JP4657638B2 - Metal-like soft molded body - Google Patents

Description

  The present invention relates to a metal-like soft molded body in which a metal-like decoration is made on the surface of a molded body such as a soft resin or an elastomer.

  Despite being a resin material, molded bodies with a unique color of metal are used in various places. In order to obtain such a metal-like resin molded body, various techniques for processing the resin surface to make it metal-like are known. Examples of such methods include electroless plating on the resin. There are methods such as sputtering and ion plating.

  However, the technology for forming the metal coating on the resin surface is that the metal is easy to adhere if the base resin is hard, and the resin can have a metallic luster similar to that of a metal plate. A soft resin not only makes it difficult for metal to adhere to it, but it also makes it difficult to maintain the initial state due to metal cracking, disordered particle orientation, and exudation of components from the resin as the resin deforms. There was a problem that the change occurred in a short time.

Therefore, techniques such as forming a base coat layer between the soft resin and the metal coating or improving the metal coating layer have been developed for forming a metal coating on the soft resin. For example, Japanese Patent Application Laid-Open No. 59-157277 (Patent Document 1) discloses a technique for depositing a crosslinkable resin film in order to improve the deposition characteristics on a flexible polymer. Japanese Patent Application Laid-Open No. 9-70920 (Patent Document 2) discloses a structure having a crystal grain boundary made of microscopically fine metal grains instead of a continuous film as an improvement of the metal coating layer. As described above, a technique in which the metal itself is not subjected to stress is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 11-34220 (Patent Document 3) discloses a technique in which the metal coating layer has a crystal grain boundary structure and the adhesive force of the base coat layer is increased.
JP 59-157277 A JP-A-9-70920 JP-A-11-34220

  However, the conventional methods for providing and improving the base coat layer have not been able to solve the problem that the metal coating layer is cracked when an external impact force or heat is applied. In addition, the method of generating the crystal grain boundary in the metal coating layer in advance is difficult to control the thickness of the metal coating layer in order to form the crystal grain boundary, and the thickness of the metal coating layer must be relatively thin. The metal gloss was not satisfactory. Furthermore, it is difficult to control the crystal grains, and depending on the size, it may appear cloudy.

  Therefore, the present invention does not have these disadvantages, can maintain an excellent metallic tone even by impact or heat, and can have a sufficient metallic luster, and can be made of a soft material such as an elastomer. It was made for the purpose of obtaining a metal-like soft molded body that can also be used as a base material.

That is, the present invention in order to achieve this object, the surface of the soft base material linear expansion coefficient of ^{60 × 10 -6 / K~220 × 10} -6 / K, the same as the linear expansion coefficient of the soft base material Provided is a metal-like soft molded article having a base coat layer having a linear expansion coefficient of smaller than that and further having a metal thin film layer having a layer thickness of 15 nm to 120 nm on the surface of the base coat layer.

A base coat layer having a linear expansion coefficient equal to or smaller than the linear expansion coefficient of the soft base material is formed on the surface of the soft base material having a linear expansion coefficient of 60 × 10 ⁻⁶ / K to 220 × 10 ⁻⁶ / K. And having a metal thin film layer with a layer thickness of 15 nm to 120 nm on the surface of the base coat layer, the surface has an excellent metallic luster that does not look whitish, and has a sufficient metallic luster. Is possible. In addition, an excellent metallic tone can be maintained even after receiving external impact or heat due to bending or the like. Furthermore, no special post-treatment is necessary.

Although it is not clear why the present invention can achieve such an excellent effect, first, a soft base material that should be made into a metallic tone has a linear expansion coefficient of 60 × 10 ⁻⁶ / K to 220. By limiting the material to x 10 ⁻⁶ / K and limiting the linear expansion coefficient of the base coat layer to the same or smaller value, even if the temperature rises during the formation of the metal thin film layer, the soft substrate Though it is a material, it can be accommodated in a predetermined amount of expansion, so that the metal adheres to the surface of the base coat layer in an orderly manner, and even if there is a subsequent shrinkage of the soft material due to a decrease in temperature, the metal adhesion state is unlikely to occur. It is done. Further, it is considered that the base coat layer that is on the metal adhesion surface side and receives a temperature rise less than the soft base material has less expansion, and even a thin base coat layer hardly causes internal stress. That is, since the linear expansion coefficient of the base coat layer is the same as or smaller than the linear expansion coefficient of the soft base material, the apparent linear expansion coefficient of the soft base material becomes small and the surface side expansion can be suppressed.

