JP2001046958A - Formation of coating film having metallic luster - Google Patents
Formation of coating film having metallic lusterInfo
- Publication number
- JP2001046958A JP2001046958A JP11223184A JP22318499A JP2001046958A JP 2001046958 A JP2001046958 A JP 2001046958A JP 11223184 A JP11223184 A JP 11223184A JP 22318499 A JP22318499 A JP 22318499A JP 2001046958 A JP2001046958 A JP 2001046958A
- Authority
- JP
- Japan
- Prior art keywords
- metallic luster
- coating film
- metal
- silver
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂成形品の表面
に金属光沢を有する塗膜の形成方法に係り、特に被塗装
物表面に金属イオンを含んだ液体を吹き付け、金属イオ
ンを還元して析出させ、この表面にクリアー塗装を行う
ことによって耐薬品性、耐候性等に優れた金属の均一な
薄膜が得られる金属光沢を有する塗膜の形成方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating film having a metallic luster on the surface of a resin molded product, and in particular, spraying a liquid containing metal ions on the surface of an object to be coated to reduce the metal ions. The present invention relates to a method for forming a coating film having a metallic luster by which a metal film having excellent chemical resistance, weather resistance and the like can be obtained by depositing and applying a clear coating on the surface.
【０００２】[0002]
【従来の技術】従来、自動車や家電部品等の樹脂成形品
の表面に金属光沢を付与するために、湿式Ｎｉ−Ｃｒめ
っき、乾式めっき(スパッタリング)が広く用いられてい
る。ところで、前記の湿式めっきでは排水の公害処理に
問題があったり、軟質の樹脂部品に適用した時に金属膜
の割れ、クラック等が生じるという問題が有り、また乾
式めっきでは設備費がかさみ製品コストが高くなるとい
う問題があった。このような背景から、塗装により金属
光沢を得る方法が各種提案されている。以下に、この従
来工法について説明する。2. Description of the Related Art Conventionally, wet Ni-Cr plating and dry plating (sputtering) have been widely used to impart metallic luster to the surface of resin molded products such as automobiles and home electric appliances. By the way, in the wet plating, there is a problem in pollution treatment of wastewater, and when applied to a soft resin part, there is a problem that a metal film is cracked or cracked. There was a problem of getting high. Against this background, various methods for obtaining metallic luster by painting have been proposed. Hereinafter, this conventional method will be described.
【０００３】特開昭５６−７０８８３号公報には、樹脂
成形品の表面に金属光沢を有する塗膜の形成方法および
その方法に使用する塗料組成物が開示されている。この
従来の金属光沢を有する塗膜の形成方法においては、ま
ず金属光沢付与成分，この成分を金属に還元し得る官能
基をもつ樹脂からなる塗膜形成成分及び溶剤を含む塗料
組成物を調整している。なお、この塗料組成物の具体的
として、金属光沢付与成分１〜５０部（硝酸銀），第１
の溶剤（例；メタノ−ル）１〜９４部，前記塗膜形成成
分５〜８０部，第２の溶剤（例；キシレン）１〜９３部
及び添加剤（例；シリコ−ンオイル）０．０１〜５部の
合計量１００部からなる塗料組成物をあげている。JP-A-56-70883 discloses a method for forming a coating film having a metallic luster on the surface of a resin molded product and a coating composition used in the method. In this conventional method for forming a coating film having a metallic luster, first, a coating composition containing a metallic luster imparting component, a film-forming component comprising a resin having a functional group capable of reducing this component to a metal, and a solvent is prepared. ing. In addition, as a specific example of this coating composition, 1 to 50 parts of a metallic luster imparting component (silver nitrate),
1 to 94 parts of a solvent (e.g., methanol), 5 to 80 parts of the above-mentioned coating film forming component, 1 to 93 parts of a second solvent (e.g., xylene) and 0.01 parts of an additive (e.g., silicone oil) To 5 parts of a coating composition consisting of 100 parts in total.
【０００４】次に、前記の塗料組成物を前処理後の素材
に塗装し，室温〜８０℃でセツテイング処理して，溶剤
類を蒸発させ，塗膜を半乾燥状態にする。次に、この状
態の塗膜表面に４００ｎｍ以下の波長の電磁波を照射し
て，金属光沢付与成分を金属に還元し，所望の塗膜を形
成させる。尚，金属光沢付与成分としては例えば硝酸銀
を，塗膜形成成分としては例えば自己架橋型熱硬化性ア
クリル樹脂を各々使用するという工法である。[0004] Next, the above-mentioned coating composition is applied to the material after the pre-treatment, and is subjected to a setting treatment at room temperature to 80 ° C to evaporate the solvents and to make the coating film semi-dry. Next, the surface of the coating film in this state is irradiated with an electromagnetic wave having a wavelength of 400 nm or less to reduce the metallic luster imparting component to metal and form a desired coating film. It is to be noted that the metal gloss imparting component is, for example, silver nitrate, and the coating film forming component is, for example, a self-crosslinking thermosetting acrylic resin.
