JP2018130832A - Molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding that prevents an iridescent color to be expressed on its surface due to thin-film interference, and does not look as if a foreign matter entered it.SOLUTION: A molding has a base material, and an undercoat layer, a silver mirror layer, and a top coat layer sequentially laminated on the base material. The top coat layer contains an inorganic or organic filler, and the filler has an average particle size of greater than 20 μm.SELECTED DRAWING: None

Description

  The present invention relates to a molded article.

The molded product is often formed of a resin, and surface coating is performed to protect the surface.
Specifically, in automobile molded products, the texture of the exterior surface is also important, so an undercoat layer that is flattened on the base material, a silver mirror layer that improves the texture, a top coat layer that protects the surface, and three layers A surface coat consisting of

The silver mirror layer has a metallic luster and can give a deep texture to the molded product. However, the silver mirror layer is covered with a top coat because it is altered in air and easily damaged.
Further, the top coat is not necessarily a single layer but may be a plurality of layers.

JP 2012-143955 A

However, a molded article as described above may show a rainbow color due to thin film interference due to a multilayer structure.
Thin film interference is a rainbow color caused by the reflected light from each layer interfering with each other. It is well known when there is an oil film in a puddle, the surface of a soap bubble, etc. May appear to be undesirable.
Moreover, in the molded article for automobiles, attention must be paid to the surface appearance, and it should not appear to contain foreign matters.

  An object of the present invention is to provide a molded article in which the appearance of rainbow colors due to thin film interference is suppressed on the surface, and further, it does not appear that foreign matter has entered.

The present invention relates to the following.
(1) A base material and an undercoat layer, a silver mirror layer, and a top coat layer that are sequentially laminated on the base material from below are provided, and the top coat layer includes an inorganic or organic filler, Molded product with an average particle size larger than 20 μm.
(2) The molded article according to item (1), wherein the topcoat layer is formed of a plurality of layers, and at least one of the plurality of layers includes a filler.
(3) The molded product in which the surface roughness Rz of the molded product formed of the layer containing the filler is 30 or less in the item (1) or (2).

ADVANTAGE OF THE INVENTION According to this invention, the expression of the rainbow color by thin film interference can be suppressed, maintaining a deep texture. And since the average particle diameter of a filler is larger than 20 micrometers, a silver mirror layer can be glimpsed from the clearance gap between fillers, and the metallic feeling peculiar to a silver mirror layer is not impaired.
When the topcoat layer is composed of a plurality of layers, the depth can be increased, and since the filler is included in a part of the layer, this is not noticeable by assimilating the filler even if some foreign matter is mixed in. Appearance defects are less likely to occur.
If the surface roughness Rz of the coating surface including the filler is 30 or less, fibers such as clothing and bags are not easily caught when the molded product is touched. Sometimes you don't have to worry about broken clothing.

<Base material>
The base material described in the present specification is for laminating an undercoat layer to be described later, and the material is not particularly limited, but a metal molded product or a synthetic resin molded product can be used. As the resin, a thermosetting resin or a thermoplastic resin can be used.
As the thermoplastic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, vinyl polymer, polyester, polyamide, ABS resin, polyester resin, thermoplastic elastomer, and the like can be used.
As the thermosetting resin, silicon resin, polyurethane resin, polyester resin, melanin resin, epoxy resin, phenol resin, urea resin, or the like can be used.
Specifically, there are polypropylene, polycarbonate, and ABS resin as long as they are used for automobile molded products. Polypropylene has a light specific gravity among the resins, is easy to process, has high tensile strength, impact strength, and compressive strength, and is excellent in weather resistance and heat resistance. ABS is a resin that is relatively easy to apply after surface treatment among plastic materials and is easy to apply after molding such as painting. It has excellent chemical resistance and rigidity, and is also resistant to shock, heat and cold. strong. Polycarbonate has high impact resistance among plastic materials, is excellent in weather resistance and heat resistance, is excellent in transparency, is easy to process, and is relatively light and durable among plastic materials.

<Undercoat layer>
The undercoat layer described in this specification is arranged on the above-described base material, and forms a smooth surface before placing a silver mirror layer to be described later, and the substrate and the silver mirror layer. It is preferable to use a material having excellent adhesion.
Specific examples include fluorine resin paints, polyester resin paints, epoxy resin paints, melanin resin paints, silicon resin paints, acrylic silicon resin paints, and acrylic urethane resin paints. Particularly preferred are acrylic silicon resin paints and acrylic resin paints. It is a urethane resin paint.
Acrylic silicone resin paint has high adhesion to the base, high gloss retention and color retention, and excellent chemical resistance, oil resistance and water resistance.
The acrylic urethane resin paint has a soft coating film, excellent adhesion, and excellent durability, weather resistance, and chemical resistance.
The thickness of the undercoat layer is not particularly limited, but is preferably about 5 to 25 μm because a smooth surface is easily secured.
In addition, a primer layer may be interposed in order to improve the adhesion between the undercoat layer and the substrate depending on the material of the substrate.

