JP4698392B2 - Metal-like soft polymer molding - Google Patents

Description

  The present invention relates to a metal-like soft polymer molded body in which a metal-like decoration is made on the surface of a soft polymer molded body.

  It is known that a metal-like resin molded body having a metal thin film layer on the surface of the resin molded body can be obtained by forming a metal thin film layer on the surface of the resin molded body by a method such as plating, vapor deposition, sputtering, or ion plating. Therefore, by vapor deposition, so-called mirror-like decoration with good glossiness can be realized, and the metal thin film layer can emit the same metallic luster as a metal plate or the like. In such a case, a metal film is generally formed on the surface of a hard resin, and a surface film with high adhesion that is difficult to peel off can be obtained.

  However, when a soft polymer molded body is used instead of the hard resin molded body, the metal thin film layer is deformed in conjunction with the deformation of the molded body, so that the metal thin film layer is cracked or clouded. There is an inconvenience that you can see. In addition, various additives for imparting softness are often mixed in the soft polymer molding, and the metal thin film layer is easily peeled off due to the exudation of the additive component, and the gloss changes. There is a problem that it is easy to do.

These problems are known to occur when the metal thin film layer is formed as a uniform continuous film. To solve this problem, the metal thin film layer is not formed as a uniform continuous film. It has been proposed to For example, in Japanese Patent Application Laid-Open No. 11-34220 (Patent Document 1), it is configured to form fine metal particles, or in Japanese Patent Application Laid-Open No. 11-131213 (Patent Document 2), a metal thin film layer formed as a continuous film It has been proposed to form a metal thin film layer having cracks by heating the metal.
JP-A-11-34220 JP-A-11-131213

  However, the metal thin film layer formed by the method of Patent Document 1 becomes cloudy when a topcoat layer is provided on the surface thereof, and may not maintain a metallic luster. The cause is not clear, but when the topcoat is formed, the topcoat layer ink enters the fine metal particles forming the metal thin film layer and disturbs the arrangement of the fine metal particles. It is presumed that this is caused by interference and causing diffuse reflection. Moreover, in the method described in Patent Document 2 in which cracks are formed in advance, there is a problem that it is difficult to control the size of the cracks and stable manufacturing conditions cannot be obtained.

  Therefore, in the present invention, an excellent metal tone is realized in the flexible polymer molded body, and even when a top coat layer is provided, the gloss is not lost and the excellent metal tone can be maintained. It was made for the purpose of obtaining a high-quality metal-like soft polymer molding that is difficult to obtain.

That is, the present invention is a metal-like soft polymer molded product having a metal thin film layer on a soft polymer molded product, and the metal thin film layer is made of vapor-deposited metal particles whose maximum length in the longitudinal direction is within 0.5 μm. Provided is a metal-like soft polymer molded article having a flat surface structure in which a large number of islands are discontinuously dense and having a layer thickness of 20 nm to 100 nm.

Since the metal thin film layer has a flat surface structure in which a large number of island portions made of vapor-deposited metal grains having a maximum length in the longitudinal direction of 0.5 μm or less are concentrated discontinuously and the layer thickness is 20 nm to 100 nm, It is possible to obtain a metal-like soft polymer molded body having an excellent metallic luster without being clouded. Moreover, even if a top coat layer is provided, it can have excellent metallic luster without causing cloudiness. Furthermore, since it can be manufactured by predetermined vapor deposition, it is possible to obtain a metal-like soft polymer molded body that can be stably manufactured, has a low manufacturing cost, and can stably obtain a defect-free quality.

According to the present invention, the metal thin film layer is within the range of 3.5 μm × 5.0 μm according to the surface photograph taken with a scanning electron microscope, and the presence of an island part having a size exceeding the maximum length is omitted. It can be set as the metal tone soft polymer molded object which is two or less places.