【０００５】一方、特開平８−３２５７４３号公報に
は、不伝導基質上の銀層沈着工法として「微生物の成長
に抵抗性の物品を製造する方法」が開示されている。こ
の工法における対象物品は非導電性基質を含み、非導電
性基質の表面の少なくとも一部は、銀層を含む薄い付着
被覆で被覆されるものである。また、この工法は、(ａ)
ＰＳ等の非導電性基質の表面の少くとも１部をスタンナ
ススズイオン溶液等で処理して活性化する。(ｂ)次いで
この表面を、沈着調整剤(定着剤)の存在下且つ電流の不
存在下で、ホルムアルデヒド等の還元剤を含む硝酸銀等
の銀塩水溶液で処理する。この沈着調整剤としては、ク
エン酸ナトリウム、酢酸ナトリウム、水酸化ナトリウ
ム、水酸化カリウム、アンモニア等が適当である。これ
により上記表面に０．２〜２００ｍｍ厚さの透明で機械
的性質の良好な銀層を高付着力で沈着させる。次いでこ
の銀層の被覆を非ミネラル水ですすいだ後、乾燥する。
その際工程中での白金族金属、金等の塩溶液処理は包含
しない。というものである。On the other hand, Japanese Patent Application Laid-Open No. 8-325743 discloses a "method for producing an article resistant to the growth of microorganisms" as a method for depositing a silver layer on a non-conductive substrate. The target article in this method includes a non-conductive substrate, and at least a part of the surface of the non-conductive substrate is covered with a thin adhesive coating including a silver layer. In addition, this method uses (a)
At least a part of the surface of a non-conductive substrate such as PS is activated by treating it with a stannath tin ion solution or the like. (b) Next, this surface is treated with a silver salt aqueous solution such as silver nitrate containing a reducing agent such as formaldehyde in the presence of a deposition control agent (fixing agent) and in the absence of an electric current. As the deposition control agent, sodium citrate, sodium acetate, sodium hydroxide, potassium hydroxide, ammonia and the like are suitable. This deposits a 0.2-200 mm thick transparent and good mechanical property silver layer on the surface with high adhesion. The silver layer coating is then rinsed with non-mineral water and dried.
At that time, treatment with a salt solution of a platinum group metal, gold or the like in the process is not included. That is.
【０００６】また、前記の工法によれば、電気的に不伝
導な基質の表面に銀の均一な薄層を沈着させる方法は、
実質的に少なくとも約０．００１ｇ／ｌのスタンナスス
ズイオンの塩を含む活性化溶液中で表面を活性化するこ
と、銀含有塩、基質の表面に銀塩を還元して金属銀を生
成させ得るに十分な濃度の還元剤および溶液中の銀を析
出を防止し、基質の表面に銀の沈着を可能にするに十分
な濃度の沈着調整剤(定着剤)からなる沈着溶液から表面
に銀を沈着させること、更に好ましくは沈着工程を暗所
で行うことを含む。必要ならば、基質の表面を処理前に
洗浄することができる。銀層は沈着後で使用前に安定化
させるのがよい。というものである。According to the above method, a method for depositing a uniform thin layer of silver on the surface of an electrically non-conductive substrate is as follows.
Activating the surface in an activating solution comprising substantially at least about 0.001 g / l of a salt of stanna stannous ions, a silver-containing salt, capable of reducing the silver salt to the surface of the substrate to form metallic silver Silver on the surface from a deposition solution consisting of a sufficient amount of a reducing agent and silver in the solution to prevent precipitation and a sufficient concentration of a deposition modifier (fixing agent) to allow silver to be deposited on the surface of the substrate. Depositing, more preferably performing the deposition step in a dark place. If necessary, the surface of the substrate can be washed before processing. The silver layer should be stabilized after deposition and before use. That is.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、前者の
特開平８−３２５７４３号公報に示される金属光沢を有
する塗膜の形成方法では、金属光沢付与成分を金属に還
元するのに際し、別の工程にて塗膜表面に４００ｎｍ以
下の波長の電磁波を照射するというものであるから、リ
ードタイムが長く生産性を上げることができず、また、
電磁波を照射装置を必要とし生産設備が高くなるという
問題があった。However, in the former method of forming a coating film having a metallic luster disclosed in Japanese Patent Application Laid-Open No. 8-325743, a separate step is required for reducing the metallic luster imparting component to metal. Since the coating film surface is irradiated with an electromagnetic wave having a wavelength of 400 nm or less, the lead time is long and the productivity cannot be increased.
There is a problem that an electromagnetic wave irradiation device is required and production equipment becomes expensive.
【０００８】後者の特開平８−３２５７４３号公報に示
される不伝導基質上の銀層沈着工法は、沈着調整剤(定
着剤)を用いる工程において、ホルムアルデヒド等の還
元剤を含む硝酸銀等の銀塩水溶液で処理するものである
から、本件出願発明の還元剤を空中で混合させる方式に
比べると銀塩水溶液および還元剤を多量に必要としコス
トアップをまねくという問題があった。In the latter method of depositing a silver layer on a non-conductive substrate disclosed in JP-A-8-325743, a silver salt such as silver nitrate containing a reducing agent such as formaldehyde is used in the step of using a deposition control agent (fixing agent). Since the treatment is carried out with an aqueous solution, there is a problem in that the silver salt aqueous solution and the reducing agent are required in large amounts and the cost is increased as compared with the method of mixing the reducing agent of the present invention in the air.
【０００９】また、不伝導基質上の銀層沈着工法は、そ
の目的を微生物の成長に抵抗性の物品を製造する方法と
しているため、薄膜に形成される銀層は変色しやすく、
特に耐熱性・耐候性を要求される自動車部品等の表面処
理に適用することができないという問題点があった。In addition, the method of depositing a silver layer on a non-conductive substrate is a method for producing an article resistant to the growth of microorganisms, so that the silver layer formed on the thin film is easily discolored.
In particular, there is a problem that it cannot be applied to surface treatment of automobile parts and the like that require heat resistance and weather resistance.
【００１０】[0010]
【課題を解決するための手段】本発明は、樹脂成形品の
表面に金属光沢を有する塗膜の形成するにあたり、特に
被塗装物表面に金属イオンを含んだ液体を吹き付け、金
属イオンを還元して析出させ、余剰分を水洗した後に定
着材を吹き付け、この表面にクリアー塗装を行うことに
よって耐薬品性、耐候性等に優れた金属の均一な薄膜が
得られる金属光沢を有する塗膜の形成方法の提供を目的
とすものである。According to the present invention, in forming a coating film having a metallic luster on the surface of a resin molded product, a liquid containing metal ions is sprayed on the surface of an object to be coated, and the metal ions are reduced. After washing the excess, water is sprayed with a fixing material, and a clear coating is applied to this surface to form a coating film having a metallic luster that provides a uniform thin film of metal having excellent chemical resistance, weather resistance, etc. It is intended to provide a method.