<Silver mirror layer>
The silver mirror layer described in the present specification means a silver thin film layer, a vapor deposition method in which metallic silver is sublimated and deposited, a sputtering method using a vacuum vessel, a transfer method in which a silver thin film is previously formed and transferred on a film, It can be formed by a plating method or the like.
The thickness of the silver mirror layer is not particularly limited, but is preferably about 50 to 200 nm. When the thickness is 50 nm or more, the transparency is low and the role of a silver mirror is easily achieved. When the thickness is 200 nm or less, the silver color is not easily changed.

<Topcoat layer>
The top coat layer described in the present specification protects the silver mirror layer described above, and uses a clear or transparent colored paint that does not hide the silver mirror layer or a colored color clear resin coating. Specifically, a thermosetting resin can be used.
Specific thermosetting resins include fluorine resin paint, polyester resin paint, epoxy resin paint, melanin resin paint, silicon resin paint, acrylic silicon resin paint, acrylic urethane resin paint, and the like. It is particularly preferable to use an acrylic urethane paint.
Acrylic silicone resin paint has high adhesion to the base, high gloss retention and color retention, and excellent chemical resistance, oil resistance and water resistance.
The acrylic urethane resin paint has a soft coating film, excellent adhesion, and excellent durability, weather resistance, and chemical resistance.
The top coat layer is not necessarily a single layer, and may be a plurality of layers.
When the top coat layer is a plurality of layers, the depth of the top coat is increased and a glossy texture is easily produced.
Although the thickness of a topcoat layer is not specifically limited, About 20-40 micrometers is preferable.
When the thickness is 20 μm or more, the above-described silver mirror layer can be sufficiently protected, and when it is 40 μm or less, cracks, peeling, poor adhesion, and the like due to secular change are difficult to occur.

<Filler>
The filler described in the present invention is made of an inorganic or organic material, and the shape can be appropriately selected from a substantially spherical shape, a scale shape, a true sphere, and the like.
Examples of inorganic substances include calcium carbonate, silicon dioxide (silica), silicate minerals (talc and mica), aluminum silicate (clay), aluminum oxide (alumina), ceramic (titanium oxide), and the like as main components. It may be a powder.
As the organic material, a powder obtained by finely pulverizing and granulating polyimide, poro tp lafilylethylene (PTFE), nylon, acrylic ester, styrene, or the like can be used.
The filler may be colorless or colored, but is preferably colorless and transparent or cloudy. In order to make use of the silver mirror film in the lower layer of the layer with the filler as a design, it is desirable that the filler is not a colored object (except for colored and transparent) that makes the filler feel crisp.
In addition, when using a colored thing, it is preferable to use the color clear of the same color system as a filler in the layer containing a filler or the layer which overlaps on it. If it is the same color system, the filler which is black may be sufficient.
The filler has an average particle size larger than 20 μm, thereby suppressing the appearance of rainbow colors. The average particle diameter means a 50% particle diameter (median diameter) of the intensity distribution of the diffracted / scattered light when the particle is irradiated with laser light using a laser diffraction particle size distribution measuring apparatus.
A filler is disperse | distributed in a topcoat layer, and when a topcoat layer is comprised by multiple layers, it is disperse | distributed to at least 1 layer in it.
It can be arbitrarily determined whether the filler is dispersed in a plurality of topcoat layers. However, when the filler is dispersed in the outermost layer of the topcoat layer, the reflectance is suppressed and the atmosphere becomes calm. The feel of the filler can be obtained. When the filler is dispersed in a layer other than the outermost layer, the gloss can be increased and a metallic feeling can be obtained.

<Surface roughness Rz>
The surface roughness Rz described in this specification is defined by “JIS-B0601-2013”, and is the sum of the highest height and the deepest valley depth.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.
<Example 1>
(Formation of undercoat layer)
Prepare a flat ABS substrate of length: 70 mm x width: 150 mm x thickness: 3 mm, and degrease and clean the surface of this substrate with a waste cloth containing IPA (isopropyl alcohol) to remove oil film, dirt and dust. did. The removed substrate was dried, and MSPS undercoat clear D manufactured by Ohashi Chemical Industry Co., Ltd. and MSPS undercoat thinner No. 15, MSPS undercoat additive L and MSPS undercoat curing agent N were blended in a ratio of 25: 35: 0.5: 4 (ratio by weight), stirred, and sprayed with a spray gun. Then, it was dried in a drying furnace set at 80 ° C. for 1 hour to form an undercoat layer having an average film thickness of 15 μm.

