WO2019175941A1

WO2019175941A1 - Molded article, and display device

Info

Publication number: WO2019175941A1
Application number: PCT/JP2018/009553
Authority: WO
Inventors: 潤美森原; 将博岩永
Original assignee: 日立化成株式会社
Priority date: 2018-03-12
Filing date: 2018-03-12
Publication date: 2019-09-19
Also published as: JP7099516B2; JPWO2019175941A1

Abstract

This molded article has a silver mirror layer, resin layers provided on both surfaces of the silver mirror layer, and a substrate provided to at least one outer surface of the resin layers. At least one of the resin layers contains a filller and is optically translucent.

Description

Molded product and display device

The present invention relates to a molded product and a display device.

The surface of the molded product may be decorated with a metallic tone from a design standpoint. Examples of the metallic decoration method include an electrolytic plating method, a vacuum deposition method, and a hot stamping method. Electrolytic plating methods are widely used for decorating vehicle parts such as bumpers. For example, a method is disclosed in which a nickel layer is coated on the surface of a component by electrolytic plating and further a chromium layer is coated. (For example, refer to Patent Document 1).

However, there is a problem that the weight of the parts becomes heavy in the decoration of the metal tone by the electrolytic plating method. In addition, the electroplating method, the vacuum deposition method, and the hot stamping method all require a specific apparatus and are complicated to operate.

Therefore, there is a method of forming a silver mirror layer using a silver mirror reaction (see, for example, Patent Document 2). In this method, an undercoat layer (undercoat layer), a silver mirror layer, and an overcoat layer (topcoat layer) are sequentially formed on a substrate. The method using the silver mirror reaction can be decorated with a simple device, and the increase in the weight of the component can be suppressed to a very low level as compared with the electrolytic plating method.

Japanese Patent Laid-Open No. 2016-216783 JP 2003-19765 A

However, a molded article having a silver mirror layer has a multilayer structure, and a resin layer such as a topcoat layer is provided on the outermost surface on the viewing side. In some cases, rainbow colors due to interference fringes appear on the surface of the product. In the case of electrolytic plating, since no resin layer is provided on the outermost surface, such interference fringes are not generated, which is a problem specific to a molded product having a silver mirror layer. The rainbow color expressed by the interference fringes may appear as uneven color, which is not preferable. In addition, a molded article for a vehicle must not appear to contain foreign matter.

In view of the above situation, an object of the present invention is to provide a molded article that has a silver mirror layer and suppresses the appearance of rainbow colors due to interference fringes on the surface.

Means for solving the above problems include the following embodiments.
<1> Silver mirror layer,
A resin layer provided on both sides of the silver mirror layer;
A substrate provided on the outer surface of at least one of the resin layers,
A molded product in which at least one of the resin layers contains a filler and has light transmittance.
<2> The molded article according to <1>, wherein the silver mirror layer has a thickness of 100 nm or less.
<3> The molded article according to <1> or <2>, wherein the resin layer containing the filler is provided on the viewing side with respect to the silver mirror layer.
<4> The molded article according to any one of <1> to <3>, wherein the base material is provided on the outer surface on the viewing side.
<5> The molded article according to any one of <1> to <4>, wherein a light-shielding image layer is further provided on a side farther from the viewing side than the silver mirror layer.
<6> The molded product according to any one of <1> to <5>,
With backlight,
A display device.

According to the present invention, it is possible to provide a molded article having a silver mirror layer and suppressing the appearance of rainbow colors due to interference fringes on the surface.

It is a schematic sectional drawing explaining an example of a structure of the molded article of this indication. It is a schematic sectional drawing explaining an example of a structure of the molded article of this indication. It is a schematic sectional drawing explaining an example of a structure of the molded article of this indication.