【００１１】すなわち、本願の第１の発明は、樹脂製被
塗装物の表面に金属を含むベース溶液を吹き付け、純水
にて余剰分を水洗し、その後この表面に金属イオンを含
む水溶液と還元剤水溶液を同時に吹き付け、金属イオン
を還元して被塗装物表面に金属を析出させ、その後、純
水にて余剰分を水洗し、クエン酸ナトリウム、水酸化ナ
トリウム、水酸化カリウム、アンモニア等の定着剤を吹
き付け、この定着剤を乾燥させた後クリアー塗装を行う
ようにしたことを特徴とする金属光沢を有する塗膜の形
成方法である。That is, the first invention of the present application is to spray a base solution containing a metal onto the surface of a resin-made article to be coated, wash the surplus with pure water, and then reduce the surface with an aqueous solution containing metal ions. Simultaneously sprays an aqueous solution of the agent to reduce metal ions and precipitate the metal on the surface of the object to be coated, then wash the excess with pure water and fix sodium citrate, sodium hydroxide, potassium hydroxide, ammonia, etc. This is a method for forming a coating film having a metallic luster, wherein a clear coating is performed after spraying an agent and drying the fixing agent.
【００１２】本願の第１の発明によれば、１つの生産ラ
インにて、樹脂製被塗装物の表面に金属光沢を有する塗
膜を形成できるためリードタイムが短く生産性を上げる
ことができる。また、還元剤を空中で混合させて吹き付
けるものであるから、従来硝酸銀等の銀塩水溶液で処理
するものに比べて、銀塩水溶液および還元剤が少なくて
すみ、生産コストを低減させることができる。なお、前
記の樹脂製被塗装物としては、樹脂成形品に限らず紙、
粘土等材質を選ばず、また耐熱の低いもの、耐薬品に弱
いものにも適用が可能である。また、めつきの種類とし
ては、銀、ニッケル等無電解めっきがある。According to the first aspect of the present invention, a coating film having a metallic luster can be formed on the surface of the resin-made article to be coated in one production line, so that the lead time is short and the productivity can be improved. Further, since the reducing agent is mixed and sprayed in the air, the amount of the silver salt aqueous solution and the reducing agent can be reduced as compared with the conventional treatment with a silver salt aqueous solution such as silver nitrate, and the production cost can be reduced. . In addition, the above-mentioned resin-coated object is not limited to a resin molded product, but may be paper,
It can be applied to any material such as clay, low heat resistance and weak chemical resistance. In addition, as a type of plating, there is electroless plating such as silver and nickel.
【００１３】また、第２の発明は、前記ベース溶液の金
属としては錫とし、金属イオンを含む水溶液としてはア
ンモニア性硝酸銀水溶液とし、還元する金属イオンを銀
として被塗装物表面に銀を析出させ、定着剤としては水
酸化ナトリウムを用いたことを特徴とする請求項１記載
の金属光沢を有する塗膜の形成方法である。In a second aspect of the present invention, silver is deposited on the surface of the workpiece by using tin as a metal of the base solution, an aqueous solution of ammonium nitrate as an aqueous solution containing metal ions, and silver as a metal ion to be reduced. The method according to claim 1, wherein sodium hydroxide is used as the fixing agent.
【００１４】本願の第２の発明によれば、樹脂成形品の
表面に、耐薬品性、耐候性等に優れた銀めっき調の金属
薄膜を形成させることができるため、例えば自動車の内
装部品や外装部品に適用させることができる。According to the second aspect of the present invention, a silver-plated metal thin film having excellent chemical resistance and weather resistance can be formed on the surface of a resin molded product. It can be applied to exterior parts.
【００１５】また、第３の発明は、前記の樹脂製被塗装
物が軟質樹脂の成形品であることを特徴とする請求項２
記載の金属光沢を有する塗膜の形成方法である。According to a third aspect of the present invention, the object to be coated with a resin is a molded product of a soft resin.
A method for forming a coating film having the described metallic luster.
【００１６】本願の第３の発明によれば、樹脂製被塗装
物を軟質樹脂の成形品とすることにより、金属イオンを
還元して被塗装物表面に銀を析出させるに際し、プライ
マーおよびクリアーを軟質系にすることにより変形に追
従し、クラックの発生しない金属光沢を付与させること
ができる。According to the third invention of the present application, by forming the resin-coated object into a molded product of a soft resin, a primer and a clear material are used for reducing metal ions and depositing silver on the surface of the object to be coated. By using a soft system, deformation can be followed and a metallic luster free of cracks can be imparted.
【００１７】上記の軟質の製品としては、例えば、ラヂ
エータグリルのめっき品、バンパーガードのめっきガー
ニッシュ、ステアリングハンドル、車名マーク等があ
る。The above-mentioned soft products include, for example, a plated product of a radiator grill, a plated garnish of a bumper guard, a steering handle, a car name mark, and the like.