That is, the surface structure in which many islands of the metal thin film layer are discontinuously densely packed is in the range of 3.5 μm × 5.0 μm of the surface of the metal thin film layer by the surface photograph taken with a scanning electron microscope. Thus, it can be considered that there are two or less island portions that are missing or larger than the maximum length. Metal-like soft polymer that has excellent metallic luster without white turbidity as long as there are two or less total locations of islands with a size exceeding the maximum length and omission of islands within a predetermined range It can be set as a molded body, and even if a top coat layer is provided, it does not become cloudy.

  A rubber-like elastic body having an A hardness of 50 to 95 according to JIS K 6253 can be used as the soft polymer molded body. Since the rubber-like elastic body in which the hardness of the soft polymer molded body is 50 to 95 in A hardness of JIS K 6253 hardness is used, even if the soft polymer molded body is greatly deformed, the metal is The metal particles constituting the thin film layer follow, and the metal thin film layer is not easily cracked or peeled off. And it can be set as the metal tone soft polymer molded object which does not become cloudy and has the outstanding metallic luster, and even if it provides a topcoat layer, it does not become cloudy. Therefore, even if it is used for applications requiring flexibility, the metallic luster is not inferior, and a stable metallic appearance can be maintained. Furthermore, since it can manufacture by predetermined vapor deposition, it can be set as the metal tone soft polymer molded object which can be manufactured stably at low manufacturing cost.

  The soft polymer molded body can be made of a thermoplastic elastomer. By using a soft polymer molded body as a thermoplastic elastomer, a soft molded body having an excellent metallic luster and the same appearance as a metal can be obtained. Moreover, it can be set as the metal tone soft polymer molded object which has a thermoplasticity and is hard to produce a crack and peeling of a metal thin film layer.

  Moreover, this invention can provide a topcoat layer in the surface on the opposite side to the soft polymer molded object side of a metal thin film layer. A metal-like soft polymer molded product that has a topcoat layer on the surface opposite to the soft polymer molded product side of the metal thin film layer has excellent metallic luster and ease of manufacturing, but also wear resistance It becomes a metal-like soft polymer molding excellent in properties and the like.

  It can be set as the metal tone soft polymer molded object which has a basecoat layer between a soft polymer molded object and a metal thin film layer. If the metal-like soft polymer molded body has a base coat layer between the soft polymer molded body and the metal thin film layer, even if the adhesion of the metal thin film layer is good and the surface state of the soft polymer molded body is somewhat poor In addition, a metal-like soft polymer molded body having a metallic luster and capable of being stably manufactured can be obtained.

  According to the metal-like soft polymer molded body of the present invention, even when a topcoat layer is provided on the metal thin film layer, the metal-like soft polymer molding has excellent metallic luster without being clouded. Is the body. Moreover, the manufacture is easy.

  The metal-like soft polymer molding of the present invention will be described in more detail. In the description of each embodiment, duplicate description is omitted when the same material and the same manufacturing method as those described in the previous embodiment are used.

First Embodiment FIG. 1 shows a layer structure of a metallic soft polymer molded body 10 according to a first embodiment of the present invention. The metal-like soft polymer molded body 10 has a base coat layer 11 made of a resin film on the surface of the soft polymer molded body 11, a metal thin film layer 13 on the surface, and a top coat layer 14 on the surface. ing.

  A polymer material having a hardness of 20 to 100 according to JIS K 6253 can be used for the flexible polymer molded body 11, and in particular, a soft high material having a hardness of 50 to 95 according to JIS K 6253 can be used. Molecular materials can be used. These materials include rubber-like elastic bodies such as soft resins and thermoplastic elastomers. Specific examples of the soft resin include soft acrylic, vinyl chloride, and olefin resins, and examples of the rubber-like elastic body include ethylene, styrene, urethane, olefin, polyester, ether, polyamide, and the like. And various types of thermoplastic elastomers, synthetic rubbers such as styrene butadiene rubber, butadiene rubber, butyl rubber, isoprene rubber, acrylonitrile butadiene rubber, ethylene propylene rubber, chloroprene rubber, silicone rubber, acrylic rubber, and fluoro rubber, and natural rubber.

