JP2019077920A - Metallic tone decorative component and production method thereof - Google Patents

Abstract

To provide a metallic tone decorative component that can be produced by a method in which adhesion between a resin substrate and a metal plating layer is excellent, the safety of work can be simply and easily secured, and a load to environment is small.SOLUTION: A metallic tone decorative component is configured by layer formation in a manner that a first middle layer composed of a coupling agent, a second middle layer composed of a dried and solidified object from conductive paste, and a metal plating layer are laminated on the surface of a resin substrate in this order viewed from the resin substrate side.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metallic decorative component and a method of manufacturing the same, and in particular, a metallic decorative component that can be advantageously used as various automotive interior components, and such a metallic decorative component. It relates to methods that can be manufactured.

  2. Description of the Related Art Conventionally, metal-modified decorative parts in which metal-colored decoration is applied to the surface of a base material (resin base material) made of a resin molded product are widely adopted, for example, in vehicles and the like. In addition, as an example of such a metal-modified decorative component, it is known that a metal thin film is formed by performing a plating process on the surface of a resin base material, and a metal-colored decoration is applied. ing.

  Here, although the plating process is classified into electroplating (electrolytic plating), electroless plating, hot-dip plating, etc. depending on the difference in the film forming mechanism, it is particularly suitable for vehicles from the reason that the treatment process is simple. Generally, electroplating (electrolytic plating) is employed when producing a metallic decorative component. Moreover, in order to carry out electroplating, it is required that the object to be plated has conductivity, but the synthetic resin constituting the resin molded product (resin base material) usually has conductivity. Various techniques have been developed in order to enable electroplating (electrolytic plating) on a synthetic resin substrate, as it is a non-conductor that does not occur.

  For example, when the resin base material to be plated is made of ABS (acrylonitrile-butadiene-styrene copolymer) resin, the ABS resin base material to be plated is made of chromic acid-sulfuric acid By treating with the mixed acid, micropores are formed on the surface of the resin base material, the plating film is grown up to the inside of the micropores (anchor effect), and on the resin base material surface by the treatment using the mixed acid. By the generated polar groups such as nitrile group, carbonyl group and carboxyl group participating in the bond with the plating metal, and further, their actions mutually affect each other, thereby forming a plating film on a substrate made of ABS resin. It is known that adhesion can be advantageously improved (see Non-Patent Document 1).

  In addition, in Patent Document 1 (Japanese Patent No. 4776033), as a method of producing a decorative plated product using resin conductivity conversion by sputtering, an electroplating process is performed on a resin molded product (W) made of PA-based resin. There is proposed a method including the steps of forming a metal thin film made of a nickel alloy by sputtering, and forming a conductive film by sputtering after the film forming step before implementation.

  However, in the treatment using the above-mentioned mixed acid of chromic acid and sulfuric acid, the chromic acid used therein contains hexavalent chromium which is known as a carcinogen, and improvement of working environment and plating Problems such as later wastewater treatment and soil pollution have been pointed out before. Moreover, although the decorative plating product obtained according to the manufacturing method disclosed in Patent Document 1 suppresses the occurrence of the plating floating phenomenon due to inter-resin peeling, it is necessary to carry out the sputtering process twice, and the manufacturing process is complicated. The problem of being there is inherent.

Patent No. 4776033

Hidehiko Enomoto, et al., “Current Status and Future of Plating on Plastics,” Surface Technology, 2008, Volume 59, No. 5, pp. 282-287

  Here, the present invention is made on the background of the above circumstances, and the problem to be solved is the metallic decorative component with excellent adhesion between the resin substrate and the metal plating layer. An object of the present invention is to provide a metallic decorative component that has a low impact on the environment and can be manufactured by a simple method. Another object of the present invention is to provide a method by which such a metallic decorative component can be advantageously manufactured.

  And in order to solve this subject, in the present invention, on the surface of a resin base material, the 1st middle class which consists of a coupling agent, the 2nd middle class which consists of a dry solidification thing of conductive paste, and metal A metal-modified decorative component, characterized in that a plating layer is laminated in this order from the side of the resin base is the gist of the invention.

  In the present invention, a first intermediate layer comprising a coupling agent is formed on the surface of a resin substrate, and then a conductive paste is applied to the surface of the first intermediate layer and dried. A second intermediate layer comprising a dried solidified product of the conductive paste is formed, and a metal plating layer is further formed on the surface of the second intermediate layer by plating. The method of manufacturing parts is also the gist of the invention.