  And since the metal thin film layer made of a metal strongly adhered to the base coat layer has a thickness of 15 nm to 120 nm, it does not crack even if it is bent due to the malleability and ductility of the metal, and clouding occurs such that the surface looks whitish. A metal-like soft molded article excellent in metal gloss is obtained.

  Examples of the soft base material in the present invention include a base material having a degree of flexibility that can be deformed by the force of a human fingertip. By pressing with the fingertip, a dent is generated or pinched with a fingertip. Resin or elastomer that bends like a bow can be included. Moreover, the linear expansion coefficient shown by this specification is the value determined in the range of 290K-370K.

  The thickness of the metal thin film layer is preferably 80 nm to 120 nm. When the thickness is 80 nm to 120 nm, the metal thin film layer is not seen through, has a feeling of weight, and a metallic tone having a sufficient metallic luster like a metal plate can be obtained.

  The metal-like soft molded article of the present invention can be configured as having a topcoat layer on the surface of the metal thin film layer. By providing the top coat layer, the metal thin film layer is protected from external rubbing, scratching, and the like, and is not exposed to the outside air, and is protected from oxidation and dirt adhesion. Furthermore, it can be set as the metal genus soft molded body excellent in moisture resistance.

  The top coat layer has a linear expansion coefficient equal to or smaller than that of the base coat layer. If the linear expansion coefficient of the topcoat layer is equal to or smaller than that of the basecoat layer, the metal thin film layer is sandwiched between the basecoat layer and the topcoat layer, which have a smaller linear expansion coefficient than the soft substrate. , Excellent adhesion to a soft substrate and followability, and stress for bending is alleviated. In addition, the metal-like soft molded body is less susceptible to temperature changes and is more excellent in durability, weather resistance, and moisture resistance.

  The resin used for the top coat layer can be a cross-linked resin such as a heat curable resin or an ultraviolet curable resin. If the linear expansion coefficient of the topcoat layer is equal to or smaller than the linear expansion coefficient of the basecoat layer, the surface does not look whitish even if the thermal history during formation of the topcoat layer is applied. Tones can be maintained.

  According to the metal-like soft molded article of the present invention, the base material is a soft material such as a soft resin or elastomer, but has the gloss and color of the metal, and can only have a sufficient metal gloss. In addition, the surface does not look whitish even after receiving an impact due to bending or heat, and an excellent metallic tone can be maintained.

  The metal-like soft molded article of the present invention will be described in more detail. In the following description of the embodiment and the like, the overlapping description is omitted when the structure is an overlapping structure or when an overlapping method is used.

First Embodiment FIG. 1 shows a layer structure of a metallic soft molded body 11 according to an embodiment of the present invention. The metal-like soft molded body 11 has a base coat layer 13 made of a predetermined resin on the surface of a soft substrate 12 made of a soft molded body, and further has a metal thin film layer 14 on the surface thereof.

A soft molded body made of a soft base material 12, there like a rubber-like elastic material and a soft resin, its linear expansion coefficient is in the range of ^{60 × 10 -6 / K~220 × 10} -6 / K Material is used. The reason why the linear expansion coefficient is set to 60 × 10 ⁻⁶ / K to 220 × 10 ⁻⁶ / K is that a soft material smaller than 60 × 10 ⁻⁶ / K is difficult to obtain, and 220 × 10 ⁻⁶ / K. This is because the surface of the metal thin film layer 14 may appear whitish (white turbidity) and the metallic luster may deteriorate.

Examples of the material to be the soft substrate 12 include various elastomers such as ethylene, urethane, olefin, polyester, and ether as rubber-like elastic bodies, styrene butadiene rubber, butadiene rubber, butyl rubber, Synthetic rubbers and natural rubbers such as isoprene rubber, acrylonitrile butadiene rubber, ethylene propylene rubber, chloroprene rubber, silicone rubber, acrylic rubber, and fluorine rubber can be mentioned. Examples of the soft resin include soft acrylic, vinyl chloride, and olefin resin. In general, the values of linear expansion coefficients are 140 to 160 × 10 ⁻⁶ / K for olefin-based thermoplastic elastomers, 100 to 220 × 10 ⁻⁶ / K for ether-based thermoplastic elastomers, and 100 for polyester-based thermoplastic elastomers. ˜230 × 10 ⁻⁶ / K, butyl rubber is 180 × 10 ⁻⁶ / K, chloroprene rubber is 200 × 10 ⁻⁶ / K, and natural rubber is about 150 to 180 × 10 ⁻⁶ / K.

