JP5315667B2

JP5315667B2 - METALLIC COATED PRODUCT AND METHOD FOR FORMING THE METALLIC COATED PRODUCT

Info

Publication number: JP5315667B2
Application number: JP2007283548A
Authority: JP
Inventors: 正樹重盛
Original assignee: Pentel Co Ltd
Current assignee: Pentel Co Ltd
Priority date: 2007-10-31
Filing date: 2007-10-31
Publication date: 2013-10-16
Anticipated expiration: 2027-10-31
Also published as: JP2009106888A

Description

本発明は、少なくとも手で直接及び／又は間接的に触れる部分に塗膜を設けたメタリック塗装物及び、その形成方法に関するものであり、例えば万年筆やボールペンやシャープペンシルなどの筆記具や、口紅やアイライナーなどの容器、釣り竿、ドアノブ、手摺りなどが挙げられる。 The present invention relates to a metallic paint having a coating film at least directly and / or indirectly touched by hand, and a method for forming the same. Containers such as liners, fishing rods, door knobs, handrails and the like can be mentioned.

メタリック塗装物は、外観の意匠性を向上させるために様々な発明がなされている。特に蒸着金属膜を粉砕した金属片を用いたメタリック塗膜は、金属光沢を有することから新規高輝度メタリック塗装物として様々な分野で使用されている。 Various inventions have been made for metallic paints in order to improve the design of the appearance. In particular, a metallic coating film using a metal piece obtained by pulverizing a vapor-deposited metal film has a metallic luster, and thus is used in various fields as a new high-brightness metallic coating.

特開２００５−１６２９７７号公報JP 2005-162977 A

メタリック塗膜の金属光沢を効果的に発現させるためには、乾燥塗膜中での金属片を規則的に配向させることが重要である。そこでバインダー樹脂の主成分に鎖状高分子を用いたメタリック塗料による塗装方法が提案されている。
しかし、バインダー樹脂の主成分として鎖状高分子を用いた場合、加熱等により可塑性が発現し、添加されている金属片の配向を阻害しないものの、塗膜を硬化させるための再加熱等により金属片の配向が変化し、金属光沢感が得られない問題があった。 In order to effectively express the metallic luster of the metallic coating film, it is important to regularly orient the metal pieces in the dry coating film. Thus, a coating method using a metallic paint using a chain polymer as the main component of the binder resin has been proposed.
However, when a chain polymer is used as the main component of the binder resin, plasticity is manifested by heating or the like, and it does not impair the orientation of the added metal piece, but the metal is reheated to cure the coating film. There was a problem that the orientation of the piece was changed and the metallic luster was not obtained.

そこで本発明は、積層塗膜からなるメタリック塗装物において、少なくともメタリック塗膜と、メタリック塗膜の下層と上層に同一の鎖状高分子材料を主成分とする有機溶剤系塗料により形成した塗膜とが、一体の複合塗膜層となることを要旨とするものである。 Accordingly, the present invention provides a metallic coating comprising a multilayer coating film, at least a metallic coating film, and a coating film formed from an organic solvent-based paint mainly comprising the same chain polymer material as a lower layer and an upper layer of the metallic coating film. Is a gist of an integrated composite coating layer.

被塗物の材質は、塗装できる材料であればよく特に限定されない。具体的には、アルミニウムまたはその合金、銅またはその合金、鉄またはその合金、亜鉛またはその合金、マグネシウムまたはその合金、チタンまたはその合金、金またはその合金、銀またはその合金、白金またはその合金、スズまたはその合金、ニッケルまたはその合金などの金属材料、塩化ビニル、ポリスチレン、アクリル、ポリカーボネート、アクリロニトリルブタジエンスチレン共重合体、アクリロニトリルスチレン共重合体、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリアミド、ナイロン、ポリアセタールなどの熱可塑性樹脂材料、ポリスチレン系、ポリオレフィン系、ポリ塩化ビニル系、ポリウレタン系、ポリエステル系、ポリアミド系などの熱可塑性エラストマー、シリコーン、スチレンブタジエン、ウレタン、ブタジエン、イソプレン、フッ素などの合成ゴムや天然ゴム、エポキシ樹脂、フェノール樹脂、シアネート樹脂、尿素樹脂、グアナミン樹脂などの熱硬化樹脂材料、アルミナ、ジルコニア、陶磁器、ガラスなどのセラミック材料、木材、紙、石などの天然材料などを用いることができる。
また、これらの材料は１種または２種以上の混合物であってもよい。さらに、これらの材質には、予め湿式めっき法や乾式めっき法、塗装、印刷、化成処理やクロメート処理などの公知の方法により、ニッケルやクロムや黒クロムなどの金属めっき層、あるいは金や銀やパラジウムなどの貴金属めっき層、塗膜層、印刷層、接着層、酸化物層などの下地処理層を形成してもよい。 The material of the object to be coated is not particularly limited as long as it can be painted. Specifically, aluminum or its alloy, copper or its alloy, iron or its alloy, zinc or its alloy, magnesium or its alloy, titanium or its alloy, gold or its alloy, silver or its alloy, platinum or its alloy, Metal material such as tin or its alloy, nickel or its alloy, vinyl chloride, polystyrene, acrylic, polycarbonate, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate , Thermoplastic resin materials such as polybutylene naphthalate, polyamide, nylon, polyacetal, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester Thermoplastic resins such as thermoplastic elastomers such as rubbers and polyamides, synthetic rubbers such as silicone, styrene butadiene, urethane, butadiene, isoprene and fluorine, natural rubber, epoxy resins, phenol resins, cyanate resins, urea resins and guanamine resins Materials, ceramic materials such as alumina, zirconia, ceramics, and glass, natural materials such as wood, paper, and stone can be used.
These materials may be one kind or a mixture of two or more kinds. In addition, these materials are preliminarily formed by a known method such as a wet plating method, a dry plating method, painting, printing, chemical conversion treatment or chromate treatment, a metal plating layer such as nickel, chromium, black chrome, gold, silver, or the like. You may form base treatment layers, such as noble metal plating layers, such as palladium, a coating layer, a printing layer, an adhesion layer, and an oxide layer.