【００１８】[0018]
【実施例】以下、本発明に係る金属光沢を有する塗膜の
形成方法を、図面を参照しながら説明する。図１は、本
発明に係る金属光沢を有する塗膜の形成方法の工程図で
あり、本発明では、次の手順により樹脂製被塗装物の表
面に金属光沢を有する塗膜が形成される。 樹脂製被塗装物の表面性状を調えるためにプライマー
塗装を行ない、６０度にて２時間程乾燥させる。 金属（錫）を含むベース溶液の吹き付けをおこない、
その後純水にて余剰分を水洗する。 その後、ベース塗装された表面に金属イオン（銀）を
含む水溶液と還元剤水溶液を同時に吹き付け（約１
分)、金属イオンを還元して被塗装物表面に金属を析出
させ、その後純水にて余剰分を水洗し、１５分程放置す
る。 次いでクエン酸ナトリウム、水酸化ナトリウム、水酸
化カリウム、アンモニア等の定着剤を吹き付けて(約１
分)、１５分程放置する。 その後クリアー塗装を行う。DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for forming a coating film having a metallic luster according to the present invention will be described below with reference to the drawings. FIG. 1 is a process chart of a method for forming a coating film having a metallic luster according to the present invention. In the present invention, a coating film having a metallic luster is formed on the surface of a resin-made workpiece by the following procedure. A primer is applied to adjust the surface properties of the resin-coated object, and dried at 60 degrees for about 2 hours. Spray a base solution containing metal (tin),
Then, the excess is washed with pure water. Thereafter, an aqueous solution containing metal ions (silver) and a reducing agent aqueous solution are simultaneously sprayed on the base-coated surface (approximately 1
Min), metal ions are reduced to deposit metal on the surface of the object to be coated, and then the excess is washed with pure water and left for about 15 minutes. Next, a fixing agent such as sodium citrate, sodium hydroxide, potassium hydroxide, or ammonia is sprayed (about 1
Minutes) and leave for about 15 minutes. After that, clear coating is performed.
【００１９】また、ベース塗装に用いる溶液は、塩化錫
を塩酸溶液へ溶解させたものであり、３％〜１５％の水
溶液である。また、金属イオンを含む水溶液としては濃
度０．１％〜１５％のアンモニア性硝酸銀水溶液であ
る。この場合、還元する金属イオンは銀であり、被塗装
物表面には銀が析出する。The solution used for the base coating is obtained by dissolving tin chloride in a hydrochloric acid solution, and is a 3% to 15% aqueous solution. Further, the aqueous solution containing metal ions is an aqueous solution of ammonium silver nitrate having a concentration of 0.1% to 15%. In this case, the metal ion to be reduced is silver, and silver precipitates on the surface of the object to be coated.
【００２０】[0020]
【発明の効果】本発明の金属光沢を有する塗膜の形成方
法は、樹脂成形品の表面に金属光沢を有する塗膜の形成
するに当たり、特に被塗装物表面に金属イオンを含んだ
液体を吹き付け、金属イオンを還元して析出させ、余剰
分を水洗した後に定着材を吹き付け、この表面にクリア
ー塗装を行うものであるから、クリアー塗装を除き一貫
した生産ラインで行うことができるため、安価なコスト
で且つリードタイムを短くし生産性を上げることができ
る。また、金属イオンを還元して析出させた金属の表面
にクリアー塗装を行うものであるから、金属の変色がな
く、特に耐薬品性・耐候性を要求される自動車部品等の
表面処理に適用することができる。また、従来めっき等
では不可能だった軟質樹脂への金属光沢を付与すること
が可能となり産業上有益な効果がある。According to the method for forming a coating film having a metallic luster of the present invention, a liquid containing metal ions is sprayed on the surface of an object to be coated, particularly when a coating film having a metallic gloss is formed on the surface of a resin molded product. After reducing and precipitating the metal ions, washing the excess with water, spraying the fixing material, and applying clear coating on this surface, it can be performed on a consistent production line except for clear coating, so it is inexpensive The cost and the lead time can be shortened to increase the productivity. In addition, since the surface of the metal deposited by reducing metal ions is subjected to clear coating, there is no discoloration of the metal, and it is particularly applied to surface treatment of automobile parts and the like that require chemical resistance and weather resistance. be able to. In addition, it is possible to impart a metallic luster to a soft resin, which has been impossible with conventional plating and the like, which has an industrially beneficial effect.
【図１】 本発明に係る金属光沢を有する塗膜の形成工
程図。FIG. 1 is a process chart for forming a coating film having a metallic luster according to the present invention.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年８月１９日（１９９９．８．１
９）[Submission Date] August 19, 1999 (1999.8.1)
9)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【書類名】 明細書[Document Name] Statement
【発明の名称】 金属光沢を有する塗膜の形成方法Patent application title: Method for forming a coating film having metallic luster
【特許請求の範囲】[Claims]
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂成形品の表面
に金属光沢を有する塗膜の形成方法に係り、特に被塗装
物表面に金属イオンを含んだ液体を吹き付け、金属イオ
ンを還元して析出させ、この表面にクリアー塗装を行う
ことによって耐薬品性、耐候性等に優れた金属の均一な
薄膜が得られる金属光沢を有する塗膜の形成方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating film having a metallic luster on the surface of a resin molded product, and in particular, spraying a liquid containing metal ions on the surface of an object to be coated to reduce the metal ions. The present invention relates to a method for forming a coating film having a metallic luster by which a metal film having excellent chemical resistance, weather resistance and the like can be obtained by depositing and applying a clear coating on the surface.
【０００２】[0002]
【従来の技術】従来、自動車や家電部品等の樹脂成形品
の表面に金属光沢を付与するために、湿式Ｎｉ−Ｃｒめ
っき、乾式めっき(スパッタリング)が広く用いられてい
る。ところで、前記の湿式めっきでは排水の公害処理に
問題があったり、軟質の樹脂部品に適用した時に金属膜
の割れ、クラック等が生じるという問題が有り、また乾
式めっきでは設備費がかさみ製品コストが高くなるとい
う問題があった。このような背景から、塗装により金属
光沢を得る方法が各種提案されている。以下に、この従
来工法について説明する。2. Description of the Related Art Conventionally, wet Ni-Cr plating and dry plating (sputtering) have been widely used to impart metallic luster to the surface of resin molded products such as automobiles and home electric appliances. By the way, in the wet plating, there is a problem in pollution treatment of wastewater, and there is a problem that cracks, cracks, etc. occur in a metal film when applied to a soft resin part, and in dry plating, equipment costs are increased and product costs are increased. There was a problem of getting high. Against this background, various methods for obtaining metallic luster by painting have been proposed. Hereinafter, this conventional method will be described.