  These soft base materials 12 are preferably made of a material having good adhesion to the base coat layer 13. In particular, when the metal thin film layer 14 is formed by vapor deposition or the like, it is preferable that the component in the soft base material 12 does not ooze out. From this point of view, it is preferable to use a material with a small amount of unreacted monomers and a small content of liquid additives and the like, and a polymer composed of a single or fewer constituent units is preferable.

  The base coat layer 13 is a layer having a function of supporting the metal thin film layer 14, and is a layer interposed between the soft base material 12 and the metal thin film layer 14. It is preferable that the adhesiveness with respect to both is high. The base coat layer 13 is made of an evaporative drying type such as an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, an alkyd resin, a fluororesin, an ether resin, a nitrified cotton (nitrocellulose) resin, an ultraviolet curable type, The coating is formed using a thermosetting resin. Among these resins, it is preferable to use a urethane-based or acrylic-urethane-based resin in terms of good followability to the soft base material 12 and excellent flexibility and flexibility, and adhesion to the soft base material 12. In this respect, it is preferable to use a cross-linked resin such as a heat curable type or an ultraviolet curable type.

  The metal thin film layer 14 is a thin metal layer, and can be formed by using, for example, vapor deposition or sputtering. Examples of the metal used include aluminum, chromium, copper, germanium, gold, indium, iron, lead, magnesium, nickel, palladium, platinum, silver, tin, titanium, and zinc. Aluminum, silver, indium, magnesium, tin and the like are preferable in that their melting points are low and a metal thin film can be easily formed.

  The layer thickness of the metal thin film layer 14 is 15 nm to 120 nm, preferably 80 nm to 120 nm. This is because if the thickness is less than 15 nm, sufficient metallic luster that can be said to be metallic can not be obtained, and if it is 80 nm or more, sufficient metallic luster can be obtained as much as the metal plate. Further, if it exceeds 120 nm, cracks may occur when an external force is applied. Therefore, if the layer thickness of the metal thin film layer 14 is set to 80 nm to 120 nm, the metallic luster can be sufficiently exhibited, and a high-quality metal-like soft molded body can be obtained, and defects such as cracks do not occur. .

  The metal-like soft molded body 11 having such a configuration is a metal-like material that has flexibility and excellent surface gloss, and is used for soft robot toys, members that require a metal-like design, In addition, it can be used for various applications such as use for members that require a reduction in mass.

Second Embodiment : The metal-like soft molded body 21 according to the second embodiment has a structure in which a topcoat layer 25 is provided on the surface of the metal thin film layer 14 of the metal-like soft molded body 21 shown in the first embodiment. It is. The structure below the top coat layer 25 is the same as that of the metal-like soft molded body 11 shown in the first embodiment.

  The topcoat layer 25 is a layer having a function of protecting the metal thin film layer 14 and preventing scratches, such as adhesion to the metal thin film layer 14, wear resistance, chemical resistance, and followability to deformation of the soft base material 12. It is preferable to have excellent properties. Examples of materials that can be used as the top coat layer 25 include evaporation of acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, fluororesins, ether resins, and nitrified cotton (nitrocellulose) resins. Examples thereof include dry type, ultraviolet curable type, and heat curable type resins. Among these resins, it is preferable to use a resin having a hydroxyl group in terms of adhesion to the metal thin film layer 14. In addition, from the viewpoint of improving the strength, wear resistance, and chemical resistance of the top coat layer 25, it is preferable to use a cross-linked resin such as a heat curable type or an ultraviolet curable type.

  The linear expansion coefficient of the top coat layer 25 is the same as or smaller than the linear expansion coefficient of the base coat layer 13. The reason why the coefficient of linear expansion of the top coat layer 25 is set to be equal to or less than the coefficient of linear expansion of the base coat layer 13 is to maintain an excellent metallic tone on the surface even after receiving impact or heat due to bending or the like. Because it can. The reason for this is that if the coefficient of linear expansion of the base coat layer 13 is larger, the degree of expansion differs between the top coat layer 25 that is susceptible to external influences and the base coat layer 13 that is difficult to receive, and is sandwiched between both layers. The metal thin film layer 14 is adversely affected, but it is thought that this is not the case. Having the top coat layer 25 is preferable in that the metal thin film layer 14 is protected.

  The metal-like soft molded body 21 having the top coat layer 25 is excellent in that the metal thin film layer 14 is protected and deformation, heat resistance, and moisture resistance are increased by applying force.