メタリック塗膜を形成する塗料は、少なくともメタリック粉体と液媒体を含んでいればよく、液媒体として有機溶剤を使用した有機溶剤系塗料であれば特に限定しない。
メタリック粉体としては、ガラスフレークやガラスフレークの表面をニッケルや銀などの金属もしくは金属酸化物で被覆した特殊顔料や、アルミニウムまたはその合金、銅またはその合金、鉄またはその合金、亜鉛またはその合金、マグネシウムまたはその合金、チタンまたはその合金、金またはその合金、銀またはその合金、白金またはその合金、スズまたはその合金、ニッケルまたはその合金、クロムまたはその合金、コバルトまたはその合金などの金属や、前記金属の酸化物や窒化物などを公知の方法により粉砕したメタリック顔料などが使用できる。また、メタリック粉体の形状としては鱗片状が好ましい。さらに、蒸着金属膜を粉砕した金属片をメタリック粉体とすることにより、金属調の外観を有し、且つ金属光沢の優れたメタリック塗膜を形成することが出来る。
メタリック粉体の重量濃度は、乾燥塗膜中に１ｗｔ％以上で、特に１５ｗｔ％以上で優れた金属調の外観を有するメタリック塗膜が得られる。また、１ｗｔ％以下では、金属調の外観は得られず、外観特性が悪化する。また前記金属片のメタリック顔料の重量濃度を１００ｗｔ％にすることで、金属調の外観を有し、且つ金属光沢の優れたメタリック塗膜が得られる。 The paint for forming the metallic coating film is not particularly limited as long as it contains at least metallic powder and a liquid medium, and is an organic solvent-based paint using an organic solvent as the liquid medium.
Metallic powders include glass flakes, special pigments whose surfaces are coated with a metal or metal oxide such as nickel or silver, aluminum or alloys thereof, copper or alloys thereof, iron or alloys thereof, zinc or alloys thereof. Metal such as magnesium or its alloy, titanium or its alloy, gold or its alloy, silver or its alloy, platinum or its alloy, tin or its alloy, nickel or its alloy, chromium or its alloy, cobalt or its alloy, Metallic pigments obtained by pulverizing the metal oxides or nitrides by a known method can be used. Further, the shape of the metallic powder is preferably scaly. Furthermore, by using a metallic powder obtained by pulverizing the deposited metal film as a metallic powder, it is possible to form a metallic coating film having a metallic appearance and excellent in metallic luster.
The weight concentration of the metallic powder is 1 wt% or more in the dry coating film, particularly 15 wt% or more, and a metallic coating film having an excellent metallic appearance can be obtained. On the other hand, if it is 1 wt% or less, the metallic appearance cannot be obtained and the appearance characteristics deteriorate. Moreover, by setting the weight concentration of the metallic pigment of the metal piece to 100 wt%, a metallic coating film having a metallic appearance and excellent in metallic luster can be obtained.

鎖状高分子材料を含む塗料は、少なくとも鎖状高分子材料と液媒体を含んでいればよい。液媒体として有機溶剤を使用した有機溶剤系塗料であれば特に限定しない。さらに、鎖状高分子材料を含む塗料は、透明もしくは半透明の所謂クリヤー塗料やカラークリヤー塗料が好ましい。
特に、前記鎖状高分子材料は、前記液媒体に可溶で、加熱等により可塑性を発現し、且つ接着性を有する樹脂がよく、熱可塑性接着剤が好適に使用できる。具体的には、ポリエチレン樹脂、エチレン−酢酸ビニル共重合樹脂、エチレン−イソブチルアクリレート共重合樹脂、ポリアミド樹脂、ポリエステル樹脂、ブチラール樹脂、ポリ酢酸ビニルおよび共重合体、ポリメチルメタクリレート樹脂、ポリビニルエーテル樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリプロピレン樹脂、又はこれら樹脂を主成分とする混合物が挙げられ、これらは一種もしくは二種以上の混合物でもよい。またこれらに、テルペン系樹脂やロジン系樹脂などの粘着性付与剤や、パラフィン系オイルなどの柔軟剤、カーボンブラック、タルク、クレー、シリカ、炭酸カルシウム、無機顔料、有機顔料などの充填剤、ゼオライト、シリカゲルなどの吸着剤などを必要に応じて添加することもできる。特に吸水性が少ないポリエステル樹脂が好適に使用できる。
さらに、前記塗料に硬化剤を添加することにより、前記鎖状高分子材料を時間の経過とともに反応硬化させることができる。硬化剤の具体例としては、メラミン樹脂やポリイソシアネート樹脂など挙げられる。 The coating material containing a chain polymer material only needs to contain at least a chain polymer material and a liquid medium. There is no particular limitation as long as it is an organic solvent-based paint using an organic solvent as a liquid medium. Further, the paint containing the chain polymer material is preferably a transparent or translucent so-called clear paint or color clear paint.
In particular, the chain polymer material is preferably a resin that is soluble in the liquid medium, exhibits plasticity by heating or the like, and has adhesiveness, and a thermoplastic adhesive can be suitably used. Specifically, polyethylene resin, ethylene-vinyl acetate copolymer resin, ethylene-isobutyl acrylate copolymer resin, polyamide resin, polyester resin, butyral resin, polyvinyl acetate and copolymer, polymethyl methacrylate resin, polyvinyl ether resin, A polyurethane resin, a polycarbonate resin, a polypropylene resin, or a mixture containing these resins as a main component may be mentioned, and these may be one kind or a mixture of two or more kinds. In addition, tackifiers such as terpene resins and rosin resins, softeners such as paraffinic oils, fillers such as carbon black, talc, clay, silica, calcium carbonate, inorganic pigments and organic pigments, zeolites An adsorbent such as silica gel can be added as necessary. In particular, a polyester resin with low water absorption can be suitably used.
Furthermore, by adding a curing agent to the coating material, the chain polymer material can be reaction-cured over time. Specific examples of the curing agent include melamine resin and polyisocyanate resin.