In the present disclosure, numerical ranges indicated using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

In the present disclosure, each component may contain a plurality of corresponding substances. When multiple types of substances corresponding to each component are present in the layer, the content or content of each component is the total content or content of the multiple types of substances present in the layer unless otherwise specified. means.
In the present disclosure, a plurality of particles corresponding to each component may be included. When a plurality of kinds of particles corresponding to each component are present in the layer, the particle diameter of each component means a value for a mixture of the plurality of kinds of particles present in the layer unless otherwise specified.

In the present disclosure, the term “layer” refers to a case where the layer is formed only in a part of the region in addition to the case where the layer is formed over the entire region. included.

In the present disclosure, when an embodiment is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Moreover, the magnitude | size of the member in each figure is notional, The relative relationship of the magnitude | size between members is not limited to this. Moreover, the same code | symbol is provided to the member which has the substantially same function through all the drawings, and the overlapping description may be abbreviate | omitted.

〔Molding〕
The molded article of the present disclosure includes a silver mirror layer, a resin layer provided on both surfaces of the silver mirror layer, and a base material provided on at least one outer surface of the resin layer, and the resin layer At least one of them contains a filler. And the molded article of this indication has optical transparency. The molded article of the present disclosure may further include other members.

According to this configuration, the appearance of rainbow colors due to interference fringes on the surface of the molded product is suppressed. Moreover, the weight increase of a molded article is suppressed compared with the electroplating method.
In addition, a so-called half mirror having light transmittance, which is difficult to manufacture by the electrolytic plating method, can be manufactured. Furthermore, although the metallic decoration part provided by the electrolytic plating method feels cold when touched in an environment where the temperature is low, coldness is suppressed in a molded article having a silver mirror layer.

Hereinafter, an example of the configuration of the molded product of the present disclosure will be described with reference to the drawings. However, the molded article of the present disclosure is not limited to these embodiments.

FIG. 1 is a schematic sectional view of a molded product 100. The molded product 100 is provided with a base material 10, an undercoat layer 20, a silver mirror layer 30, and a topcoat layer 40 in order from the viewing side (arrow in the figure). In the molded product 100, the base material 10 is provided on the outer surface on the viewing side. The undercoat layer 20 and the topcoat layer 40 are resin layers.

In the molded product 100, the undercoat layer 20 contains a filler. By containing the filler in the undercoat layer 20, the reflected light from the silver mirror layer 30 is diffused, optical interference is suppressed, and the appearance of rainbow colors due to interference fringes on the surface of the molded product 100 is suppressed. Although not shown, the top coat layer 40 may also contain a filler.

FIG. 2 is a schematic sectional view of the molded product 110. The molded product 110 is provided with a top coat layer 40, a silver mirror layer 30, an undercoat layer 20, and a base material 10 in order from the viewing side. In the molded product 110, the top coat layer 40 contains a filler. By containing the filler in the top coat layer 40, the reflected light from the silver mirror layer 30 is diffused, light interference is suppressed, and the appearance of rainbow colors due to interference fringes on the surface of the molded product 110 is suppressed. Although not shown, the undercoat layer 20 may also contain a filler.

As shown in FIGS. 1 and 2, it is preferable to use the molded product in such a manner that the resin layer containing the filler is closer to the viewing side than the silver mirror layer 30. By using in such an arrangement, optical interference is effectively suppressed, and the appearance of rainbow colors due to interference fringes is effectively suppressed.

In addition, as shown in FIG. 1, when the undercoat layer 20 which is not the outermost layer contains a filler, the gloss is increased and the metal feeling is increased.
On the other hand, as shown in FIG. 2, when the filler is contained in the top coat layer 40 which is the outermost layer, the reflectance is suppressed, the atmosphere becomes calm, and the feel of the filler can be obtained. In addition, scratching is prevented, and fingerprint adhesion and stickiness are suppressed.

The molded product 100 in FIG. 1 and the molded product 110 in FIG. 2 have light transmittance. Therefore, the base material 10, the undercoat layer 20, the silver mirror layer 30, and the topcoat layer 40 each have light transmittance. Therefore, an article placed on the side opposite to the viewing side can be confirmed via the molded product 100 or the molded product 110.