  Thus, in the metallic decorative component according to the present invention, the first intermediate layer made of the coupling agent and the dried solidified product of the conductive paste are provided between the resin base material and the metal plating layer. By interposing the second intermediate layer in this order from the resin base side, the adhesion between the resin base and the metal plating layer becomes excellent. In addition, metal-modified decorative parts that exhibit such excellent properties can be manufactured without using substances having a large load on the environment, such as hexavalent chromium, and multiple sputtering processes. And the like without being subjected to complicated processes such as

It is a partial expanded cross-section explanatory drawing which shows one Embodiment of the metal-modified decorating components according to this invention.

  Hereinafter, in order to clarify the present invention more specifically, representative embodiments of the present invention will be described in detail with reference to the drawings. In addition, in order to make an understanding of the present invention easy, the thickness etc. of the metal plating layer is exaggerated and drawn for the metallic-metal decorative component for vehicles illustrated by drawing attached to this application. Is where it is understood.

  FIG. 1 is a part of a cross section obtained by cutting a metal-modified decorative component for a vehicle used in an automobile according to one embodiment of the present invention in a plane parallel to the laminating direction, such as a metal plating layer on a resin substrate. And FIG. As apparent from FIG. 1, in the metallic decorative component for vehicle 10 according to the present invention, the first intermediate layer 14, the second intermediate layer 16 and the metal plating layer 18 are formed on the surface of the resin base 12. The layers are formed by laminating in this order from the resin base 12 side.

  Specifically, the resin base 12 in the present embodiment is a flat plate made of synthetic resin. In the present invention, the shape of the resin base 12 is not limited to a flat plate, and a shape according to the application of the metallic decorative component 10 for a vehicle can be appropriately adopted. Moreover, even if it is in the synthetic resin material which comprises the resin base material 12, it is not limited to a specific thing, For example, ABS resin, AAS resin, AES resin, PC resin, PMMA resin, PET resin, PBT resin Etc. are commonly used as a forming material of resin-made metallic decorative parts for vehicles, which may be used alone or in combination of two or more depending on the application of the parts. .

  In addition, with regard to the metal material constituting the metal plating layer 18, also from among various metal materials conventionally employed in resin-made metal-modified decorative parts made of resin, applications of the parts, characteristics required, etc. Depending on the necessity, it can be selected and adopted. Examples of such metal materials include gold, silver, nickel, chromium, copper, zinc, tin, nickel-tin alloys and the like. In the present invention, the thickness of the metal plating layer 18 is generally about 1 μm to 100 μm.

  And, in the metallic decorative component 10 for a vehicle according to the present invention, the first intermediate layer 14 made of a coupling agent and the conductive paste are provided between the resin base 12 and the metal plating layer 18 described above. A large technical feature exists in that the second intermediate layer 16 made of the dried solidified material is formed and configured in this order from the resin base 12 side. That is, by interposing two middle layers (16, 18) made of a predetermined material between the resin base 12 and the metal plating layer 18, the metallic decorative component 10 for a vehicle according to the present invention can be obtained. In such a case, very good adhesion is exhibited between the resin base 18 and the metal plating layer.

  Here, as the coupling agent constituting the first intermediate layer 14, a dried and solidified product of the resin base 12 and the conductive paste constituting the second intermediate layer 16 (conductive particles constituting the conductive paste) Any material can be used as long as it can improve the adhesion to the resin. As such a coupling agent, a silane coupling agent can be exemplified. If the thickness of the first intermediate layer 14 made of a coupling agent is too thin, it may not contribute to the improvement of the adhesion between the resin base 12 and the second intermediate layer 16. The thickness of the first intermediate layer 14 made of a coupling agent is preferably 1 μm to 10 μm, since it is not advantageous from the viewpoint of cost effectiveness even if the thickness of the intermediate layer 14 is too thick.

  The second intermediate layer 16 is formed of a dried and solidified product of the conductive paste. The conductive paste is composed of a mixture of conductive particles and a solvent (solvent) and exhibits a liquid or paste form (paste form). The conductive paste used in the present invention is a resin base. Any material may be used as long as the material 12 can be provided with sufficient conductivity to form the metal plating layer 18 by plating (electroplating) described later. It is. Silver particles and copper particles can be exemplified as conductive particles constituting the conductive paste, and organic solvents such as benzyl alcohol can be exemplified as a solvent (solvent) constituting the conductive paste.