本発明は、メタリック塗膜の下層と上層に同一の鎖状高分子材料を主成分とする有機溶剤系塗料により塗膜を形成し、前記鎖状高分子材料の軟化点以上の温度で加熱することで可塑性が発現し、メタリック塗膜が鎖状高分子材料を含む塗料により形成した塗膜と一体となり、金属光沢感の低下を防止できる。
また、鎖状高分子材料を主成分とする有機溶剤系塗料により形成した塗膜の形成とメタリック塗膜を形成とを別々の工程とすることで、前記鎖状高分子材料を主成分とする有機溶剤系塗料により形成した塗膜の反応硬化前に、メタリック塗膜を乾燥させることが可能となり、塗膜を硬化させるための再加熱によりメタリック粉体の配向が変化しないため金属光沢感の低下を防止できる。
さらに、前記鎖状高分子材料として熱可塑性接着剤を使用することにより、鎖状高分子材料を主成分とする有機溶剤系塗料により形成した塗膜内に取り込まれたメタリック粉体との接着性が向上し、その結果、積層塗膜全体の密着性の低下を防止できる。また、硬化剤を併用することにより、時間とともに塗膜が反応硬化することで環境中の水分等による積層塗膜全体の密着性の低下を防止できる。 In the present invention, the lower layer and the upper layer of the metallic coating film are formed with an organic solvent-based paint mainly composed of the same chain polymer material, and heated at a temperature equal to or higher than the softening point of the chain polymer material. As a result, plasticity is developed, and the metallic coating film is integrated with a coating film formed of a coating material containing a chain polymer material, thereby preventing a decrease in metallic luster.
In addition, the formation of a coating film formed of an organic solvent-based paint mainly composed of a chain polymer material and the formation of a metallic coating film are performed as separate steps, so that the chain polymer material is a main component. It becomes possible to dry the metallic coating film before the reaction curing of the coating film formed with organic solvent-based paint, and the metallic powder orientation is not changed by reheating to cure the coating film. Can be prevented.
Furthermore, by using a thermoplastic adhesive as the chain polymer material, the adhesiveness with the metallic powder incorporated in the coating film formed by the organic solvent-based paint mainly composed of the chain polymer material As a result, it is possible to prevent a decrease in the adhesion of the entire laminated coating film. In addition, by using a curing agent in combination, the coating film reacts and cures over time, so that it is possible to prevent a decrease in the adhesion of the entire laminated coating film due to moisture in the environment.

本発明は、メタリック塗膜の下層と上層に同一の鎖状高分子材料を主成分とする有機溶剤系塗料により形成した塗膜を形成したことを最も主要な特徴とし、鎖状高分子材料の軟化点以上の温度で加熱と反応硬化により、再加熱しても金属光沢感の低下を抑制する目的を実現した。
また、本発明のメタリック塗装物の形成は、下記の工程を施すことにより実現した。
（１）被塗物１上に、鎖状高分子材料を主成分とする有機溶剤系塗料を塗布してなる塗膜２を形成する工程。
（２）前記塗膜を乾燥する工程（図１）。
（３）前記塗膜の上層部に、メタリック粉体４を介在したメタリック塗膜３を形成する工程。
（４）メタリック塗膜３を前記鎖状高分子材料の軟化点以下の温度で乾燥する工程（図２）。
（５）メタリック塗膜３の上層部に、（１）で使用した鎖状高分子材料と同一の鎖状高分子材料を主成分とする有機溶剤系塗料を塗布してなる塗膜５を形成する工程（図３）。
（６）前記鎖状高分子材料の軟化点以上の温度で鎖状高分子材料を含む塗料を塗布してなる塗膜２とメタリック塗膜３と鎖状高分子材料を含む塗料を塗布してなる塗膜５とを一体化（複合塗膜層６）した後、反応硬化する工程（図４）。 The main feature of the present invention is that a coating film formed of an organic solvent-based paint mainly composed of the same chain polymer material is formed on the lower layer and the upper layer of the metallic coating film . By heating and reaction hardening at a temperature above the softening point, the purpose of suppressing the decrease in metallic luster even when reheated was realized.
Moreover, formation of the metallic coating material of this invention was implement | achieved by giving the following process.
(1) The process of forming the coating film 2 formed by apply | coating the organic solvent type coating material which has a chain polymer material as a main component on the to-be-coated article 1.
(2) A step of drying the coating film (FIG. 1).
(3) The process of forming the metallic coating film 3 which interposed the metallic powder 4 in the upper layer part of the said coating film.
(4) A step of drying the metallic coating film 3 at a temperature below the softening point of the chain polymer material (FIG. 2).
(5) A coating film 5 is formed by applying an organic solvent-based paint mainly composed of the same chain polymer material used in (1) to the upper layer of the metallic coating film 3. Step (FIG. 3)
(6) A coating film 2 formed by applying a coating material containing a chain polymer material at a temperature equal to or higher than the softening point of the chain polymer material, a metallic coating film 3, and a coating material containing a chain polymer material. The process (FIG. 4) which carries out reaction hardening after integrating the coating film 5 which becomes (composite coating film layer 6).