  Further, the material used for the soft polymer molded body 11 is preferably of a type that has good adhesion to the base coat layer 11 and does not exude the components of the soft polymer molded body 11. From this point of view, it is preferable to use a material with a small amount of unreacted monomers and a small amount of liquid additives and the like, and a polymer consisting of a single or fewer constituent units is preferable. In addition, it is preferable to use a thermoplastic elastomer as the flexible polymer molding. This is because if a thermoplastic elastomer is used, the surface can be decorated in a metallic style with a soft material. The soft polymer molded body 11 can be obtained by molding a soft polymer as a raw material by injection molding or the like.

  The base coat layer 12 has adhesion to both the soft polymer molded body 11 and the metal thin film layer 13 which are base materials, and is a layer provided to increase the adhesion of the metal thin film layer 13 to the soft polymer molded body 11. It is. Specifically, evaporative drying, ultraviolet curable, and heat curable resins made of acrylic resin, urethane resin, polyester resin, epoxy resin, alkyd resin, fluororesin, ether resin, and nitrified cotton (nitrocellulose) resin are used. Can be formed. The base coat layer 12 is preferably made of a material that flexes flexibly following the deformation when the flexible polymer molded body 11 is deformed. From this viewpoint, it is preferable to use a urethane-based or acrylic urethane-based resin. The base coat layer 12 can be formed by coating the surface of the soft polymer molded body 11 by various methods such as printing and coating.

  The metal thin film layer 13 is a thin metal layer and can be formed by a vapor deposition method. 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 metal thin film layer 13 can be formed on the soft polymer molded body 11 by using a vapor deposition device and dispersing the metal uniformly and linearly in the space of the vapor deposition device. The metal thin film layer 13 composed of uniformly discontinuous metal particles can be formed on the soft polymer molded body 11 by scattering the metal uniformly and linearly in the space of the vapor deposition apparatus. On the other hand, when the evaporated metal does not scatter evenly and linearly, the metal concentration is non-uniform in the vapor deposition apparatus, resulting in a metal thin film layer having unevenness on the surface.

  By setting the thickness of the metal thin film layer 13 to 20 nm to 100 nm, the metallic luster is sufficiently exhibited, and a high-quality metallic tone soft molded body can be obtained. If it is thinner than 20 nm, sufficient metallic luster that cannot be said to be metallic can not be obtained, and a blackish color will be exhibited. Moreover, when it exceeds 100 nm, when the topcoat layer 14 is provided, it becomes a cloudy metallic luster, and the metal thin film layer 13 tends to crack.

  The topcoat layer 14 is a layer having functions of protecting the metal thin film layer 13 and preventing scratches, and adheres to the metal thin film layer 13, wear resistance, chemical resistance, and follows deformation of the flexible polymer molded body 11. It is preferable to have excellent properties such as properties. Materials that can be used as the top coat layer 14 include evaporation drying type, ultraviolet curing, and acrylic resin, urethane resin, polyester resin, epoxy resin, alkyd resin, fluororesin, ether resin, and nitrified cotton (nitrocellulose) resin. Examples of the resin include a mold and a thermosetting resin, and it is particularly preferable to use a cross-linked resin. The top coat layer 14 can be formed by coating the surface of the metal thin film layer 13 by various methods such as printing and coating.

The surface state of the metal thin film layer 13 of the metal-like soft polymer molded body 10 thus obtained is shown in FIG. 2, and for comparison, the metal of the metal-type soft polymer molded body as a comparative example formed with various deposition conditions changed. The surface photograph of a thin film layer is shown in FIGS. In all the photographs, the surface after the metal thin film layer is formed is enlarged 25,000 times with a scanning electron microscope. In any of FIGS. 2 to 5, one scale (point-to-point pitch) on the photograph represents 0.2 μm.