  Hereinafter, as examples and comparative examples, Sample A1 to Sample A8 and Sample B1 to Sample B6 shown below were manufactured.

Sample A1 : Polyester thermoplastic elastomer (“Primalloy B193ON” (trade name); manufactured by Mitsubishi Chemical Corporation) having a hardness of Shore D60 and a linear expansion coefficient of 160 × 10 ⁻⁶ / K was used as the soft substrate (12). An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 140 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 80 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of tin having a layer thickness of 40 nm was formed on the surface of the base coat layer (13) by vacuum deposition under the conditions of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . Furthermore, for surface protection, an acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 120 × 10 ⁻⁶ / K is applied and cured under curing conditions of 60 ° C. for 60 minutes. A top coat layer (25) having a layer thickness of 20 μm was formed. The obtained metal-like soft molded body (21) was designated as Sample A1.

Sample A2 : Polyester thermoplastic elastomer (“Gloax EH620” (trade name); manufactured by Dainippon Ink & Chemicals, Inc.) having a hardness of Shore D40 and a linear expansion coefficient of 200 × 10 ⁻⁶ / K as a soft substrate (12) Using. A base coat layer (13) having the same material and layer thickness as the sample A1 was formed on the surface of the soft substrate (12) in the same manner as the sample A1. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed on the surface of the base coat layer (13) by vacuum deposition under a condition of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . Further, a top coat layer (25) having the same material and layer thickness as the sample A1 was formed in the same manner as the sample A1. The obtained metal-like soft molded body (21) was designated as Sample A2.

Sample A3 : Polyester soft engineering plastic (“Dia Alloy SR-50” (trade name); manufactured by Mitsubishi Rayon Co., Ltd.) having a hardness of Shore D57 and a linear expansion coefficient of 60 × 10 ⁻⁶ / K was used as the soft substrate (12). . A urethane acrylate ultraviolet curable coating material prepared so that the linear expansion coefficient after curing is 60 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the integrated light quantity is 1000 mJ / cm ² . Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 120 nm was formed on the surface of the base coat layer (13) by vacuum deposition under the condition of 1 × 10 ⁻² Pa. Furthermore, an acrylic silicone-based thermosetting paint prepared so that the linear expansion coefficient after curing is 50 × 10 ⁻⁶ / K is applied and cured under curing conditions at 60 ° C. for 60 minutes, and the layer thickness is 20 μm. The top coat layer (25) was formed. The obtained metal-like soft molded body (21) was designated as Sample A3.

Sample A4 : The same base coat layer (13) as Sample A3 was formed on the soft substrate (12) used in Sample A3. On the surface of this base coat layer (13), a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed by vacuum deposition under the conditions of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. Furthermore, the same topcoat layer (25) as Sample A3 was formed. The obtained metal-like soft molded body (21) was designated as Sample A4.

Sample A5 : A polyester thermoplastic elastomer (“Primalloy A1800N” (trade name); manufactured by Mitsubishi Chemical Corporation) having a hardness of Shore A85 and a linear expansion coefficient of 220 × 10 ⁻⁶ / K was used as the soft substrate (12). An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 220 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 90 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 120 nm was formed on the surface of the base coat layer (13) by vacuum deposition under the condition of 1 × 10 ⁻² Pa. Furthermore, an acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 160 × 10 ⁻⁶ / K is applied and cured under curing conditions at 60 ° C. for 60 minutes, and the layer thickness is 20 μm. The top coat layer (25) was formed. The obtained metal-like soft molded body (21) was designated as Sample A5.

Sample A6 : The same base coat layer (13) as Sample A5 was formed on the soft substrate (12) used in Sample A5. On the surface of this base coat layer (13), a metal thin film layer (14) made of aluminum having a layer thickness of 15 nm was formed by vacuum deposition under the condition of 1 × 10 ⁻² Pa. Furthermore, the same topcoat layer (25) as Sample A5 was formed. The obtained metal-like soft molded body (21) was designated as Sample A6.

Sample A7 : A metal-like soft molded article (11) similar to Sample A5 was produced except that the topcoat layer was not provided, and this was designated as Sample A7.

Sample A8 : A metal-like soft molded article (11) similar to Sample A1 except that the metal thin film layer (14) was changed to 20 nm indium was produced as Sample A8.