（参考例１）
真鍮製の、外径１０ｍｍ、長さ１００ｍｍである横断面外形状が円形の材料の、塗料を塗布する面（塗布面）に、バフ研磨を施して表面を平滑にし、ジクロロメタンで脱脂処理し被塗物とした。次いで鎖状高分子材料としてアクリル樹脂を含む塗料、所謂アクリルラッカー塗料（トアインクラック（クリヤー）、（株）トウペ製）をスプレー塗装した後、５０℃、３０分の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に前記アクリルラッカー塗料で得られた透明アクリル塗膜の軟化点以上の温度である１００℃で１０分間加熱し、透明アクリル塗膜とメタリック塗膜の２層とが一体の複合塗膜となったメタリック塗装物を得た。 (Reference Example 1)
A surface made of brass with an outer diameter of 10 mm and a length of 100 mm and having a circular cross-sectional outer shape is smoothened by buffing the coating surface (coating surface), degreased with dichloromethane, and coated. Painted. Subsequently, a paint containing an acrylic resin as a chain polymer material, a so-called acrylic lacquer paint (Toray ink rack (Clear), manufactured by Toupe Co., Ltd.) was spray-coated, and then dried at 50 ° C. for 30 minutes. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, it is heated for 10 minutes at 100 ° C., which is a temperature higher than the softening point of the transparent acrylic coating obtained with the acrylic lacquer coating, and the two layers of the transparent acrylic coating and the metallic coating become an integrated composite coating. A metallic paint was obtained.

（実施例１）
参考例１と同様の被塗物を用いた。次いで鎖状高分子材料としてアクリル樹脂を含む塗料、所謂アクリルラッカー塗料（トアインクラック（クリヤー）、（株）トウペ製）をスプレー塗装した後、５０℃、３０分の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料としてアクリル樹脂を含む塗料、所謂アクリルラッカー塗料（トアインクラック（クリヤー）、（株）トウペ製）をスプレー塗装した後、５０℃、３０分の条件で乾燥した。次いで前記アクリルラッカー塗料で得られた透明アクリル塗膜の軟化点以上の温度である１００℃で１０分間加熱し、透明アクリル塗膜とメタリック塗膜と透明アクリル塗膜の３層とが一体の複合塗膜となったメタリック塗装物を得た。 Example 1
The same coated object as in Reference Example 1 was used. Subsequently, a paint containing an acrylic resin as a chain polymer material, a so-called acrylic lacquer paint (Toray ink rack (Clear), manufactured by Toupe Co., Ltd.) was spray-coated, and then dried at 50 ° C. for 30 minutes. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a paint containing an acrylic resin as a chain polymer material, so-called acrylic lacquer paint (Toray ink rack (Clear), manufactured by Toupe Co., Ltd.) was spray-coated, and then dried at 50 ° C. for 30 minutes. Next, it is heated for 10 minutes at 100 ° C., which is a temperature equal to or higher than the softening point of the transparent acrylic coating obtained with the acrylic lacquer coating, and the three layers of the transparent acrylic coating, the metallic coating, and the transparent acrylic coating are combined into one. A metallic paint that became a coating film was obtained.

（参考例２）
真鍮製の、外径１０ｍｍ、長さ１００ｍｍである横断面外形状が円形の材料の、塗料を塗布する面（塗布面）に、バフ研磨を施して表面を平滑にし、ジクロロメタンで脱脂処理した後、公知の方法により黒クロムめっき層を形成し被塗物とした。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に前記ホットメルト接着剤で得られた半透明オレフィン樹脂塗膜の軟化点以上の温度である１５０℃で１０分間加熱し、半透明オレフィン樹脂塗膜とメタリック塗膜の２層とが一体の複合塗膜となったメタリック塗装物を得た。 (Reference Example 2)
After buffing the surface to which the paint is applied (applied surface) of a brass material having an outer diameter of 10 mm and a length of 100 mm and having a circular outer cross section, the surface is smoothed and degreased with dichloromethane. Then, a black chrome plating layer was formed by a known method to obtain an article to be coated. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) was spray-coated. Thereafter, it was dried at 80 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, it is heated for 10 minutes at 150 ° C., which is a temperature higher than the softening point of the semitransparent olefin resin coating film obtained with the hot melt adhesive, and the two layers of the semitransparent olefin resin coating film and the metallic coating film are integrated. A metallic paint that became a composite coating film was obtained.

（実施例２）
参考例２と同様の被塗物を用いた。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次に前記ホットメルト接着剤で得られた半透明オレフィン樹脂塗膜の軟化点以上の温度である１５０℃で１０分間加熱し、半透明オレフィン樹脂塗膜とメタリック塗膜と半透明オレフィン樹脂塗膜の３層とが一体の複合塗膜となったメタリック塗装物を得た。 (Example 2)
The same coated object as in Reference Example 2 was used. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) was spray-coated. Thereafter, it was dried at 80 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) was spray-coated. Thereafter, it was dried at 80 ° C. for 2 hours. Next, the semitransparent olefin resin coating film, the metallic coating film, and the semitransparent olefin resin coating film were heated at 150 ° C., which is a temperature higher than the softening point of the semitransparent olefin resin coating film obtained by the hot melt adhesive, for 10 minutes. Thus, a metallic coating was obtained in which the three layers were combined composite films.

（参考例３）
参考例２と同様の被塗物を用いた。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次に前記ホットメルト接着剤で得られた半透明オレフィン樹脂塗膜の軟化点以上の温度である１５０℃で１０分間加熱し、メタリック塗膜と半透明オレフィン樹脂塗膜の２層とが一体の複合塗膜となったメタリック塗装物を得た。 (Reference Example 3)
The same coated object as in Reference Example 2 was used. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) was spray-coated. Thereafter, it was dried at 80 ° C. for 2 hours. Next, it is heated for 10 minutes at 150 ° C., which is a temperature equal to or higher than the softening point of the semitransparent olefin resin coating film obtained by the hot melt adhesive, and the two layers of the metallic coating film and the semitransparent olefin resin coating film are integrated. A metallic paint that became a composite coating film was obtained.