The electron micrograph shown in FIG. 2 is a surface photograph of the metal thin film layer 13 of the metal-like soft polymer molding 10 used as the sample 1. Details of the sample 1 will be described later. When the metal thin film 10 of the sample 1 is provided with the metal thin film layer 13 and also when the subsequent top coat layer 14 is provided, it has a mirror-like metallic luster and does not become cloudy. Excellent metallic luster. This is presumably because the metal thin film layer 13 is formed flat with discontinuously dense metal particles and is stable with respect to the topcoat layer 14 and there is no change in the metal particles. That is, the surface of the metal-like soft polymer molded body 10 has a flat surface structure in which a large number of island portions made of vapor-deposited metal grains having a maximum length in the longitudinal direction of 0.5 μm or less are discontinuously densely packed. It appears that there is no island part that is visible in white because the island part is missing or there is an island part with a size exceeding the maximum length, or the surrounding island part is different in contrast. Further, even when the other surface of the metal thin film layer 13 is observed, the surface state by a surface photograph with a scanning electron microscope is within the range of 3.5 μm × 5.0 μm of the surface of the metal thin film layer. There are no more than two locations. When the resistance value between two predetermined points of the metal thin film layer 13 is measured, it becomes about 1 GΩ, and the metal thin film layer 13 is a discontinuous body formed of metal grains, and is considered to be electrically insulated.

  On the other hand, the metal-like soft polymer molded body of Sample 2 as a comparative example shows a surface photograph of the metal thin film layer in FIG. 3, and when the metal thin film layer was provided, it was excellent in that it did not become cloudy. Although it has a metallic luster, it becomes cloudy after the top coat layer is provided, resulting in a metallic soft polymer molded body without metallic luster. This is probably because the metal grains forming the metal thin film layer collapse. The surface of the metal-like soft polymer molded body has a contrast with the surrounding islands and is visible as white and has irregularities on the adjacent islands, and is not a flat plane. Guessed. This is because the metal was not scattered uniformly and linearly in the space of the vapor deposition tank, but was scattered with an uneven distribution, and the metal thin film layer is considered to be a continuous body.

In addition, the metal-like soft polymer molded body of Sample 3 as a comparative example shows a surface photograph of the metal thin film layer in FIG. 4, but when the metal thin film layer is provided as in Sample 2, it may become cloudy. However, after providing the top coat layer, it becomes cloudy and becomes a metal-like soft polymer molded body having no metallic luster. This is presumably because the variation in the metal thin film layer appears to be amplified by the formation of the topcoat layer because of the variation in the density of the metal grains. The surface of this metal-like soft polymer molded body has a surface structure in which a large number of islands made of vapor-deposited metal grains whose maximum length in the longitudinal direction is within 0.5 μm are discontinuously densely formed, as in Sample 1. However, there are 3-4 places where the islands appear to be missing, in other words, where the islands are not dense. This is because the metal thin film layer was formed with a variation in the height direction in the vapor deposition tank because the gap between the filament and the adherend was widened, and the metal thin film layer was considered to be a continuous body. It is done.

Further, the metal-like soft polymer molded body of Sample 4 as a comparative example shows a surface photograph of the metal thin film layer in FIG. 5, but becomes a metal-like soft polymer molded body that becomes clouded from the stage of forming the metal thin film layer. . On the surface of the metal-like soft polymer molded body, large metal particles having a maximum length in the longitudinal direction exceeding 0.5 μm are visible. This is considered to be because the metal thin film layer is a continuous body because the deposition time is increased and the metal grains grow or are continuous because the thickness of the metal thin film layer is increased.

  Thus, even when the topcoat layer is provided on the metal thin film layer, the metal thin film layer does not become cloudy and determines whether it is a metal-like soft polymer molded article having excellent metallic luster. By observing the surface state with a scanning electron microscope, it can be determined by the size of the island portions that appear to be granular, the state of the island portions missing, and the flatness of the surface.

  The more specific manufacturing conditions and photographing conditions with an electron microscope of the metal-like soft polymer molded body for forming the metal thin film layer shown in each of FIGS.

