JP2018024903A - Antifouling plated article and manufacturing method therefor - Google Patents
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Description
本発明は、防汚被膜を有するめっき品に関するものである。 The present invention relates to a plated product having an antifouling coating.
めっき品は、加飾バリエーションが拡充され、様々な外観のものが生産されるようになった。車両用加飾部品や電気製品用筐体樹品などの分野における近年のめっき品のデザイントレンドとしては、黒味を強調しためっき(漆黒調めっき)や、光沢を抑えていぶした感じのめっき(サテン調めっき)が挙げられる。 As for plated products, decorative variations have been expanded, and products with various appearances have been produced. Recent design trends of plated products in fields such as decorative parts for vehicles and housings for electrical appliances include plating with emphasis on blackness (lacquer black plating) and plating with a feeling of reduced luster ( Satin tone plating).
しかしながら、これらのめっき外観は、手油等の汚れが色目の兼ね合いにより目立ちやすく且つ取れにくいという問題があった。従来、このような手油等の汚れの問題を解消できる防汚技術は見当たらなかった。 However, these plating appearances have a problem that stains such as hand oil are easily noticeable and difficult to remove due to color balance. Conventionally, there has been no antifouling technique capable of solving such a problem of dirt such as hand oil.
なお、特許文献1には、セラミックスを充填したタンクに通水して生成したホウ酸シリカ水を、高圧で直接自動車等の被洗浄物に当てることで、被洗浄物を洗浄するとともに、被洗浄物の表面に被膜を形成する方法が開示されている。
しかしながら、特許文献1には、実施例での通水時間については記載されていない。また、実施例において実際に被膜の存在を確認したことは記載されていない。
In Patent Document 1, the boric acid silica water generated by passing water through a tank filled with ceramics is directly applied to an object to be cleaned such as an automobile at a high pressure, thereby cleaning the object to be cleaned. A method of forming a film on the surface of an object is disclosed.
However, Patent Document 1 does not describe the water passage time in the examples. Moreover, it is not described that the presence of the coating was actually confirmed in the examples.
また、特許文献2には、セラミックスを充填したタンクに通水して生成したホウ酸シリカ水をめっき液として用い、金属材料からなる基材を電極として用いて、めっき処理によりホウ酸シリカを含む粒子を基材表面に物理的に吸着した後、化学的吸着が生じてシリカを基材表面に固着させる方法が開示されている。
しかしながら、特許文献2には、実施例での通水時間については記載されていない。また、実施例の表面に、光学顕微鏡で多数のランダムな模様を観察したこと、エネルギー分散型X線分析装置で、C(炭素)、Mg(マグネシウム)、Si(ケイ素)の成分増加を認めたことが記載されているが、B(ホウ素)の析出を確認できたことは記載されていない。
Further, Patent Document 2 includes silica borate by plating treatment using silica borate water generated by passing water through a tank filled with ceramics as a plating solution and using a base material made of a metal material as an electrode. A method is disclosed in which, after the particles are physically adsorbed on the substrate surface, chemical adsorption occurs to fix the silica to the substrate surface.
However, Patent Document 2 does not describe the water passage time in the examples. Further, on the surface of the example, many random patterns were observed with an optical microscope, and an increase in the components of C (carbon), Mg (magnesium), and Si (silicon) was observed with an energy dispersive X-ray analyzer. However, it is not described that the precipitation of B (boron) could be confirmed.
本発明の目的は、最表面に水接触角が10°以下である親水性の防汚被膜を有し、手油等の油性の汚れが付着にくく且つ落ちやすい防汚めっき品を提供することにある。 An object of the present invention is to provide an antifouling plating product that has a hydrophilic antifouling coating having a water contact angle of 10 ° or less on the outermost surface, and that oily dirt such as hand oil is difficult to adhere and is easy to fall off. is there.
(1)本発明の防汚めっき品は、めっき層を有するめっき品において、前記めっき層よりも上の最表面に、Mg、Si及びBを主成分として含む、実質的に透明で、水接触角が10°以下である防汚被膜を有することを特徴とする。 (1) The antifouling plating product of the present invention is a plating product having a plating layer, and contains Mg, Si and B as main components on the outermost surface above the plating layer. It has an antifouling film whose angle is 10 ° or less.
前記めっき層が、漆黒調めっき層又はサテン調めっき層である場合、前述のとおり、これらのめっき層は手油等の汚れが色目の兼ね合いにより目立ちやすく且つ取れにくいから、これを防ぐ本発明は特に効果的である。 When the plating layer is a jet black tone plating layer or a satin tone plating layer, as described above, since these plating layers are easily noticeable and difficult to remove due to the balance of color, the present invention prevents this. It is particularly effective.