【０００３】特開昭５６−７０８８３号公報には、樹脂
成形品の表面に金属光沢を有する塗膜の形成方法および
その方法に使用する塗料組成物が開示されている。この
従来の金属光沢を有する塗膜の形成方法においては、ま
ず金属光沢付与成分，この成分を金属に還元し得る官能
基をもつ樹脂からなる塗膜形成成分及び溶剤を含む塗料
組成物を調整している。なお、この塗料組成物の具体的
として、金属光沢付与成分１〜５０部（硝酸銀），第１
の溶剤（例；メタノ−ル）１〜９４部，前記塗膜形成成
分５〜８０部，第２の溶剤（例；キシレン）１〜９３部
及び添加剤（例；シリコ−ンオイル）０．０１〜５部の
合計量１００部からなる塗料組成物をあげている。JP-A-56-70883 discloses a method for forming a coating film having a metallic luster on the surface of a resin molded product and a coating composition used in the method. In this conventional method for forming a coating film having a metallic luster, first, a coating composition containing a metallic luster imparting component, a film-forming component comprising a resin having a functional group capable of reducing this component to a metal, and a solvent is prepared. ing. In addition, as a specific example of this coating composition, 1 to 50 parts of a metallic luster imparting component (silver nitrate),
1 to 94 parts of a solvent (e.g., methanol), 5 to 80 parts of the above-mentioned coating film forming component, 1 to 93 parts of a second solvent (e.g., xylene) and 0.01 parts of an additive (e.g., silicone oil) To 5 parts of a coating composition consisting of 100 parts in total.
【０００４】次に、前記の塗料組成物を前処理後の素材
に塗装し，室温〜８０℃でセツテイング処理して，溶剤
類を蒸発させ，塗膜を半乾燥状態にする。次に、この状
態の塗膜表面に４００ｎｍ以下の波長の電磁波を照射し
て，金属光沢付与成分を金属に還元し，所望の塗膜を形
成させる。尚，金属光沢付与成分としては例えば硝酸銀
を，塗膜形成成分としては例えば自己架橋型熱硬化性ア
クリル樹脂を各々使用するという工法である。[0004] Next, the above-mentioned coating composition is applied to the material after the pre-treatment, and is subjected to a setting treatment at room temperature to 80 ° C to evaporate the solvents and to make the coating film semi-dry. Next, the surface of the coating film in this state is irradiated with an electromagnetic wave having a wavelength of 400 nm or less to reduce the metallic luster imparting component to metal and form a desired coating film. It is to be noted that the metal gloss imparting component is, for example, silver nitrate, and the coating film forming component is, for example, a self-crosslinking thermosetting acrylic resin.
【０００５】一方、特開平８−３２５７４３号公報に
は、不伝導基質上の銀層沈着工法として「微生物の成長
に抵抗性の物品を製造する方法」が開示されている。こ
の工法における対象物品は非導電性基質を含み、非導電
性基質の表面の少なくとも一部は、銀層を含む薄い付着
被覆で被覆されるものである。また、この工法は、(ａ)
ＰＳ等の非導電性基質の表面の少くとも１部をスタンナ
ススズイオン溶液等で処理して活性化する。(ｂ)次いで
この表面を、沈着調整剤(定着剤)の存在下且つ電流の不
存在下で、ホルムアルデヒド等の還元剤を含む硝酸銀等
の銀塩水溶液で処理する。この沈着調整剤としては、ク
エン酸ナトリウム、酢酸ナトリウム、水酸化ナトリウ
ム、水酸化カリウム、アンモニア等が適当である。これ
により上記表面に０．２〜２００ｍｍ厚さの透明で機械
的性質の良好な銀層を高付着力で沈着させる。次いでこ
の銀層の被覆を非ミネラル水ですすいだ後、乾燥する。
その際工程中での白金族金属、金等の塩溶液処理は包含
しない。というものである。On the other hand, Japanese Patent Application Laid-Open No. 8-325743 discloses a "method for producing an article resistant to the growth of microorganisms" as a method for depositing a silver layer on a non-conductive substrate. The target article in this method includes a non-conductive substrate, and at least a part of the surface of the non-conductive substrate is covered with a thin adhesive coating including a silver layer. In addition, this method uses (a)
At least a part of the surface of a non-conductive substrate such as PS is activated by treating it with a stannath tin ion solution or the like. (b) Next, this surface is treated with a silver salt aqueous solution such as silver nitrate containing a reducing agent such as formaldehyde in the presence of a deposition control agent (fixing agent) and in the absence of an electric current. As the deposition control agent, sodium citrate, sodium acetate, sodium hydroxide, potassium hydroxide, ammonia and the like are suitable. This deposits a 0.2-200 mm thick transparent and good mechanical property silver layer on the surface with high adhesion. The silver layer coating is then rinsed with non-mineral water and dried.
At that time, treatment with a salt solution of a platinum group metal, gold or the like in the process is not included. That is.
【０００６】また、前記の工法によれば、電気的に不伝
導な基質の表面に銀の均一な薄層を沈着させる方法は、
実質的に少なくとも約０．００１ｇ／ｌのスタンナスス
ズイオンの塩を含む活性化溶液中で表面を活性化するこ
と、銀含有塩、基質の表面に銀塩を還元して金属銀を生
成させ得るに十分な濃度の還元剤および溶液中の銀を析
出を防止し、基質の表面に銀の沈着を可能にするに十分
な濃度の沈着調整剤(定着剤)からなる沈着溶液から表面
に銀を沈着させること、更に好ましくは沈着工程を暗所
で行うことを含む。必要ならば、基質の表面を処理前に
洗浄することができる。銀層は沈着後で使用前に安定化
させるのがよい。というものである。According to the above method, a method for depositing a uniform thin layer of silver on the surface of an electrically non-conductive substrate is as follows.