  Sample 1: A flexible polymer molded body 12 obtained by molding a polyester-based thermoplastic elastomer having JIS K 6253 hardness 60, and 4 parts of “Origid Plate Z Clear” (trade name: manufactured by Origin Electric Co., Ltd.) as a base coat layer 12 On the other hand, 1 part of “Polyhard R Curing Agent” (trade name: manufactured by Origin Electric Co., Ltd.) was mixed, and “Origin Thinner # 210 No. 3” (trade name: manufactured by Origin Electric Co., Ltd.) was added to adjust the viscosity. A urethane paint was applied, and the layer thickness after drying and curing at 80 ° C. for 30 minutes was set to 10 μm. Then, indium (purity 99.9) was appropriately adjusted with a vacuum deposition apparatus in which the space between the compact and the filament was 100 mm to 200 mm, with a current value of 100 amperes to 200 amperes and a time of 30 seconds to 2 minutes. %, Manufactured by Niraco Co., Ltd.) was vapor-deposited on the molded body to form a metal thin film layer 13 having a layer thickness of 20 nm. Photographing with a scanning electron microscope was performed by using a “scanning electron microscope S-3000N” (trade name: manufactured by Hitachi High-Technologies Corporation) and photographing the surface of the metal thin film layer 13 at a magnification of 25,000 times. It is. Then, as the top coat layer 14, 1 part of the polyhard R curing agent was mixed with 4 parts of the main ingredient of “Origid Plate Set MP Clear” (trade name: Origin Electric Co., Ltd.), and the origin thinner # 210No. An acrylic urethane paint whose viscosity was adjusted by adding 3 was applied, and the layer thickness after drying and curing at 90 ° C. for 30 minutes was set to 10 μm. In this way, a metal-like soft polymer molding 10 as Sample 1 was obtained.

  Sample 2: Manufactured in the same manner as Sample 1 except that the type of filament was changed, and photographed in the same manner.

  Sample 3: Manufactured in the same manner as Sample 1 except that the distance between the molded body to be vapor-deposited and the filament was about 240 mm, and photographed in the same manner.

  Sample 4: A metal thin film layer was formed in the same manner as Sample 1 except that the formation time of the metal thin film layer was longer than that of Sample 1 and the thickness of the metal thin film layer was 120 nm.

Second Embodiment : FIG. 6 shows a metallic soft polymer molded body 20 according to a second embodiment. The metal-like soft polymer molded body 20 has a structure in which the base coat layer 12 is not provided in the metal-like soft polymer molded body 10 shown in the first embodiment, and the soft polymer molded body 11 and the metal thin film layer 13 are provided. The top coat layer 14 is laminated.

  About the material and manufacturing method which comprise the metal tone soft polymer molded object 20, except a basecoat layer, it is the same as the material and manufacturing method which were shown in 1st Embodiment.

  Further, when the surface state of the metal thin film layer 13 was observed with a scanning electron micrograph, the same surface state as that of the sample 1 in the first embodiment was observed.

Third Embodiment : FIG. 7 shows a metallic soft polymer molded body 30 according to a third embodiment. The metal-like soft polymer molded body 30 has a layer structure in which the metal thin film layer 13 is laminated on the soft polymer molded body 11. The same as the first embodiment except that the base coat layer 12 and the top coat layer 14 are not formed.

  About the material and manufacturing method which comprise the metal tone soft polymer molded object 30, except the basecoat layer 12 and the topcoat layer 14, it is the same as the material and manufacturing method which were shown in 1st Embodiment.

  Further, when the surface state of the metal thin film layer 13 was observed with a scanning electron micrograph, the same surface state as that of the sample 1 in the first embodiment was observed.

Example of change of embodiment ; For each of the above embodiments, in addition to the base coat layer 12, the metal thin film layer 13, and the top coat layer 14, a colored layer that imparts color to the metallic soft polymer molded body 10, 20, 30; It is also possible to form a coating layer for preventing the metallic thin film layer 13 from exhibiting metallic luster, a display layer for imparting characters, symbols, and the like.