Sample B1 : Polyester thermoplastic elastomer (“Primalloy B1700N” (trade name); manufactured by Mitsubishi Chemical Corporation) having a hardness of Shore A77 and a linear expansion coefficient of 230 × 10 ⁻⁶ / K was used as the soft substrate (12). An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 300 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 80 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed on the surface of the base coat layer (13) by vacuum deposition under a condition of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . The obtained metal-like soft molded body (11) was designated as Sample B1.

Sample B2 : Chloroprene rubber having a hardness of Shore A60 and a linear expansion coefficient of 150 × 10 ⁻⁶ / K was used as the soft base material (12), and the same base coat layer (13) as that of the sample B1 was formed on the surface of the soft base material (12). Formed. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 120 nm was formed on the surface of the base coat layer (13) by vacuum deposition under conditions of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . The obtained metal-like soft molded body (11) was designated as Sample B2.

Sample B3 : As a soft base material (12), a polyester-based thermoplastic elastomer (“Grease EH620” (trade name); manufactured by Dainippon Ink & Chemicals, Inc.) having a hardness of Shore D40 and a linear expansion coefficient of 200 × 10 ⁻⁶ / K Using. An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 300 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 90 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed on the surface of the base coat layer (13) by vacuum deposition under the condition of 1 × 10 ⁻² Pa. Further, the topcoat layer (25) was formed under the same material and conditions as the basecoat layer (13). The obtained metal-like soft molded body (21) was designated as Sample B3.

Sample B4 : Polyester thermoplastic elastomer (“Primalloy A1600N” (trade name); manufactured by Mitsubishi Chemical Corporation) having a hardness of Shore A67 and a linear expansion coefficient of 220 × 10 ⁻⁶ / K was used as the soft base material (12). An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 220 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 90 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 200 nm was formed on the surface of the base coat layer (13) by vacuum deposition under the condition of 1 × 10 ⁻² Pa. Further, the topcoat layer (25) was formed under the same material and conditions as the basecoat layer (13). The obtained metallic soft flexible body (21) was designated as Sample B4.

Sample B5 : Polyester soft engineering plastic (“Dia Alloy SR-50” (trade name); manufactured by Mitsubishi Rayon Co., Ltd.) having a hardness of Shore D57 and a linear expansion coefficient of 60 × 10 ⁻⁶ / K was used as the soft substrate (12). . An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 140 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 80 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed on the surface of the base coat layer (13) by vacuum deposition under a condition of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . The obtained metal-like soft molded body (11) was designated as Sample B5.

Sample B6 : As the soft substrate (12), a polyester-based thermoplastic elastomer (“Primalloy A1800N” (trade name); manufactured by Mitsubishi Chemical Corporation) having a hardness of Shore A85 and a linear expansion coefficient of 220 × 10 ⁻⁶ / K was used. An acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 300 × 10 ⁻⁶ / K is applied to the surface of the soft substrate (12), and the curing condition is 80 ° C. for 30 minutes. Curing was performed to form a base coat layer (13) having a layer thickness of 15 μm. Next, a metal thin film layer (14) made of aluminum having a layer thickness of 80 nm was formed on the surface of the base coat layer (13) by vacuum deposition under a condition of 1 × 10 ⁻² Pa to 1 × 10 ⁻³ Pa. . Furthermore, an acrylic urethane thermosetting paint prepared so that the linear expansion coefficient after curing is 160 × 10 ⁻⁶ / K is applied and cured under curing conditions at 60 ° C. for 60 minutes, and the layer thickness is 20 μm. The top coat layer (25) was formed. The obtained metal-like soft molded body (21) was designated as Sample B6. The results of the peel test are shown in Table 3 below.

  Tables 1 and 2 summarize the materials and configurations of the above samples.

  The following tests were performed on each sample.

Peel test of metal thin film layer: The adhesion of the metal thin film layer (14) to the soft substrate (12) body was tested. The side having the metal thin film layer (14) of each metal-like soft molded body (11, 21) is cut with a cutter in a grid pattern at intervals of 1 mm, and an adhesive tape (“Cello Tape (registered trademark) CT405-18”) is formed on the surface thereof. (Product name: Nichiban Co., Ltd.) was rubbed with a force of 4.9 N and pasted. And this adhesive tape was peeled off in the direction of 90 degrees with respect to the adhesion surface rapidly. The case where the metal thin film layer (14) did not peel and remained on the metal-like soft molded body (11, 21) was evaluated as “◯”. On the other hand, the case where the metal adhered to the adhesive tape side was evaluated as “x”. The results of the peel test are shown in Table 3 below.