（参考例４）
真鍮製の、外径１０ｍｍ、長さ１００ｍｍである横断面外形状が円形の材料の、塗料を塗布する面（塗布面）に、バフ研磨を施して表面を平滑にし、ジクロロメタンで脱脂処理した後、公知の方法により黒クロムめっき層を形成した。次に熱硬化性アクリル塗料（マジクロン１０００（ディープブラック）、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装し、１８０℃、２０分の条件で乾燥し被塗物とした。次に鎖状高分子材料としてポリエステル樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＥＳ３１０Ｓ３０（透明）、東亜合成（株）製）にポリイソシアネート樹脂を主成分とする硬化剤（コロネートＬ、日本ポリウレタン工業（株）製）を添加した塗料をスプレー塗装した後、１００℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に前記ホットメルト接着剤で得られた透明ポリエステル樹脂塗膜の軟化点以上の温度である１８０℃で１０分間加熱し、透明ポリエステル樹脂塗膜とメタリック塗膜の２層とが一体の複合塗膜となったメタリック塗装物を得た。 (Reference Example 4)
After buffing the surface to which the paint is applied (applied surface) of a brass material having an outer diameter of 10 mm and a length of 100 mm and having a circular outer cross section, the surface is smoothed and degreased with dichloromethane. Then, a black chromium plating layer was formed by a known method. Next, a thermosetting acrylic paint (Magiclon 1000 (Deep Black), manufactured by Kansai Paint Co., Ltd., diluted twice with a special thinner) was spray-coated, and dried at 180 ° C. for 20 minutes to obtain a coating object. Next, a thermoplastic adhesive mainly comprising a polyester resin as a chain polymer material, a so-called hot melt adhesive (PES310S30 (transparent), manufactured by Toa Gosei Co., Ltd.) and a curing agent mainly comprising a polyisocyanate resin ( After spray-coating the paint to which Coronate L and Nippon Polyurethane Industry Co., Ltd. were added, the coating was dried at 100 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, it is heated for 10 minutes at 180 ° C., which is a temperature equal to or higher than the softening point of the transparent polyester resin coating film obtained with the hot melt adhesive, so that the two layers of the transparent polyester resin coating film and the metallic coating film are integrated. A metallic paint that became a film was obtained.

（実施例３）
参考例４と同様の被塗物を用いた。次に鎖状高分子材料としてポリエステル樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＥＳ３１０Ｓ３０（透明）、東亜合成（株）製）にポリイソシアネート樹脂を主成分とする硬化剤（コロネートＬ、日本ポリウレタン工業（株）製）を添加した塗料をスプレー塗装した後、１００℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料としてポリエステル樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＥＳ３１０Ｓ３０（透明）、東亜合成（株）製）にポリイソシアネート樹脂を主成分とする硬化剤（コロネートＬ、日本ポリウレタン工業（株）製）を添加した塗料をスプレー塗装した後、１００℃、２時間の条件で乾燥した。次に前記ホットメルト接着剤で得られた透明ポリエステル樹脂塗膜の軟化点以上の温度である１８０℃で１０分間加熱し、透明ポリエステル樹脂塗膜とメタリック塗膜と透明ポリエステル樹脂塗膜の３層とが一体の複合塗膜となったメタリック塗装物を得た。 Example 3
The same coated object as in Reference Example 4 was used. Next, a thermoplastic adhesive mainly comprising a polyester resin as a chain polymer material, a so-called hot melt adhesive (PES310S30 (transparent), manufactured by Toa Gosei Co., Ltd.) and a curing agent mainly comprising a polyisocyanate resin ( After spray-coating the paint to which Coronate L and Nippon Polyurethane Industry Co., Ltd. were added, the coating was dried at 100 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a thermoplastic adhesive mainly comprising a polyester resin as a chain polymer material, a so-called hot melt adhesive (PES310S30 (transparent), manufactured by Toa Gosei Co., Ltd.) and a curing agent mainly comprising a polyisocyanate resin ( After spray-coating the paint to which Coronate L and Nippon Polyurethane Industry Co., Ltd. were added, the coating was dried at 100 ° C. for 2 hours. Next, it is heated for 10 minutes at 180 ° C., which is a temperature equal to or higher than the softening point of the transparent polyester resin coating film obtained with the hot melt adhesive, and consists of a transparent polyester resin coating film, a metallic coating film, and a transparent polyester resin coating film. And a metallic paint that became a composite film.

（参考例５）
参考例４と同様の被塗物を用いた。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料としてポリエステル樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＥＳ３１０Ｓ３０（透明）、東亜合成（株）製）にポリイソシアネート樹脂を主成分とする硬化剤（コロネートＬ、日本ポリウレタン工業（株）製）を添加した塗料をスプレー塗装した後、１００℃、２時間の条件で乾燥した。次に前記ホットメルト接着剤で得られた透明ポリエステル樹脂塗膜の軟化点以上の温度である１８０℃で１０分間加熱し、メタリック塗膜と透明ポリエステル樹脂塗膜の２層とが一体の複合塗膜となったメタリック塗装物を得た。 (Reference Example 5)
The same coated object as in Reference Example 4 was used. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a thermoplastic adhesive mainly comprising a polyester resin as a chain polymer material, a so-called hot melt adhesive (PES310S30 (transparent), manufactured by Toa Gosei Co., Ltd.) and a curing agent mainly comprising a polyisocyanate resin ( After spray-coating the paint to which Coronate L and Nippon Polyurethane Industry Co., Ltd. were added, the coating was dried at 100 ° C. for 2 hours. Next, it is heated for 10 minutes at 180 ° C., which is a temperature equal to or higher than the softening point of the transparent polyester resin coating film obtained with the hot melt adhesive, so that the two layers of the metallic coating film and the transparent polyester resin coating film are integrated. A metallic paint that became a film was obtained.