  Samples 1 to 4 described in the first embodiment are all formed by a vacuum deposition apparatus, but the same surface structure is formed by a method such as ion plating or sputtering in addition to vacuum deposition. You can also

  The metal-like soft polymer moldings 10, 20, and 30 are metal-like materials that have flexibility and excellent surface gloss, and are soft members that require a metal-like design, such as soft jack covers and It can be used for various purposes such as use for flexible materials such as robot toys and use for members that require mass reduction.

The schematic cross section of the metal-like soft polymer molded object by 1st Embodiment of this invention. The electron micrograph figure of the metal thin film layer surface of the metal tone soft polymer molded object by 1st Embodiment of this invention made into the sample 1. FIG. The electron micrograph figure of the metal thin film layer surface of the metal tone soft polymer molded object by the comparative example made into the sample 2. FIG. The electron micrograph figure of the metal thin film layer surface of the metal tone soft polymer molded object by the comparative example made into the sample 3. FIG. The electron micrograph figure of the metal thin film layer surface of the metal tone soft polymer molded object by the comparative example made into the sample 4. FIG. The schematic cross section of the metal tone soft polymer molded object by 2nd Embodiment of this invention. The schematic cross section of the metal tone soft polymer molded object by 3rd Embodiment of this invention.

Explanation of symbols

10, 20, 30 Metal-like soft polymer molding 11 Soft polymer molding 12 Base coat layer 13 Metal thin film layer 14 Top coat layer

Claims (5)

A metal-like soft polymer molded article having a metal thin film layer, a top coat layer and a base coat layer on a soft polymer molded article,
A base coat layer, a metal thin film layer, and a top coat layer are laminated in this order on the surface of the flexible polymer molded body.
The metal thin film layer is an indium thin film layer formed by uniformly and linearly scattering indium in the space of the vapor deposition apparatus, and has a large number of island portions made of vapor deposited metal grains having a maximum length in the longitudinal direction of 0.5 μm or less. Within a range of 3.5 μm × 5.0 μm by a surface photograph taken with a scanning electron microscope, it has a flat surface structure with no shading , and has a gap between islands or exceeding the maximum length. The metal-like soft polymer molded article having two or less island portions and a layer thickness of 20 nm to 100 nm. A metal-like soft polymer molding having a metal thin film layer and a topcoat layer on a soft polymer molding,
A metal thin film layer and a topcoat layer are laminated in this order on the surface of the flexible polymer molded body.
The metal thin film layer is an indium thin film layer formed by uniformly and linearly scattering indium in the space of the vapor deposition apparatus, and has a large number of island portions made of vapor deposited metal grains having a maximum length in the longitudinal direction of 0.5 μm or less. Within a range of 3.5 μm × 5.0 μm by a surface photograph taken with a scanning electron microscope, it has a flat surface structure with no shading , and has a gap between islands or exceeding the maximum length. The metal-like soft polymer molded article having two or less island portions and a layer thickness of 20 nm to 100 nm. A metal-like soft polymer molded product having a metal thin film layer on a soft polymer molded product,
The metal thin film layer is an indium thin film layer formed by uniformly and linearly scattering indium in the space of the vapor deposition apparatus, and has a large number of island portions made of vapor deposited metal grains having a maximum length in the longitudinal direction of 0.5 μm or less. Within a range of 3.5 μm × 5.0 μm by a surface photograph taken with a scanning electron microscope, it has a flat surface structure with no shading , and has a gap between islands or exceeding the maximum length. The metal-like soft polymer molded article having two or less island portions and a layer thickness of 20 nm to 100 nm. The metal-like soft polymer molded body according to any one of claims 1 to 3 , wherein the soft polymer molded body is a rubber-like elastic body having an A hardness of JIS K 6253 of 50 to 95. The metal-like soft polymer molding according to any one of claims 1 to 4 , wherein the soft polymer molding is a thermoplastic elastomer.

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