(2)本発明の防汚めっき品の製造方法は、めっき層を有するめっき品を、Mg、Si及びBを含む電解液にて電気めっき処理することにより、前記めっき層よりも上の最表面に、Mg、Si及びBが主成分として析出してなる、実質的に透明で、水接触角が10°以下である防汚被膜を形成することを特徴とする。 (2) The method for producing an antifouling plating product of the present invention is such that a plating product having a plating layer is electroplated with an electrolytic solution containing Mg, Si and B, whereby the outermost surface above the plating layer. Further, it is characterized by forming a substantially transparent antifouling film having Mg, Si and B deposited as main components and having a water contact angle of 10 ° or less.
前記めっき層を、漆黒調めっき層又はサテン調めっき層として形成することが好ましい。 The plating layer is preferably formed as a jet black tone plating layer or a satin tone plating layer.
<作用>
Mg、Si及びBを主成分として含む、実質的に透明で、水接触角が10°以下である防汚被膜は、水との親和性が高く、空気中の水分を吸着して、表面に水の極薄い膜を形成する。このため、手油等の汚れは、その水の膜に付着しにくく、また付着したとしてもその水の膜の上に浮くことになり、拭き取りや水洗いで落ちやすい。
<Action>
The antifouling coating which contains Mg, Si and B as main components and is substantially transparent and has a water contact angle of 10 ° or less has a high affinity with water and adsorbs moisture in the air to the surface. Forms a very thin film of water. For this reason, dirt such as hand oil does not easily adhere to the water film, and even if it adheres, it will float on the water film and is easily removed by wiping or washing with water.
本発明の防汚めっき品及びその製造方法によれば、Mg、Si及びBを主成分として含む、実質的に透明で、最表面に水接触角が10°以下である親水性の防汚被膜を有することにより、手油等の油性の汚れが付着にくく且つ落ちやすいという優れた効果を奏する。 According to the antifouling plating product of the present invention and the method for producing the same, the hydrophilic antifouling coating which contains Mg, Si and B as main components and is substantially transparent and has a water contact angle of 10 ° or less on the outermost surface. By having this, oily dirt such as hand oil is difficult to adhere and has an excellent effect of being easily removed.
1.めっき品の基材
めっき品の基材の素材としては、特に限定されないが、樹脂、金属、ガラス等を例示できる。樹脂基材の樹脂は、熱可塑性でも熱硬化性でもよく、特に限定されないが、アクリロニトリル・ブタジエン・スチレン共重合体(ABS)樹脂、ポリカーボネート(PC)樹脂、PC/ABS樹脂、アクリル樹脂、スチレン樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリプロピレン樹脂、塩化ビニル樹脂、ポリウレタン樹脂等を例示できる。ABS樹脂、PC/ABS樹脂が強度、耐久性等の観点から好ましい。
樹脂基材の上には、めっき層を電気めっきするときに必要な導電層が形成される。導電層としては、特に限定されないが、無電解ニッケルめっき層を例示できる。
1. The base material of the plated product The material of the base material of the plated product is not particularly limited, and examples thereof include resin, metal, and glass. The resin of the resin base material may be thermoplastic or thermosetting, and is not particularly limited, but acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, PC / ABS resin, acrylic resin, styrene resin Polyamide resin, polycarbonate resin, polypropylene resin, vinyl chloride resin, polyurethane resin and the like can be exemplified. ABS resin and PC / ABS resin are preferable from the viewpoints of strength, durability and the like.
A conductive layer necessary for electroplating the plating layer is formed on the resin substrate. Although it does not specifically limit as a conductive layer, An electroless nickel plating layer can be illustrated.
2.めっき層
めっき層としては、特に限定されないが、Cu(銅)めっき層、Ni(ニッケル)めっき層、Cr(クロム)めっき層、これらの組み合わせ等を例示できる。めっき層の具体的構成は、特に限定されず、単層でも複数層でもよい。
めっき層が漆黒調めっき層又はサテン調めっき層である場合、上述したとおり、本発明は特に効果的である。
2. Plating layer Although it does not specifically limit as a plating layer, Cu (copper) plating layer, Ni (nickel) plating layer, Cr (chromium) plating layer, these combinations, etc. can be illustrated. The specific configuration of the plating layer is not particularly limited, and may be a single layer or a plurality of layers.
When the plating layer is a jet black tone plating layer or a satin tone plating layer, the present invention is particularly effective as described above.
5.防汚めっき品の用途
防汚めっき品の用途としては、特に限定されないが、車両用加飾部品(ラジエータグリル、フェンダ、ガーニッシュ、ホイールキャップ、バックパネル、エアスポイラー、エンブレム等)、電気製品(携帯電話、スマートホン、携帯情報端末、ゲーム機等)用筐体部品等を例示できる。
5. Applications of antifouling plating products The applications of antifouling plating products are not particularly limited, but include decorative parts for vehicles (radiator grills, fenders, garnishes, wheel caps, back panels, air spoilers, emblems, etc.) For example, case parts for telephones, smart phones, portable information terminals, game machines, etc.).