（実施例４）
参考例４と同様の被塗物を用いた。次に鎖状高分子材料としてポリエステル樹脂を主成分とする熱可塑性接着剤、所謂ホットメルト接着剤（ＰＥＳ３１０Ｓ３０（透明）、東亜合成（株）製）にポリイソシアネート樹脂を主成分とする硬化剤（コロネートＬ、日本ポリウレタン工業（株）製）を添加した塗料をスプレー塗装した後、１００℃、２時間の条件で乾燥した。次に蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に１ｗｔ％となるように配合したメタリック塗料（下記の組成物Ａ）をスプレー塗装した後、１００℃、１０分の条件で乾燥した。次に前記ホットメルト接着剤で得られた透明ポリエステル樹脂塗膜の軟化点以上の温度である１８０℃で２０分間加熱し、透明ポリエステル樹脂塗膜とメタリック塗膜の３層とが一体の複合塗膜となったメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ａ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）９．０９ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９０．８６ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック粉体：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）０．０５ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 (Example 4)
The same coated object as in Reference Example 4 was used. Next, a thermoplastic adhesive mainly comprising a polyester resin as a chain polymer material, a so-called hot melt adhesive (PES310S30 (transparent), manufactured by Toa Gosei Co., Ltd.) and a curing agent mainly comprising a polyisocyanate resin ( After spray-coating the paint to which Coronate L and Nippon Polyurethane Industry Co., Ltd. were added, the coating was dried at 100 ° C. for 2 hours. Next, after spray-coating a metallic paint (composition A described below) in which the metallic pigment obtained by pulverizing the vapor-deposited metal film into a metal piece so as to be 1 wt% in the dry coating film is obtained, the temperature is 100 ° C. for 10 minutes. Dried under conditions. Next, it is heated for 20 minutes at 180 ° C., which is a temperature higher than the softening point of the transparent polyester resin coating film obtained with the hot melt adhesive, and the transparent polyester resin coating film and the metallic coating film are combined into an integral composite coating. A metallic paint that became a film was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Composition of metallic coating material obtained by pulverizing vapor-deposited metal film (composition A)>
Magiclon 1000 Clear (Synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 9.09 wt%
Camping baking thinner No4 (organic solvent: manufactured by Kansai Paint Co., Ltd.) 90.86 wt%
Ciba METASHEEN 41-0010 (metallic powder: manufactured by Ciba Specialty Chemicals, PLC) 0.05 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例５）
実施例４における組成物Ａを下記組成物Ｂ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に３ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｂ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）９．０８ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９０．７８ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック粉体：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）０．１４ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 (Example 5)
The same metallic except that the composition A in Example 4 was replaced with the following composition B (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film so as to be 3 wt% in the dry coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Combination of metallic coating material obtained by pulverizing vapor-deposited metal film (composition B)>
Magiclon 1000 Clear (Synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 9.08 wt%
Campe baking thinner No4 (Organic solvent: Kansai Paint Co., Ltd.) 90.78 wt%
Ciba METASHEEN 41-0010 (Metallic powder: Ciba Specialty Chemicals, PLC) 0.14 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例６）
実施例４における組成物Ａを下記組成物Ｃ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に７ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｃ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）９．０６ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９０．６０ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック粉体：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）０．３４ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 (Example 6)
The same metallic except that the composition A in Example 4 was replaced with the following composition C (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film so as to be 7 wt% in the dry coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Composition of metallic coating material obtained by pulverizing vapor-deposited metal film (composition C)>
Magiclon 1000 Clear (synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 9.06 wt%
Campe baking thinner No4 (organic solvent: manufactured by Kansai Paint Co., Ltd.) 90.60 wt%
Ciba METASHEEN 41-0010 (Metallic powder: Ciba Specialty Chemicals, PLC) 0.34 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例７）
実施例４における組成物Ａを下記組成物Ｄ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に１２ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｄ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）９．０３ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９０．３５ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック粉体：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）０．６２ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 (Example 7)
The same metallic except that the composition A in Example 4 was replaced by the following composition D (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film and blended so as to be 12 wt% in the dried coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Composition of metallic coating material obtained by pulverizing vapor-deposited metal film (composition D)>
Magiclon 1000 Clear (Synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 9.03 wt%
Campe baking thinner No4 (Organic solvent: Kansai Paint Co., Ltd.) 90.35 wt%
Ciba METASHEEN 41-0010 (Metallic powder: Ciba Specialty Chemicals, PLC) 0.62 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例８）
実施例４における組成物Ａを下記組成物Ｅ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に１５ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｅ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）９．０２ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９０．１８ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック顔料：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）０．８０ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 (Example 8)
The same metallic except that the composition A in Example 4 was replaced by the following composition E (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film and blended so as to be 15 wt% in the dry coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Composition of metallic coating material obtained by pulverizing vapor-deposited metal film (composition E)>
Magiclon 1000 Clear (Synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 9.02 wt%
Camper baking thinner No4 (organic solvent: Kansai Paint Co., Ltd.) 90.18 wt%
Ciba METASHEEN 41-0010 (metallic pigment: manufactured by Ciba Specialty Chemicals, PLC) 0.80 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例９）
実施例４における組成物Ａを下記組成物Ｆ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に５０ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｆ）＞
マジクロン１０００クリヤー（合成樹脂塗料：関西ペイント（株）製）８．７０ｗｔ％
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）８６．９５ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック顔料：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）４．３５ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック・アクリル樹脂塗料を得た。 Example 9
The same metallic material except that the composition A in Example 4 was replaced with the following composition F (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film and blended so as to be 50 wt% in the dry coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Combination of metallic coating material obtained by pulverizing vapor-deposited metal film (composition F)>
Magiclon 1000 Clear (Synthetic resin paint: manufactured by Kansai Paint Co., Ltd.) 8.70wt%
Campe baking thinner No4 (organic solvent: manufactured by Kansai Paint Co., Ltd.) 86.95 wt%
Ciba METASHEEN 41-0010 (metallic pigment: manufactured by Ciba Specialty Chemicals, PLC) 4.35 wt%
The above components were dispersed with a ball mill for 60 minutes to obtain a metallic acrylic resin paint.