Activating the surface in an activating solution comprising substantially at least about 0.001 g / l of a salt of stanna stannous ions, a silver-containing salt, capable of reducing the silver salt to the surface of the substrate to form metallic silver Silver on the surface from a deposition solution consisting of a sufficient amount of a reducing agent and silver in the solution to prevent precipitation and a sufficient concentration of a deposition modifier (fixing agent) to allow silver to be deposited on the surface of the substrate. Depositing, more preferably performing the deposition step in a dark place. If necessary, the surface of the substrate can be washed before processing. The silver layer should be stabilized after deposition and before use. That is.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、前者の
特開平８−３２５７４３号公報に示される金属光沢を有
する塗膜の形成方法では、金属光沢付与成分を金属に還
元するのに際し、別の工程にて塗膜表面に４００ｎｍ以
下の波長の電磁波を照射するというものであるから、リ
ードタイムが長く生産性を上げることができず、また、
電磁波を照射装置を必要とし生産設備が高くなるという
問題があった。However, in the former method of forming a coating film having a metallic luster disclosed in Japanese Patent Application Laid-Open No. 8-325743, a separate step is required for reducing the metallic luster imparting component to metal. Since the coating film surface is irradiated with an electromagnetic wave having a wavelength of 400 nm or less, the lead time is long and the productivity cannot be increased.
There is a problem that an electromagnetic wave irradiation device is required and production equipment becomes expensive.
【０００８】後者の特開平８−３２５７４３号公報に示
される不伝導基質上の銀層沈着工法は、沈着調整剤(定
着剤)を用いる工程において、ホルムアルデヒド等の還
元剤を含む硝酸銀等の銀塩水溶液で処理するものである
から、本件出願発明の還元剤を空中で混合させる方式に
比べると銀塩水溶液および還元剤を多量に必要としコス
トアップをまねくという問題があった。In the latter method of depositing a silver layer on a non-conductive substrate disclosed in JP-A-8-325743, a silver salt such as silver nitrate containing a reducing agent such as formaldehyde is used in the step of using a deposition control agent (fixing agent). Since the treatment is carried out with an aqueous solution, there is a problem in that the silver salt aqueous solution and the reducing agent are required in large amounts and the cost is increased as compared with the method of mixing the reducing agent of the present invention in the air.
【０００９】また、不伝導基質上の銀層沈着工法は、そ
の目的を微生物の成長に抵抗性の物品を製造する方法と
しているため、薄膜に形成される銀層は変色しやすく、
特に耐熱性・耐候性を要求される自動車部品等の表面処
理に適用することができないという問題点があった。In addition, the method of depositing a silver layer on a non-conductive substrate is a method for producing an article resistant to the growth of microorganisms, so that the silver layer formed on the thin film is easily discolored.
In particular, there is a problem that it cannot be applied to surface treatment of automobile parts and the like that require heat resistance and weather resistance.
【００１０】[0010]
【課題を解決するための手段】本発明は、樹脂成形品の
表面に金属光沢を有する塗膜の形成するにあたり、特に
被塗装物表面に金属イオンを含んだ液体を吹き付け、金
属イオンを還元して析出させ、この表面にクリアー塗装
を行うことによって耐薬品性、耐候性等に優れた金属の
均一な薄膜が得られる金属光沢を有する塗膜の形成方法
の提供を目的とすものである。According to the present invention, in forming a coating film having a metallic luster on the surface of a resin molded product, a liquid containing metal ions is sprayed on the surface of an object to be coated, and the metal ions are reduced. It is an object of the present invention to provide a method for forming a coating film having a metallic luster by which a uniform thin film of a metal having excellent chemical resistance and weather resistance can be obtained by performing a clear coating on this surface.
【００１１】すなわち、本願の第１の発明は、樹脂製被
塗装物の表面に金属を含むベース溶液を吹き付け、純水
にて余剰分を水洗し、その後この表面に金属イオンを含
む水溶液と還元剤水溶液を同時に吹き付け、金属イオン
を還元して被塗装物表面に金属を析出させ、その後、純
水にて余剰分を水洗し、アクリル酸エステル系の定着剤
を吹き付け、この定着剤を乾燥させた後クリアー塗装を
行うようにしたことを特徴とする金属光沢を有する塗膜
の形成方法である。That is, the first invention of the present application is to spray a base solution containing a metal onto the surface of a resin-made article to be coated, wash the surplus with pure water, and then reduce the surface with an aqueous solution containing metal ions. Simultaneously spray an aqueous solution of the agent to reduce metal ions to precipitate metal on the surface of the object to be coated, then wash the excess with pure water, spray an acrylic ester-based fixing agent, and dry the fixing agent. And a method of forming a coating film having metallic luster, wherein clear coating is performed after the coating.
【００１２】本願の第１の発明によれば、１つの生産ラ
インにて、樹脂製被塗装物の表面に金属光沢を有する塗
膜を形成できるためリードタイムが短く生産性を上げる
ことができる。また、還元剤を空中で混合させて吹き付
けるものであるから、従来硝酸銀等の銀塩水溶液で処理
するものに比べて、銀塩水溶液および還元剤が少なくて
すみ、生産コストを低減させることができる。なお、前
記の樹脂製被塗装物としては、樹脂成形品に限らず紙、
粘土等材質を選ばず、また耐熱の低いもの、耐薬品に弱
いものにも適用が可能である。また、めつきの種類とし
ては、銀、ニッケル等無電解めっきがある。According to the first aspect of the present invention, a coating film having a metallic luster can be formed on the surface of the resin-made article to be coated in one production line, so that the lead time is short and the productivity can be improved. Further, since the reducing agent is mixed and sprayed in the air, the amount of the silver salt aqueous solution and the reducing agent can be reduced as compared with the conventional treatment with a silver salt aqueous solution such as silver nitrate, and the production cost can be reduced. . In addition, the above-mentioned resin-coated object is not limited to a resin molded product, but may be paper,
It can be applied to any material such as clay, low heat resistance and weak chemical resistance. In addition, as a type of plating, there is electroless plating such as silver and nickel.