まず、Cuめっき層を有するめっき品の代用としてCuハルセル板(山本鍍金試験機製)を用い、表1に示すように、試験例1ではCuハルセル板をそのままテストピースとし、試験例2〜6ではCuハルセル板を後述する電解液にて電気めっき処理してテストピースとし、防汚特性を調べた。 First, as a substitute for a plated product having a Cu plating layer, a Cu hull cell plate (manufactured by Yamamoto plating tester) was used, and as shown in Table 1, in test example 1, the Cu hull cell plate was directly used as a test piece, The Cu hull cell plate was electroplated with an electrolyte described later to obtain a test piece, and the antifouling properties were examined.
電解液は、セラミックス(株式会社エヌエム社製の商品名「NMセラミックス」)を充填したタンク(株式会社エヌエム社製の商品名「ウォーターコートWS−04」)に、試験例2では1時間、試験例3では5時間、試験例4では12時間、試験例5では36時間、試験例6では504時間、通水して得た液を用いた。通水時間以外の通水条件は、水量が5L、流量が2L/分、水温が室温である。
試験例2〜6の各電解液の組成を、誘導結合プラズマ発光分光分析装置(ICP−AES)により、分析した結果を表1に示す。
The electrolyte was tested in a tank (trade name “Water Coat WS-04” manufactured by NM Corporation) filled with ceramics (trade name “NM Ceramics” manufactured by NM Corporation) for 1 hour in Test Example 2. The liquid obtained by passing water for 5 hours in Example 3, 12 hours in Test Example 4, 36 hours in Test Example 5, and 504 hours in Test Example 6 was used. The water flow conditions other than the water flow time are a water volume of 5 L, a flow rate of 2 L / min, and a water temperature of room temperature.
Table 1 shows the results obtained by analyzing the compositions of the electrolyte solutions of Test Examples 2 to 6 using an inductively coupled plasma emission spectrometer (ICP-AES).
こうして得た試験例2〜6の各電解液に、Cuハルセル板を陰極として浸漬し、液温40℃、エアー攪拌あり、電流密度0.1A/dm2、めっき時間300秒のめっき条件により、電気めっき処理した。
試験例2〜6の各Cuハルセル板の被膜の有無及び組成を、X線光電子分光装置(XPS)により、分析した結果を表1に示す。試験例2〜4では、被膜が検出されなかった(ND)。試験例5,6では、Mg、Si及びBを含む実質的に透明な被膜が検出され、上記電気めっき処理で電気析出により被膜(防汚被膜)が生成したものと考えられる。
In each of the electrolytic solutions of Test Examples 2 to 6 thus obtained, a Cu Hull cell plate was immersed as a cathode, the liquid temperature was 40 ° C., air stirring was performed, and the plating conditions were a current density of 0.1 A / dm 2 and a plating time of 300 seconds. Electroplated.
Table 1 shows the results of analyzing the presence / absence and composition of the Cu hull cell plates of Test Examples 2 to 6 using an X-ray photoelectron spectrometer (XPS). In Test Examples 2 to 4, no coating was detected (ND). In Test Examples 5 and 6, a substantially transparent film containing Mg, Si, and B was detected, and it is considered that a film (antifouling film) was generated by electrodeposition in the electroplating process.
こうして作製した試験例1〜6の各テストピースについて、水との接触角を、接触角計(協和界面科学社「DM−501」)により測定した。その結果を表1に示すように、電気めっき処理していない試験例1に対し、試験例2〜4の水との接触角は実質的に同等であったが、試験例5,6の水との接触角は顕著に小さくなった。 About each test piece of Test Examples 1-6 produced in this way, the contact angle with water was measured with the contact angle meter (Kyowa Interface Science Co., Ltd. "DM-501"). As shown in Table 1, the contact angles with water in Test Examples 2 to 4 were substantially equal to Test Example 1 that was not electroplated, but the water in Test Examples 5 and 6 was the same. The contact angle with was significantly reduced.