（実施例１０）
実施例４における組成物Ａを下記組成物Ｇ（蒸着金属膜を粉砕して金属片としたメタリック顔料を乾燥塗膜中に１００ｗｔ％となるように配合したメタリック塗料）に代えた以外同様のメタリック塗装物を得た。さらに、メタリック塗装物の上層部に熱硬化性アクリル塗料（マジクロン１０００クリヤー、関西ペイント（株）製を専用シンナーで２倍希釈）をスプレー塗装した後、１８０℃、２０分の条件で乾燥しクリヤー塗膜を形成した。
＜蒸着金属膜を粉砕して金属片としたメタリック塗料の配合（組成物Ｇ）＞
カンペ焼付用シンナーＮｏ４（有機溶剤：関西ペイント（株）製）９９．００ｗｔ％
ＣｉｂａＭＥＴＡＳＨＥＥＮ４１−００１０（メタリック顔料：ＣｉｂａＳｐｅｃｉａｌｔｙＣｈｅｍｉｃａｌｓ，ＰＬＣ製）１．００ｗｔ％
上記成分をボールミルにて６０分間分散し、メタリック塗料を得た。 (Example 10)
The same metallic material except that the composition A in Example 4 was replaced with the following composition G (a metallic paint in which a metallic pigment was pulverized from a vapor-deposited metal film and blended so as to be 100 wt% in the dry coating film). A painted product was obtained. Furthermore, after spray-coating a thermosetting acrylic paint (Magiclon 1000 Clear, manufactured by Kansai Paint Co., Ltd., twice diluted with a special thinner) on the upper layer of the metallic paint, it is dried at 180 ° C. for 20 minutes and then cleared. A coating film was formed.
<Combination of metallic coating material obtained by pulverizing vapor-deposited metal film (composition G)>
Campe baking thinner No4 (organic solvent: manufactured by Kansai Paint Co., Ltd.) 99.00 wt%
Ciba METASHEEN 41-0010 (metallic pigment: manufactured by Ciba Specialty Chemicals, PLC) 1.00 wt%
The above components were dispersed in a ball mill for 60 minutes to obtain a metallic paint.

（比較例１）
真鍮製の、外径１０ｍｍ、長さ１００ｍｍである横断面外形状が円形の材料の、塗料を塗布する面（塗布面）に、バフ研磨を施して表面を平滑にし、ジクロロメタンで脱脂処理し被塗物とした。次いで鎖状高分子材料としてアクリル樹脂を含む塗料、所謂、アクリルラッカー塗料（トアインクラック（クリヤー）、（株）トウペ製）をスプレー塗装した後、５０℃、３０分の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥しメタリック塗装物を得た。 (Comparative Example 1)
A surface made of brass with an outer diameter of 10 mm and a length of 100 mm and having a circular cross-sectional outer shape is smoothened by buffing the coating surface (coating surface), degreased with dichloromethane, and coated. Painted. Next, a paint containing an acrylic resin as a chain polymer material, a so-called acrylic lacquer paint (Toray ink rack (Clear), manufactured by Tope Co., Ltd.) was spray-coated, and then dried at 50 ° C. for 30 minutes. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) is spray-coated with a special thinner) and then dried at 25 ° C for 10 minutes to obtain a metallic paint. It was.

（比較例２）
真鍮製の、外径１０ｍｍ、長さ１００ｍｍである横断面外形状が円形の材料の、塗料を塗布する面（塗布面）に、バフ研磨を施して表面を平滑にし、ジクロロメタンで脱脂処理した後、公知の方法により黒クロムめっき層を形成し被塗物とした。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂、ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥しメタリック塗装物を得た。 (Comparative Example 2)
After buffing the surface to which the paint is applied (applied surface) of a brass material having an outer diameter of 10 mm and a length of 100 mm and having a circular outer cross section, the surface is smoothed and degreased with dichloromethane. Then, a black chrome plating layer was formed by a known method to obtain an article to be coated. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) is spray-coated. And then dried at 80 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) is spray-coated with a special thinner) and then dried at 25 ° C for 10 minutes to obtain a metallic paint. It was.

（比較例３）
実施例３と同様の被塗物を用いた。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂、ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥した。次にメタリック塗料（ｎａｘアドミラ（００９コスモシルバーベース）、日本ペイント（株）製）を専用シンナーで５倍希釈）をスプレー塗装した後、２５℃、１０分の条件で乾燥した。次に鎖状高分子材料として変性オレフィン樹脂を主成分とする熱可塑性接着剤、所謂、ホットメルト接着剤（ＰＰＥＴ１３０３Ｓ（半透明）、東亜合成（株）製をトルエンで１０倍希釈）をスプレー塗装した後、８０℃、２時間の条件で乾燥しメタリック塗装物を得た。 (Comparative Example 3)
The same coated object as in Example 3 was used. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) is spray-coated. And then dried at 80 ° C. for 2 hours. Next, metallic paint (nax Admira (009 Cosmo Silver Base), manufactured by Nippon Paint Co., Ltd.) was spray-coated with a special thinner) and then dried at 25 ° C. for 10 minutes. Next, a thermoplastic adhesive mainly composed of a modified olefin resin as a chain polymer material, so-called hot melt adhesive (PPET1303S (translucent), manufactured by Toa Gosei Co., Ltd. diluted 10 times with toluene) is spray-coated. Then, it was dried at 80 ° C. for 2 hours to obtain a metallic paint.