【００１３】また、第２の発明は、前記ベース溶液の金
属としては錫とし、金属イオンを含む水溶液としてはア
ンモニア性硝酸銀水溶液とし、還元する金属イオンを銀
として被塗装物表面に銀を析出させ、定着剤としてはア
クリル酸エステルを含んだ溶液を用いたことを特徴とす
る請求項１記載の金属光沢を有する塗膜の形成方法であ
る。In a second aspect of the present invention, silver is deposited on the surface of the workpiece by using tin as a metal of the base solution, an aqueous solution of ammonium nitrate as an aqueous solution containing metal ions, and silver as a metal ion to be reduced. , a is as a fixing agent
The method according to claim 1 , wherein a solution containing a acrylate is used.
【００１４】本願の第２の発明によれば、銀膜下のプラ
イマーへの密着を強固にすることと後から行なうクリア
ー塗装との相性を良くする効果が得られる。また、後か
ら行なうクリアー塗装のクリアーの中に同様の表面調整
剤を用いることで置きかえることも可能である。つま
り、樹脂成形品の表面に、耐薬品性、耐候性等に優れた
銀めっき調の金属薄膜を形成させることができるため、
例えば自動車の内装部品や外装部品に適用させることが
できる。According to the second aspect of the present invention, the plug under the silver film is provided.
Enhancing the adhesion to the immer and clearing later
-The effect of improving compatibility with painting is obtained. Also later
Similar surface adjustment in the clear paint clear
It is also possible to replace by using an agent. Toes
Since a silver-plated metal thin film with excellent chemical resistance and weather resistance can be formed on the surface of the resin molded product,
For example, it can be applied to interior parts and exterior parts of automobiles.
【００１５】また、第３の発明は、前記の樹脂製被塗装
物が軟質樹脂の成形品であることを特徴とする請求項２
記載の金属光沢を有する塗膜の形成方法である。According to a third aspect of the present invention, the object to be coated with a resin is a molded product of a soft resin.
A method for forming a coating film having the described metallic luster.
【００１６】本願の第３の発明によれば、樹脂製被塗装
物を軟質樹脂の成形品とすることにより、金属イオンを
還元して被塗装物表面に銀を析出させるに際し、プライ
マーおよびクリアーを軟質系にすることにより変形に追
従し、クラックの発生しない金属光沢を付与させること
ができる。According to the third invention of the present application, by forming the resin-coated object into a molded product of a soft resin, a primer and a clear material are used for reducing metal ions and depositing silver on the surface of the object to be coated. By using a soft system, deformation can be followed and a metallic luster free of cracks can be imparted.
【００１７】上記の軟質の製品としては、例えば、ラヂ
エータグリルのめっき品、バンパーガードのめっきガー
ニッシュ類、ステアリングハンドル、会社、車名エンブ
レム等がある。The above-mentioned soft products include, for example, a plated product of a radiator grill, a plated garnish of a bumper guard, a steering handle, a company, and a car name emblem.
【００１８】[0018]
【発明の実施の形態】BEST MODE FOR CARRYING OUT THE INVENTION
【実施例】以下、本発明に係る金属光沢を有する塗膜の
形成方法を、図面を参照しながら説明する。図１は、本
発明に係る金属光沢を有する塗膜の形成方法の工程図で
あり、本発明では、次の手順により樹脂製被塗装物の表
面に金属光沢を有する塗膜が形成される。 樹脂製被塗装物の表面性状を調えるためにプライマー
塗装を行ない、６０度にて２時間程乾燥させる。 金属（錫）を含むベース溶液の吹き付けをおこない、
その後純水にて余剰分を水洗する。 その後、ベース塗装された表面に金属イオン（銀）を
含む水溶液と還元剤水溶液を同時に吹き付け（約１
分)、金属イオンを還元して被塗装物表面に金属を析出
させ、その後純水にて余剰分を水洗し、１５分程放置す
る。 次いで珪酸エステルを含んだアクリル酸エステル系の
定着剤を吹き付けて(約１分)、１５分程放置する。 その後クリアー塗装を行う。DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for forming a coating film having a metallic luster according to the present invention will be described below with reference to the drawings. FIG. 1 is a process chart of a method for forming a coating film having a metallic luster according to the present invention. In the present invention, a coating film having a metallic luster is formed on the surface of a resin-made workpiece by the following procedure. A primer is applied to adjust the surface properties of the resin-coated object, and dried at 60 degrees for about 2 hours. Spray a base solution containing metal (tin),
Then, the excess is washed with pure water. Thereafter, an aqueous solution containing metal ions (silver) and a reducing agent aqueous solution are simultaneously sprayed on the base-coated surface (approximately 1
Min), metal ions are reduced to precipitate metal on the surface of the object to be coated, and then the excess is washed with pure water and left for about 15 minutes. Next , an acrylic ester-based fixing agent containing a silicate ester is sprayed (about 1 minute) and left for about 15 minutes. After that, clear coating is performed.
【００１９】また、ベース塗装に用いる溶液は、塩化錫
を塩酸溶液へ溶解させたものであり、３％〜１５％の水
溶液である。また、金属イオンを含む水溶液としては濃
度０．１％〜１５％のアンモニア性硝酸銀水溶液であ
る。この場合、還元する金属イオンは銀であり、被塗装
物表面には銀が析出する。The solution used for the base coating is obtained by dissolving tin chloride in a hydrochloric acid solution, and is a 3% to 15% aqueous solution. Further, the aqueous solution containing metal ions is an aqueous solution of ammonium silver nitrate having a concentration of 0.1% to 15%. In this case, the metal ion to be reduced is silver, and silver precipitates on the surface of the object to be coated.