(Formation of silver mirror layer)
After spray-cleaning the substrate on which the undercoat layer is formed with pure water, MSPS-Sa1A (trade name) manufactured by Mitsubishi Paper Industries Co., Ltd. is spray-coated, and after sufficient spray cleaning with pure water, Mitsubishi Paper Industries Co., Ltd. After applying MSPS-Sa2A (trade name) made by the company and activating silver mirror deposition, MSPS-Ag (trade name) and MSPS-Do made by Mitsubishi Paper Industries Co., Ltd. (product) No. 2) were simultaneously applied to form a silver mirror layer by silver mirror reaction, and then spray-washed with pure water, MSPS-R1A manufactured by Mitsubishi Paper Industries Co., Ltd. was applied, and further spray-washed with pure water. Next, in order to remove the water | moisture content of a silver mirror layer, after blowing compressed air (air blow), it was dried for 30 minutes in the drying furnace set to 45 degreeC.

(Formation of top coat)
After confirming that the temperature of the molded product after drying of the silver mirror layer became room temperature (25 ° C.), the top coat was changed to Examples 1 to 12 and Comparative Examples 1 to 10 as shown in Table 1 described later. Then, each was formed by changing.

Example 1
A top coat clear M for MSPS, a top coat thinner P-7 for MSPS, a top coat curing agent W for MSPS, and a color black for MSPS manufactured by Ohashi Chemical Co., Ltd., 20: 20: 5: 0. 4 (ratio in parts by mass: TC-A) and filler a (Sekisui Plastics Kogyo Co., Ltd .: MBX-25H, average particle size 25 μm, approximately spherical shape) are mixed in 0.2 parts by mass, stirred, and sprayed. It sprayed with the gun | gun and it dried for 45 minutes within the drying furnace set to 80 degreeC, and formed the topcoat layer with an average film thickness of 25 micrometers.

(Example 2)
It was formed in the same manner as in Example 1 except that the filler was changed to filler b (manufactured by Sekisui Plastics Kogyo Co., Ltd .: MBX-30, average particle diameter 30 μm, substantially spherical shape).

(Example 3)
It was formed in the same manner as in Example 1 except that the filler was changed to the filler c (manufactured by Sekisui Plastics Co., Ltd .: MBX-50, average particle diameter: 50 μm, substantially spherical shape).

Example 4
It was formed in the same manner as in Example 1 except that the filler was changed to filler d (manufactured by Maruo Calcium Co., Ltd .: R-70H, average particle size 25 μm, irregular shape).

(Example 5)
Immediately after spraying TC-A of Example 1, MSPS topcoat clear M, MSPS topcoat thinner P-7 and MSPS topcoat curing agent W manufactured by Ohashi Chemical Industries, Ltd. 20: 20: 5 ( Ratio in parts by mass Formulation: TC-B) and 0.2 part by mass of filler a were mixed and sprayed with another spray gun, and dried in a drying furnace set at 80 ° C. for 45 minutes. A top coat layer having a total average film thickness of 35 μm was formed.

(Example 6)
It formed like Example 5 except having used the filler b as the filler b.

(Example 7)
It formed like Example 5 except having used the filler c as the filler.

(Example 8)
It was formed in the same manner as in Example 5 except that the filler was changed to the filler d.

Example 9
0.2 parts by mass of TC-B and filler a of Example 5 were mixed and stirred. Immediately after spraying, TC-A of Example 1 was sprayed with another spray gun and placed in a drying furnace set at 80 ° C. And dried for 45 minutes to form a topcoat layer having a total average film thickness of 35 μm.

(Example 10)
It formed like Example 9 except having used the filler b as the filler b.

(Example 11)
It formed like Example 9 except having used the filler c as the filler.

(Example 12)
It formed like Example 9 except having used the filler d as the filler d.

(Comparative Example 1)
It was formed in the same manner as in Example 1 except that the blending of the filler a in Example 1 was omitted.

(Comparative Example 2)
It was formed in the same manner as in Example 1 except that the filler was changed to filler e (manufactured by Sekisui Plastics Co., Ltd .: MBX-2H, average particle diameter: 2.5 μm, approximately spherical shape).

(Comparative Example 3)
It was formed in the same manner as in Example 1 except that the filler was changed to the filler f (manufactured by Sekisui Plastics Co., Ltd .: MBX-5, average particle diameter: 5 μm, substantially spherical shape).

(Comparative Example 4)
It was formed in the same manner as in Example 1 except that the filler was changed to the filler g (manufactured by Sekisui Plastics Co., Ltd .: MBX-12, average particle diameter 12 μm, substantially spherical shape).

