% hydrochloric acid (reagent grade 1) water at 20 ° C for 72 hours. Then, it was visually observed whether or not any abnormality occurred in the silver mirror film when taken out from the hydrochloric acid water. Judgment made the case where abnormality was not recognized as the pass.

[Caustic soda immersion test]
Four sides of the mirror test piece were sealed with Eponics # 3100SM Clear (Dainippon Paint Co., Ltd.), and the mirror test piece after sealing was immersed in 4wt% -caustic soda (reagent grade 1) water at 20 ° C for 96 hours. Then, when taking out from the caustic soda water, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Ammonia water immersion test]
The four sides of the mirror test piece were sealed with Eponics # 3100SM Clear (manufactured by Dainippon Paint Co., Ltd.). After the sealing, the mirror test piece was mixed with 50 parts by weight of ammonia water (reagent grade 1) and 50 parts by weight of pure water. Mixing to prepare a test ammonia water having a concentration of 14% by weight, and immersing the mirror test piece in the test ammonia water at 20 ° C. for 96 hours, and then taking out the test ammonia water from the test ammonia water for any abnormality. It was visually observed whether or not this occurred. Judgment made the case where abnormality was not recognized as the pass.

[Formalin immersion test]
The four sides of the mirror test piece are sealed with Eponics # 3100SM Clear (Dainippon Paint Co., Ltd.), and the mirror test piece after sealing is immersed in formalin (reagent grade 1) at 20 ° C for 312 hours in advance. When taken out from the formalin, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Bleach immersion test]
The four sides of the mirror test piece were sealed with Eponics # 3100SM Clear (Dainippon Paint Co., Ltd.), and the mirror test piece after sealing was placed in a household bleach (Product Name: Kitchen Bright). It was immersed for 96 hours at 20 ° C., and when it was taken out from the bleaching agent, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Detergent immersion test]
The four sides of the mirror test piece were sealed with Eponics # 3100SM Clear (Dainippon Paint Co., Ltd.), and the mirror test piece after sealing was used as a household detergent [trade name: Sunpole (patent no. No. 1,249,719 product)] at 20 ° C. for 72 hours, and when taken out from the detergent, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Salt spray test]
A salt spray test was conducted in accordance with JIS Z 2371, and after 500 hours, it was visually observed whether or not any abnormality occurred within 5 mm from the edge of the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Accelerated weathering test]
After conducting an accelerated weathering test in 240 hours in accordance with JIS K 5400 6.17, the silver coating film was visually observed to see if any abnormality occurred, and the backing coating film “wrinkled, swollen, cracked, Whether or not “peeling and chalking” occurred was visually observed. In the judgment, no abnormality was observed in the silver mirror film, and the case where there was no wrinkle, swelling, cracking or peeling was regarded as acceptable.

[Separability test]
When using a cross cutting machine to divide the mirror test piece into four horizontal and vertical characters, place a toothpick under the cut line after placing the cut line, fold the mirror test piece into four by pressing the toothpick from above Thereafter, when the toothpick was lifted, the height when the backing coating film was separated from the toothpick was measured and evaluated. The evaluation was performed in four stages of ◯: 0 to 10 mm, Δ: 10 to 20 mm, and x: 20 mm or more.

[Chamfering test]
After the mirror test piece was heat-treated at 120 ° C. for 1 hour, chamfering was performed at a back surface chamfering width of 3 mm and a speed of 25 mm / min, and the presence or absence of peeling at the formed edge portion was visually observed. The evaluation was made in three stages: ◎: no peeling was observed (accepted), ○: peeling was observed only partially (passed), and x: peeling was observed (failed).

[Boiling water immersion test]
The mirror specimen was immersed in pure water at 98 ° C. for 18 hours, and when taken out from the boiling water, it was visually observed whether or not any abnormality occurred in the silver mirror film. Judgment made the case where abnormality was not recognized as the pass.

[Appearance observation]
The appearance of the mirror specimen was observed under a halogen lamp. A case where there were no holes or coatings visually, and there was no roughness even when touched with a finger, was regarded as acceptable.