【００２０】[0020]
【発明の効果】本発明の金属光沢を有する塗膜の形成方
法は、樹脂成形品の表面に金属光沢を有する塗膜の形成
するに当たり、特に被塗装物表面に金属イオンを含んだ
液体を吹き付け、金属イオンを還元して析出させ、この
表面にクリアー塗装を行うものであるから、クリアー塗
装を除き一貫した生産ラインで行うことができるため、
安価なコストで且つリードタイムを短くし生産性を上げ
ることができる。また、金属イオンを還元して析出させ
た金属の表面にクリアー塗装を行うものであるから、金
属の変色がなく、特に耐薬品性・耐候性を要求される自
動車部品等の表面処理に適用することができる。また、
従来めっき等では不可能だった軟質樹脂への金属光沢を
付与することが可能となり産業上有益な効果がある。According to the method for forming a coating film having a metallic luster of the present invention, a liquid containing metal ions is sprayed on the surface of an object to be coated, particularly when a coating film having a metallic gloss is formed on the surface of a resin molded product. Since the metal ions are reduced and precipitated and this surface is subjected to clear coating, it can be performed on a consistent production line except for clear coating,
Inexpensive cost, shorter lead time, and higher productivity can be achieved. In addition, since the surface of the metal deposited by reducing metal ions is subjected to clear coating, there is no discoloration of the metal, and it is particularly applied to surface treatment of automobile parts and the like that require chemical resistance and weather resistance. be able to. Also,
Metallic luster can be imparted to a soft resin, which has been impossible with conventional plating and the like, and has an industrially beneficial effect.
【図面の簡単な説明】[Brief description of the drawings]
【図１】 本発明に係る金属光沢を有する塗膜の形成工
程図。FIG. 1 is a process chart for forming a coating film having a metallic luster according to the present invention.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図１[Correction target item name] Fig. 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図１】 FIG.
Claims (3)
溶液を吹き付け、純水にて余剰分を水洗し、その後この
表面に金属イオンを含む水溶液と還元剤水溶液を同時に
吹き付け、金属イオンを還元して被塗装物表面に金属を
析出させ、その後、純水にて余剰分を水洗し、クエン酸
ナトリウム、水酸化ナトリウム、水酸化カリウム、アン
モニア等の定着剤を吹き付け、この定着剤を乾燥させた
後クリアー塗装を行うようにしたことを特徴とする金属
光沢を有する塗膜の形成方法。1. A base solution containing a metal is sprayed on the surface of a resin-made object to be coated, an excess is washed with pure water, and then an aqueous solution containing a metal ion and an aqueous solution of a reducing agent are sprayed on the surface at the same time. To precipitate a metal on the surface of the object to be coated, and then wash the excess with pure water and spray a fixing agent such as sodium citrate, sodium hydroxide, potassium hydroxide, ammonia, etc. A method for forming a coating film having a metallic luster, wherein a clear coating is performed after drying.
属イオンを含む水溶液としてはアンモニア性硝酸銀水溶
液とし、還元する金属イオンを銀として、定着剤として
は水酸化ナトリウムを用いたことを特徴とする請求項１
記載の金属光沢を有する塗膜の形成方法。2. The method according to claim 1, wherein the metal of the base solution is tin, the aqueous solution containing metal ions is an aqueous ammoniacal silver nitrate solution, the metal ions to be reduced are silver, and the fixing agent is sodium hydroxide. Claim 1
A method for forming a coating film having the above-mentioned metallic luster.
であることを特徴とする請求項２記載の金属光沢を有す
る塗膜の形成方法。3. The method for forming a coating film having a metallic luster according to claim 2, wherein said resin-coated object is a molded product of a soft resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11223184A JP2001046958A (en) | 1999-08-06 | 1999-08-06 | Formation of coating film having metallic luster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11223184A JP2001046958A (en) | 1999-08-06 | 1999-08-06 | Formation of coating film having metallic luster |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001046958A true JP2001046958A (en) | 2001-02-20 |
Family
ID=16794131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11223184A Pending JP2001046958A (en) | 1999-08-06 | 1999-08-06 | Formation of coating film having metallic luster |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001046958A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004040035A1 (en) * | 2002-11-01 | 2004-05-13 | Advance Company, Ltd. | Method for forming thin silver mirror film, and method for forming coating film comprising thin silver mirror film |
| JP2006291014A (en) * | 2005-04-08 | 2006-10-26 | Origin Electric Co Ltd | Anticorrosive coating, plastic article, method for producing anticorrosive silver mirror film, and method for producing plastic article |
| KR100940773B1 (en) * | 2009-05-15 | 2010-02-10 | 나노씨엠에스(주) | Method for electroless deposition of nano metalic silver and plate deposited by nano metalic silver using the same |
| KR100983807B1 (en) * | 2009-09-28 | 2010-09-27 | 나노씨엠에스(주) | Method for electroless deposition of metalic silver and reflector of high reflectance deposited by metalic silver using the same |
| EP2253736A1 (en) | 2009-05-15 | 2010-11-24 | Nano CMS Co., Ltd. | Method for electroless deposition of nano metallic silver and reflector of high reflectance deposited by nano metallic silver using the same |
-
1999
- 1999-08-06 JP JP11223184A patent/JP2001046958A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004040035A1 (en) * | 2002-11-01 | 2004-05-13 | Advance Company, Ltd. | Method for forming thin silver mirror film, and method for forming coating film comprising thin silver mirror film |
| JP2006291014A (en) * | 2005-04-08 | 2006-10-26 | Origin Electric Co Ltd | Anticorrosive coating, plastic article, method for producing anticorrosive silver mirror film, and method for producing plastic article |
| KR100940773B1 (en) * | 2009-05-15 | 2010-02-10 | 나노씨엠에스(주) | Method for electroless deposition of nano metalic silver and plate deposited by nano metalic silver using the same |
| EP2253736A1 (en) | 2009-05-15 | 2010-11-24 | Nano CMS Co., Ltd. | Method for electroless deposition of nano metallic silver and reflector of high reflectance deposited by nano metallic silver using the same |
| KR100983807B1 (en) * | 2009-09-28 | 2010-09-27 | 나노씨엠에스(주) | Method for electroless deposition of metalic silver and reflector of high reflectance deposited by metalic silver using the same |
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