＜外観特性と金属光沢感の評価＞
ＪＩＳＫ５６００−４−３：１９９９「塗料一般試験方法−第４部：塗膜の視覚特性−第３節：色の目視比較」に準じた色観察用照明（自然昼光照明）下で目視にてメタリック塗膜の外観特性と金属光沢感を評価した。なお各評価は下記６段階とした。
◇外観特性
６：平滑でかなり光沢感がある
５：光沢感がある
４：やや光沢感がある
３：普通の感覚
２：ぼけた感じがする
１：全く光沢感がない
◇金属光沢感
６：かなり金属光沢がある
５：金属光沢がある
４：やや金属光沢がある
３：普通の感覚
２：ぼけた感じがする
１：全く金属光沢がない <Evaluation of appearance characteristics and metallic luster>
Visually observed under illumination for color observation (natural daylight illumination) in accordance with JIS K 5600-4-3: 1999 “General test method for paints—Part 4: Visual characteristics of coating film—Section 3: Visual comparison of colors” The appearance characteristics and metallic luster of the metallic coating film were evaluated. Each evaluation has the following six grades.
◇ Appearance characteristics 6: Smooth and fairly glossy 5: Glossy 4: Slightly glossy 3: Normal feeling 2: Blurred feeling 1: No glossiness ◇ Metallic glossiness 6: 5: Metallic luster 4: Slightly metallic luster 3: Normal feeling 2: Blurred feeling 1: No metallic luster

＜塗膜密着性評価（碁盤目試験）＞
実施例及び比較例で得た装飾体をＪＩＳＫ５６００−５−６「塗料一般試験方法−第５部：塗膜の機械的性質−第６節：付着性（クロスカット法）」に規定されているクロスカット法（１ｍｍの正方形を１０×１０コマ（計１００コマ））にて密着性を評価する。尚、評価は、１００コマの碁盤目内で塗膜が残ったコマ数とした。 <Evaluation of coating film adhesion (cross cut test)>
The decorative bodies obtained in Examples and Comparative Examples are defined in JIS K 5600-5-6 “General Test Methods for Paints—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesiveness (Cross Cut Method)” The cross-cut method (1 mm square 10 × 10 frames (100 frames in total)) is used to evaluate adhesion. In addition, evaluation was made into the number of the frames with which the coating film remained within 100 grids.

＜水に対する塗膜耐性評価（沸騰水試験）＞
２級の純度の水（ＩＳＯ３６９６）を沸騰状態にし、実施例及び比較例で得た光輝性塗装物を前記沸騰状態の水に２５分間浸漬した後、塗装物を沸騰状態の水の中から取りだし常温に戻す。次にＪＩＳＫ５６００−５−６「塗料一般試験方法−第５部：塗膜の機械的性質−第６節：付着性（クロスカット法）」に規定されているクロスカット法（１ｍｍの正方形を１０×１０コマ（計１００コマ））にて密着性を評価する。尚評価は、１００コマの碁盤目内で塗膜が残ったコマ数とした。 <Evaluation of paint film resistance to water (boiling water test)>
Second grade water (ISO 3696) is brought to a boiling state, and the glittering paints obtained in Examples and Comparative Examples are immersed in the boiling water for 25 minutes, and then the paint is taken out of the boiling water. Return to room temperature. Next, the cross-cut method (1 mm square) defined in JIS K 5600-5-6 “General test method for paints—Part 5: Mechanical properties of coating film—Section 6: Adhesiveness (cross-cut method)” Is evaluated at 10 × 10 frames (100 frames in total). In addition, evaluation was made into the number of the frames with which the coating film remained within the 100-frame grid.

前記４項目による評価結果を表１に示す。 Table 1 shows the evaluation results based on the four items.

メタリック塗装物の形成過程の塗膜断面図Cross section of the coating film in the process of forming a metallic paint メタリック塗装物の形成過程の塗膜断面図Cross section of the coating film in the process of forming a metallic paint メタリック塗装物の形成過程の塗膜断面図Cross section of the coating film in the process of forming a metallic paint メタリック塗装物の塗膜断面図Cross section of metallic paint film

１被塗物
２鎖状高分子材料を含む塗料を塗布してなる塗膜層
３メタリック塗膜層
４メタリック粉体
５鎖状高分子材料を含む塗料を塗布してなる塗膜層
６鎖状高分子材料を含む塗料を塗布してなる塗膜層とメタリック塗膜層と鎖状高分子材料を含む塗料を塗布してなる塗膜層とが一体となった複合塗膜層 DESCRIPTION OF SYMBOLS 1 Coating object 2 Coating layer formed by applying a coating containing a chain polymer material 3 Metallic coating layer 4 Metallic powder 5 Coating layer forming a coating containing a chain polymer material 6 Chain A composite coating layer in which a coating layer formed by applying a coating material containing a polymer material, a metallic coating layer, and a coating layer formed by applying a coating material containing a chain polymer material are integrated.

Claims

In a metallic coating comprising a multilayer coating film, at least the metallic coating film and a coating film formed of an organic solvent-based paint mainly composed of the same chain polymer material on the lower layer and the upper layer of the metallic coating film are integrated. Metallic paint characterized by being a composite coating layer.

2. The metallic paint according to claim 1, wherein the chain polymer material is a thermoplastic adhesive mainly composed of a polyester resin.

The metallic paint according to claim 1, wherein a curing agent mainly comprising a polyisocyanate resin is added to the paint containing the chain polymer material.

The paint for forming the metallic coating film contains at least a metal piece formed by pulverizing a deposited metal film, a binder resin, and a solvent, and the content of the metal piece in the dry coating film is 15 wt% or more. The metallic paint according to claim 1, wherein

The method for forming a metallic paint according to claim 1, wherein at least the following steps (1) to (6) are performed.
(1) The process of forming the coating film formed by apply | coating the organic solvent type coating material which has a chain polymer material as a main component on a to-be-coated article.
(2) A step of drying the coating film.
(3) The process of forming a metallic coating film in the upper layer part of the said coating film.
(4) A step of drying the metallic coating film at a temperature below the softening point of the chain polymer material.
(5) The process of forming the coating film formed by apply | coating the organic solvent type coating material which has the same chain polymer material as the main component used in (1) to the upper layer part of a metallic coating film as a main component .
(6) A step of reacting and curing after integrating a coating film formed by applying a coating material containing a chain polymer material and a metallic coating film at a temperature equal to or higher than the softening point of the chain polymer material.