また、試験例1〜6の各テストピースについて、手油汚れの取れやすさの試験を、次の手順で行った。
1.ガーゼに人の手油の主成分であるオレイン酸を含ませて、直径2cmの円柱形のゴム栓をそのガーゼに押し当て、ゴム栓にオレイン酸を付着させた。
2.次に、評価するテストピースの上にゴム栓を置き、ゴム栓の上に500gの錘を置き、60sec静置して、テストピースにゴム栓のオレイン酸を油汚れとして付着させた。
3.次に、乾いたベンコットをテストピースの油汚れの上に置き、引っかき試験機で2kgの加重で30回スクラッチした(加重面積1cm2、スクラッチ速度48回/分、スクラッチピッチ5cm)。
4.以上の汚れ試験の前後のテストピースの色差を、色彩計(コニカミノルタ社「CM−700B」)により測定し、次の式で示される色差変化ΔEを、手油汚れの取れやすさの指標とした。
L*a*b*表色系で、試験前色調(L1 a1 b1)、試験後色調(L2 a2 b2)とし、ΔE=√(L1−L2)2+(a1−a2)2+(b1−b2)2
Moreover, about each test piece of Test Examples 1-6, the test of the ease of removing hand oil dirt was done in the following procedure.
1. The gauze was impregnated with oleic acid, which is the main component of human hand oil, and a cylindrical rubber stopper having a diameter of 2 cm was pressed against the gauze to attach oleic acid to the rubber stopper.
2. Next, a rubber stopper was placed on the test piece to be evaluated, a 500 g weight was placed on the rubber stopper, and left to stand for 60 seconds to attach the oleic acid of the rubber stopper to the test piece as oil stains.
3. Next, the dried bencott was placed on the oil stain of the test piece, and scratched 30 times with a scratch tester with a load of 2 kg (weighted area 1 cm 2 , scratch speed 48 times / min, scratch pitch 5 cm).
4). The color difference of the test piece before and after the above stain test was measured with a colorimeter (Konica Minolta “CM-700B”), and the color difference change ΔE shown by the following equation was used as an index of ease of removing hand oil stains. did.
In the L * a * b * color system, color tone before test (L1 a1 b1), color tone after test (L2 a2 b2), ΔE = √ (L1−L2) 2 + (a1−a2) 2 + (b1− b2) 2
上記色差変化の結果を表1に示すように、電気めっき処理していない試験例1に対し、試験例2〜4の色差変化は実質的に同等であったが、試験例5,6の色差変化は顕著に小さくなった。試験例5,6では手油汚れの取れ方が大きかったことを意味する。 As shown in Table 1, the color difference change in Test Examples 2 to 4 was substantially equivalent to Test Example 1 that was not electroplated as shown in Table 1. The change was significantly smaller. In Test Examples 5 and 6, this means that hand oil stains were removed greatly.
以上のとおり、試験例5,6のように、Mgを4.1ppm以上、Siを11.2ppm以上、Bを8.7ppm以上含む電解液を用いて電気めっき処理した場合に、防汚効果が得られた。 As described above, as in Test Examples 5 and 6, when the electroplating treatment is performed using the electrolytic solution containing Mg of 4.1 ppm or more, Si of 11.2 ppm or more, and B of 8.7 ppm or more, the antifouling effect is obtained. Obtained.
次に、実施例として、めっき層を有するめっき品を、上記の試験例5又は試験例6と同様の電解液にて電気めっき処理することにより、めっき層よりも上の最表面に防汚被膜を形成した。 Next, as an example, a plating product having a plating layer is electroplated with the same electrolytic solution as in Test Example 5 or Test Example 6 above, so that an antifouling coating is formed on the outermost surface above the plating layer. Formed.
具体的には、図1(a)に示す基材の上にCuめっき層を有するめっき品、(b)に示す基材の上にNiめっき層と漆黒調Crめっき層をこの順で有するめっき品、(c)に示す基材の上にサテン調Cuめっき層とCrめっき層をこの順で有するめっき品、(d)に示す基材の上にサテン調Cuめっき層と漆黒調Crめっき層をこの順で有するめっき品の、それぞれの最表面に防汚被膜を形成した。各めっき層は電気めっきにより形成したが、無電解めっきにより形成することもできる。基材は、金属板であったが、樹脂基材でもよい。
これらの実施例においても、試験例5又は試験例6と同様の、手油汚れの取れやすさが認められた。
Specifically, a plated product having a Cu plating layer on the substrate shown in FIG. 1A, and a plating having a Ni plating layer and a jet black Cr plating layer in this order on the substrate shown in FIG. Product, a plated product having a satin-like Cu plating layer and a Cr plating layer in this order on the substrate shown in (c), a satin-like Cu plating layer and a jet black tone Cr plating layer on the substrate shown in (d) An antifouling film was formed on each outermost surface of the plated product having the above in this order. Each plating layer is formed by electroplating, but can also be formed by electroless plating. The substrate is a metal plate, but may be a resin substrate.
Also in these examples, the ease of removing hand oil stains as in Test Example 5 or Test Example 6 was recognized.
なお、本発明は前記実施例に限定されるものではなく、発明の趣旨から逸脱しない範囲で適宜変更して具体化することができる。 In addition, this invention is not limited to the said Example, In the range which does not deviate from the meaning of invention, it can change suitably and can be actualized.
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