(Comparative Example 5)
It formed like Example 5 except having changed the filler into the filler e.

(Comparative Example 6)
It formed like Example 5 except having changed the filler into the filler f.

(Comparative Example 7)
It formed like Example 5 except having changed the filler into the filler g.

(Comparative Example 8)
It formed like Example 9 except having changed the filler into the filler e.

(Comparative Example 9)
It formed similarly to Example 9 except having changed the filler into the filler f.

(Comparative Example 10)
It formed like Example 9 except having changed the filler into the filler g.

(Appearance thin film interference fringe evaluation)
The molded products of Examples and Comparative Examples were visually observed by 50 test subjects to confirm whether thin film interference fringes (rainbow colors) were generated.
Evaluation is based on the number of people who have determined that no rainbow has occurred. If it is judged that 40 or more people are not present, “◎”, if it is judged that 30 to 39 people are absent, “○”, and 20 to 29 or less people are judged to be none. In this case, “△” was given, and if it was judged that 19 or less were none, “x” was given.

(Appearance of foreign matter)
About the molded article of an Example and a comparative example, visual observation was performed by 50 test subjects, and the presence or absence of the appearance foreign material was confirmed.
The evaluation is based on the number of people who are judged to be free of foreign matter. If it is judged that there are no more than 40 people, “◎”, if it is judged that 30 to 39 people are none, “○”, and 20 to 29 people or less are judged as none. “△”, and “x” if 19 or less were judged to be absent.

(Appearance brightness evaluation)
The molded products of Examples and Comparative Examples were visually observed by 50 test subjects to confirm the presence or absence of appearance luminance.
The evaluation is based on the number of people judged to have a sense of brightness. If it is judged that there are 40 or more people, “◎”, if it is judged that there are 30 to 39 people, “○”, and 20 to 29 people or less are judged. “△”, and “x” if it was judged that there were 19 or less.

(Appearance metal texture evaluation)
About the molded article of an Example and a comparative example, visual observation was performed by 50 test subjects, and the presence or absence of the external appearance metal texture was confirmed.
The evaluation is based on the number of people who judged that there is a metal texture. If it is judged that there are 40 or more people, “◎”, if it is judged that there are 30 to 39 people, “○”, and 20 to 29 people or less are judged. “△”, and “x” if it was judged that there were 19 or less.

(Hand / Hook evaluation)
About the molded product of an Example and a comparative example, 50 test subjects performed palpation and confirmed the presence or absence of touch and a catch.
The evaluation was performed by the number of persons who asked the subjects to wear cotton gloves, and stroked the surface of the molded product with the worn cotton gloves and judged that there was no catch. When it was judged that there was no name, “◯” was given, and when it was judged that 20 to 29 or less were none, “Δ”, and when 19 or less were judged to be none, “X” was given.

(Surface roughness)
About the molded article of an Example and a comparative example, a roughness meter measurement test is done and Rz (JIS-B-0601-2013) is calculated.
The roughness meter measurement is a stylus type, and the tip of the stylus is placed on the surface to be measured, the stylus is moved along the surface to be measured, and the amount of vertical movement due to surface irregularities is electrically expanded. Is a method of measuring.

  The evaluation results are shown in Table 1 below.

From the results of Table 1, Comparative Examples 1 to 10 have a feeling of brightness and a metallic texture, and there is no catch, but it was confirmed that the appearance of the interference fringe rainbow and foreign matters was mixed.
On the other hand, in Examples 1 to 12, it was confirmed that the brightness and the metal texture were not impaired, there was no catch, and there was no appearance defect due to interference fringes of rainbows and foreign matters.
Further, regarding the surface roughness, Rz 38.4 in Example 4 and a crack evaluation by palpation “Δ”, whereas in Example 8, Rz 24.3 and a crack evaluation by palpation “O”, and in Example 12, Rz 8.42, the result of the evaluation of palpation by palpation was “◎”. In contrast to Example 4 consisting of a single layer, in Example 8 and Example 12 consisting of two layers, while maintaining the feeling of brightness and metal texture, It was confirmed that the feeling of malfunction due to catching could be suppressed.

Claims (3)

  A base material, and an undercoat layer, a silver mirror layer, and a topcoat layer that are sequentially laminated on the base material, the topcoat layer including an inorganic or organic filler, and an average particle diameter of the filler A molded product having a diameter of more than 20 μm.   The molded article according to claim 1, wherein the topcoat layer is formed of a plurality of layers, and at least one of the plurality of layers includes a filler.   The molded product according to claim 1 or 2, wherein the molded product formed of a layer containing a filler has a surface roughness Rz of 30 or less.