JP2018024903A - Antifouling plated article and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling plated article having a hydrophilic antifouling coating film on an outermost surface, and making oily stain such as hand oil hard to adhere to and easy to be cleaned off.SOLUTION: A plated article with a plating film has an antifouling coating film which mainly contains Mg, Si and B, is practically transparent and has water contact angle of 10° or less on an outermost surface upper than the plating layer. The antifouling coating film is high in compatibility with water, absorbs moisture in air and forms a very thin film of water on a surface. Stains such as hand oil hardly adhere to the film of water and are easily dropped off even when adheres because it floats on the film of water. Examples of the plating layer includes a jet-black tone plating layer or a satin tone plating layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a plated product having an antifouling coating.

  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).

  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.

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.

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.

JP 2004-50043 A JP 2012-126956 A

  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) 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.

  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) 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.

  The plating layer is preferably formed as a jet black tone plating layer or a satin tone plating layer.

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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.

  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.

It is a typical sectional view of a plating article of an example.

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. 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. 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.).

  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.

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).

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.

  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.

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

  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.

  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.

  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.

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.

  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.

Claims (4)

  In the plated product having a plating layer, the outermost surface above the plating layer has a substantially transparent antifouling film containing Mg, Si and B as main components and having a water contact angle of 10 ° or less. Antifouling plating product characterized by that.   The antifouling plating product according to claim 1, wherein the plating layer is a jet black tone plating layer or a satin tone plating layer.   By electroplating a plated product having a plating layer with an electrolyte containing Mg, Si and B, Mg, Si and B are deposited as main components on the outermost surface above the plating layer. A method for producing an antifouling plating product, comprising forming an antifouling coating that is substantially transparent and has a water contact angle of 10 ° or less.   The method for producing an antifouling plating product according to claim 3, wherein the plating layer is formed as a jet black tone plating layer or a satin tone plating layer.

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