  With regard to the thickness of the second intermediate layer 16 composed of such a dried and solidified product of the conductive paste, if it is too thin, sufficient conductivity can not be imparted to the resin substrate 10, As a result, the adhesion of the metal plating layer 18 may not be sufficiently secured. On the other hand, even if the thickness of the second intermediate layer 16 is too thick, the process for forming the second intermediate layer 16 takes time, and is necessary. As mentioned above, the amount of conductive paste used is increased, which is not advantageous from the viewpoint of cost-effectiveness. Therefore, it is preferable that the thickness of the second intermediate layer 16 in the metallic decorative component 10 according to the present invention be 1 μm to 60 μm.

  Then, a metal plating layer 18 made of a metal material selected to give the intended metallic tone is formed on the surface of the second intermediate layer 16 composed of the dried solidified product of the conductive paste, The metal-made metal decorative component 10 according to the present invention is configured. By providing such a metal plating layer 18, the metal-made metallic decorative component 18 for a vehicle exhibits a desired metallic tone. The thickness of the metal plating layer 18 is usually about 1 μm to 100 μm.

  By the way, it is possible to manufacture, for example, according to the manufacturing method described in detail below, the metal-made metal decorative component 10 for vehicles mentioned above.

  First, the flat resin base 12 is prepared according to a conventionally known production method (molding method). The flat resin base material 12 can be manufactured according to the molding method according to the resin material which comprises it.

  Next, the first intermediate layer 14 made of a coupling agent is formed on one surface (upper surface in FIG. 1) of the resin base 12. The first intermediate layer 14 is formed by, for example, applying a solution obtained by dissolving (mixing) a coupling agent in a predetermined solvent (solvent), and then drying the solution on the surface of the resin base 12. Therefore, it is possible to form by the method etc. which used the coating apparatus which is disclosed by Unexamined-Japanese-Patent No. 2006-123425.

  Furthermore, a predetermined conductive paste is applied to the surface of the first intermediate layer 14 made of a coupling agent and dried to form a second intermediate layer 16 made of a dried solidified product of the conductive paste. In addition, since the solvent (solvent) is volatilized by drying and the volume of the conductive paste is reduced, the coating amount of the conductive paste is obtained so that the required thickness of the second intermediate layer 16 can be obtained. The (coating thickness) is adjusted. Further, the method of forming the layer of the conductive paste in the unsolidified state is not limited to application, and depending on the type and configuration of the conductive paste, printing method such as screen printing method, It is also possible to adopt coating methods such as spray coating, inkjet coating, and dispenser coating. Furthermore, with respect to the drying conditions (heating temperature, heating time, etc.) of the conductive paste, conditions according to the solvent (solvent) that constitutes the conductive paste are appropriately determined.

  Then, on the surface of the second intermediate layer 16 made of the dried and solidified material of the conductive paste, a metal plating layer 18 composed of a desired metal material is formed according to a conventionally known plating treatment (electroplating treatment). By being formed, the target metal-made decorative component 10 for vehicles is obtained.

  In the metallic decorative component 10 for a vehicle obtained as described above, the first intermediate layer 14 made of a coupling agent and the conductive paste are provided between the resin base 12 and the metal plating layer 18. The adhesion between the metal plating layer 18 and the second intermediate layer 16 consisting of the dried and solidified product is very excellent.

  Moreover, the manufacturing method mentioned above does not use the substance with large load to the environment, such as hexavalent chromium, and also does not have complicated processes, such as multiple times of sputtering processes. Therefore, according to the manufacturing method as described above, the metal-modified decorative component 10 for a vehicle having excellent adhesion of the metal plating layer 18 is manufactured with less load on the environment and without going through complicated processes. It is possible.

  As mentioned above, although each embodiment of the metallic decorative component according to this invention and its manufacturing method was explained in full detail, it is needless to say that this invention is not limited to what concerns on an embodiment mentioned above.

  For example, a metal thin film is formed between the second intermediate layer (16) made of a dried solidified product of the conductive paste and the metal plating layer (18) according to a conventionally known sputtering method, You may constitute a decoration part. By interposing such a metal thin film between the second intermediate layer (16) and the metal plating layer (18), the conductivity of the resin substrate (12) is further improved, whereby the metal It is possible to enjoy the advantage that the adhesion of the plating layer (18) is further improved.