[Comparative Example 1]
As the epoxy resin, a solvent-type bisphenol-type epoxy ester resin [epoxy resin F; epoxy equivalent: 900 to 1000] prepared by the following method was used. The solvent, ethyl cellosolve, and xylene were blended in the proportions shown in Table 1 and dispersed uniformly using glass beads to obtain a solvent-type coating composition of Comparative Example 1.

  Next, the solvent-type coating composition of Comparative Example 1 is applied on a copper protective film of the same mirror base material used in Example 1 with a flow coater, and the object temperature is 150 ° C. for 10 minutes. The mirror test piece of Comparative Example 1 was formed by drying. About the obtained mirror test piece of Comparative Example 1, a performance test was conducted in the same manner as in Example 1. The results are shown in Table 2.

In addition, said epoxy resin F was prepared as follows.
In a reaction vessel equipped with a heating device, a stirrer, a thermometer, and a water separator, 950 parts by weight of bisphenol A diglycidyl ether type epoxy resin [Dainippon Ink Chemical Co., Ltd. trade name: Epiklone 4050; epoxy equivalent 900-1000] Then, 50 parts by weight of succinic acid and 430 parts by weight of xylene were charged and heated in an inert gas atmosphere. Stirring is started when the raw material is melted and stirring is possible, 25 parts by weight of 2-methylimidazole is added, the temperature is raised to 140 ° C., and the reaction is continued for 5 hours at the same temperature. At that time, the reaction was terminated and the reaction system was cooled. After cooling the reaction system, 800 parts by weight of propylene glycol monomethyl ether was added to obtain a bisphenol type epoxy ester resin solution (epoxy resin F) having a nonvolatile content of 45% by weight.

  As is clear from the results in Tables 1 and 2 above, the mirror according to each example of the present invention has good adhesion to the copper protective film, and is resistant to water vapor, water, ammonia, It excels in chemical durability such as alkalinity, acid resistance, formalin resistance and hydrogen sulfide resistance, and it also excels in mechanical properties such as adhesive strength, breaking strength and impact resistance. Further, in the mirror according to each embodiment of the present invention, since the backing coating film is formed by powder coating, this backing coating film has appropriate flexibility, elasticity, stretchability, separation. And the hardness, adhesion strength with copper protective film, residual stress, thermal expansion coefficient, etc. are improved, and as a result, the back coating is applied to the cut and chamfered parts during mirror cutting and chamfering. The film, the copper protective film, or the silver mirror surface film is not peeled off, the separation property after the mirror cutting process is good, and the mechanical damage is small.

  DESCRIPTION OF SYMBOLS 1 ... Glass substrate, 2 ... Silver mirror surface film, 3 ... Metal protective film, 4 ... Back coating film.

Claims (4)

A bisphenol A type epoxy resin in which the back coating film has an epoxy equivalent in the range of 706 to 1550 in a mirror formed by sequentially forming a silver mirror surface film, a copper protective film, and a back coating film on a glass substrate. , bisphenol F type epoxy resin, and powder coating of the powder coating composition comprising one or more epoxy resins selected from cresol novolak epoxy resin, a curing agent consisting of hydrazide adipate and / or dicyandiamide mirror, wherein the coating der Rukoto. The mirror according to claim 1, wherein the powder coating composition contains a curing accelerator and a pigment as components other than the epoxy resin and the curing agent. In the manufacturing method of the mirror which forms a silver mirror surface film | membrane, a copper protective film, and a back coating film in order on a glass substrate , the bisphenol A type whose epoxy equivalent is in the range of 706-1550 on the said copper protective film A powder coating composition containing one or more epoxy resins selected from an epoxy resin, a bisphenol F-type epoxy resin, and a cresol novolac epoxy resin, and a curing agent made of adipic hydrazide and / or dicyandiamide is used. A method of manufacturing a mirror, comprising forming a backing coating film by powder coating. The method for producing a mirror according to claim 3 , wherein the powder coating composition contains a curing accelerator and a pigment as components other than the epoxy resin and the curing agent.

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