Appearance test: The appearance of the metal-like soft molded body (11, 21) was evaluated by visual observation, reflectance using a spectrophotometer, and magnified observation of the surface with a microscope.

Visual evaluation : The sample was observed with the naked eye. It has a metallic luster, and it is “○” if it has no inconveniences that are not seen on normal metal surfaces such as whiteness or cracks. The case where the whitishness that cannot be seen on the normal metal surface can be seen or the case where cracks appear is evaluated as “x”. This appearance test was performed not only immediately after the production of the metal-like soft molded body (11, 21) but also after the bending test (bent 90 ° with the metal thin film layer side of the metal-like soft molded body as the mountain side to make an L shape) It was also performed in each case after a heat resistance test at 80 ° C. × 30 minutes and a humidity resistance test at 65 ° C. and 95% rh × 120 hours. The results are shown in Table 3.

  In Table 3, the defect indicated by * 1 is a defect in which fine wrinkles are generated in the metal thin film layer (14), and the metal thin film layer (14) appears cloudy when visually observed. The soft base material (12) and the base coat layer (13), which are thermally expanded by the heat at the time of metal thin film layer formation (during vapor deposition), are contracted when returning to room temperature. In addition, the defect indicated by * 2 is a defect in which a crack has occurred, and the metal thin film layer (14) cannot follow the expansion of the base coat layer (13) or the top coat layer (25) by applying heat. It is a failure that occurred. Furthermore, the defect indicated by * 3 is a result of decolorization.

Evaluation by reflectance using a spectrophotometer: The reflectance of the sample surface was measured using a spectrophotometer ("UV-1600PC": manufactured by Shimadzu Corporation). The measurement conditions are as follows: the size of each sample surface is 30 mm × 40 mm, the measurement wavelength is 500 nm, the incident angle of the light flux to the sample is 5 degrees, the aperture size of the sample mask is 5 mmφ, the reference mirror is two Al deposition mirrors, and the control is a mirror surface. The reflectance of the aluminum piece whose surface was polished to the state was 100%. The results are shown in Table 4.

Evaluation by microscope : Using an optical microscope (“Hisome”: manufactured by Union Optical Co., Ltd.), the surface of the sample was enlarged and observed under the conditions of eyepiece lens: × 10 and objective lens: × 20. The optical micrograph is shown in FIG.

  In FIG. 3, [1] is immediately after the production of the sample A1, [2] is immediately after the production of the sample A2, [3] is after the bending test of the sample A2, [4] is after the heat resistance test of the sample A2, [5] ] Is a micrograph immediately after manufacture of sample A8, [6] is immediately after manufacture of sample B2, [7] is a micrograph immediately after manufacture of sample B6, [7] is after the heat resistance test of sample B2.

  As can be seen by comparing the above examples, the metal-like soft molded body (11, 21) of the present invention has an excellent metal tone and is excellent without any change in gloss even after a bending test or heat resistance test. The metallic tone can be maintained. Furthermore, it can be seen that if there is a top coat layer, the moisture resistance is also excellent.

It is a partial expanded sectional view of the metal tone soft molded object by 1st Embodiment of this invention. It is a partial expanded sectional view of the metal tone soft molded object by 2nd Embodiment of this invention. It is a figure which shows the microscope picture of a metal tone soft molded object surface.

Explanation of symbols

11, 21 Metal-like soft molded body 12 Soft base material 13 Base coat layer 14 Metal thin film layer 25 Top coat layer

Claims (5)

A base coat layer having a linear expansion coefficient equal to or smaller than the linear expansion coefficient of the soft base material is provided on the surface of the soft base material having a linear expansion coefficient of 60 × 10 ⁻⁶ / K to 220 × 10 ⁻⁶ / K. and the layer thickness on the surface of the base coat layer have a metal thin film layer is 15Nm～120nm, topcoat layers having the same or smaller than the linear expansion coefficient of the linear expansion coefficient of the base coat layer on the surface of the metal thin film layer Metal-like soft molded body having The metal-like soft molded article according to claim 1, wherein the soft substrate is a rubber-like elastic body. The metal-like soft molded article according to claim 1 or 2, which can be bent by 90 ° with the metal thin film layer side as a peak side. The metal-like soft molded article according to any one of claims 1 to 3, wherein the metal thin film layer has a thickness of 80 nm to 120 nm. The metal-type flexible molded article according to any one of claims 1 to 4 , wherein the resin used for the topcoat layer is a cross-linkable resin such as a heat curable resin or an ultraviolet curable resin.