  In the following, some examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by any description of such examples. Is, of course. In addition to the specific examples described above, the present invention also includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that it is possible to add improvements, etc.

  First, a flat plate made of PC (polycarbonate) having a length of 70 mm × width: 70 mm × thickness: 3 mm was prepared as a resin substrate. A commercially available silane coupling agent solution (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903) is applied to one surface of the PC flat plate and dried. Thickness: A layer (first intermediate layer) consisting of a silane coupling agent of about 1 mm was formed on a PC flat plate.

  Next, a conductive paste containing silver particles (Ag particles) which are conductive particles in the ratio shown in the following Table 1 on the surface of the layer comprising the silane coupling agent formed as described above is shown in Table 1 below. A layer consisting of a dried solidified product of the conductive paste by applying the screen printing method at a thickness shown in the following and heating at 150 ° C. for 0.5 hours to evaporate the solvent (solvent) contained in the conductive paste The second intermediate layer was formed. In the present example, using a commercially available conductive paste containing silver particles (Ag particles) as the conductive particles at a ratio of 67% by weight and using benzyl alcohol as the solvent (solvent), the solvent is appropriately used. By adding or removing, conductive pastes containing Ag particles in the proportions shown in Table 1 below were prepared and used for preparation of samples according to each example.

  Then, electroplating was performed on the layer (the second intermediate layer) made of the dried solidified product of the conductive paste to form a chromium plating layer having a thickness of 20 μm. According to the above procedure, on a flat plate made of PC, a first intermediate layer made of a coupling agent, a second intermediate layer made of a dried and solidified conductive paste, and a metal plating (chromium plating) layer are in this order Ten types of samples formed by laminating in accordance with the above were manufactured (Examples 1 to 10).

The following evaluation tests were performed on the samples obtained as described above. In the tape peeling test in each of the following tests, a cut was made in the chromium plating layer on the sample surface, a commercially available tape was made to adhere to the cut, the tape was removed by pulling and then the tape was made to adhere The surface is visually observed and evaluated according to the following criteria.
○: Peeling off of the chromium plating layer is not observed at all.
Δ: Although peeling of the chromium plating layer is partially observed, there is no practical problem.
X: Remarkable peeling of the chromium plating layer is recognized.

-Initial evaluation-
The above-mentioned tape peeling test was conducted and evaluated 24 hours after preparation of the chromium plating layer in each sample. The evaluation results are shown as “initial evaluation” in Table 1 below.

-Evaluation after cold heat test-
Using a sample 24 hours after the preparation of the chromium plating layer, according to JIS-H-8630: 2006 “Cold Heat Repeating Test Method” specified in Annex A of “Electroplating for decoration on plastic” A thermal cycle test was conducted by repeating this cycle 20 times, with 1 hour at -30 ° C and 1 hour at 80 ° C. The above-mentioned tape peeling test was implemented and evaluated about the sample after this cold-heat test. The evaluation results are shown in Table 1 below as "Evaluation after Cold Heat Test".

  As is apparent from the results of Table 1, it is recognized that each sample having the same configuration as the metal-modified decorative part according to the present invention is excellent in the adhesion of the chromium plating layer which is a metal plating layer. Be In particular, in a sample obtained using a conductive paste having an Ag particle content of 40% by mass or more and a coating thickness of 10 mm or more, the adhesion between the resin substrate and the metal plating layer is It was confirmed to be better.

10 Metal-Modified Parts for Vehicles 12 Resin Base 14 First Intermediate Layer 16 Second Intermediate Layer 18 Metal-Plated Layer

Claims (2)

  A first intermediate layer comprising a coupling agent, a second intermediate layer comprising a dried solidified product of a conductive paste, and a metal plating layer are applied to the surface of the resin substrate in this order from the resin substrate side. A metallic decorative component characterized in that it is laminated and formed. The first intermediate layer comprising a coupling agent is formed on the surface of the resin substrate, and then the conductive paste is applied to the surface of the first intermediate layer and dried to dry the conductive paste. A method for producing a metallic decorative component, comprising: forming a second intermediate layer comprising a solidified material; and further forming a metal plating layer on the surface of the second intermediate layer by plating.

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