In the present disclosure, having light transmittance means that the visible light transmittance (visible light transmittance of at least a wavelength of 400 nm) is 10% or more. In the case of a molded product provided with a light-shielding image layer, the non-light-shielding portion only needs to have light transmittance.

FIG. 3 is a schematic sectional view of the molded product 120. The molded product 120 is provided with a base material 10, an undercoat layer 20, a silver mirror layer 30, a topcoat layer 40, and a light-shielding image layer 50 in order from the viewing side. That is, in the molded product 120, the light-shielding image layer 50 is disposed on the outermost surface on the side opposite to the viewing side in the molded product 100 described above.

When the light-shielding image layer 50 is provided on the molded product 100 and the light source 60 is disposed on the side opposite to the viewing side, the light from the light source 60 is blocked by the light-shielding portion of the light-shielding image layer 50, but the molded product 100 is light transmissive. Therefore, the light is transmitted through the non-light shielding portion. Therefore, when the molded product 120 is observed from the viewing side, an image of the light shielding image layer 50 is displayed on the surface of the base material 10 of the molded product 120.

The light-shielding image layer 50 is preferably provided on the side farther from the viewing side than the silver mirror layer 30. For example, the arrangement position of the light-shielding image layer 50 in FIG. 3 is between the silver mirror layer 30 and the top coat layer 40. You may change to
Although not shown, the light-shielding image layer 50 may be provided on the molded product 110 of FIG. 2 in which the base material 10 is provided on the side far from the viewing side. Also in this case, the light-shielding image layer 50 is preferably provided on the side farther from the viewing side than the silver mirror layer 30.

1 to 3, each of the undercoat layer 20 and the topcoat layer 40 is a single layer, but may be a plurality of layers of two or more layers. For example, when the top coat layer 40 that is the outermost layer on the viewing side in FIG. 2 is a plurality of layers, the depth is visually increased, and glossiness is easily obtained.
For example, when at least one of the undercoat layer 20 and the topcoat layer 40 is a plurality of two or more layers, it is sufficient that at least one of these layers contains a filler, and the undercoat does not contain a filler. The coat layer 20 and the top coat layer 40 may be clear layers.

1 to 3, the base material 10 is provided on one outer surface of the molded product, but may be provided on both outer surfaces. In this case, the base material 10, the undercoat layer 20, the silver mirror layer 30, the undercoat layer 20, and the base material 10 are preferably provided in this order, and at least one of the two undercoat layers 20 has a filler. It should just be contained.
Hereinafter, each material will be described.

<Base material>
The material of the substrate is not particularly limited, and an inorganic material such as metal and glass, and an organic material such as resin can be used. Examples of the resin include a thermosetting resin or a thermoplastic resin.

Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyvinyl chloride, vinyl polymer, polyester, polyamide, ABS resin, polyester resin, and thermoplastic elastomer.

Examples of the thermosetting resin include silicon resin, polyurethane resin, polyester resin, melamine resin, epoxy resin, phenol resin, urea resin and the like.

When the molded product is used for an automobile part, it is preferable to use polypropylene, polycarbonate, ABS resin (acrylonitrile-Butadiene-styrene copolymer resin) or the like as the material of the base material. 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 resin is a resin that is relatively easy to be subjected to surface treatment among plastic materials, and therefore is easy to apply after molding, etc., is excellent in chemical resistance and rigidity, and is also strong in impact resistance, heat resistance, and cold resistance. Polycarbonate has high impact resistance among plastic materials, is excellent in weather resistance and heat resistance, and has excellent transparency. Polycarbonate is easy to process and is relatively light and durable among plastic materials. It is.

The thickness of the substrate can be appropriately designed according to the use of the molded product. The shape of the substrate is not particularly limited.

<Undercoat layer>
The undercoat layer is provided from the viewpoint of improving the adhesion between the base material and the silver mirror layer and from the viewpoint of forming a smooth surface on the base material.

For the formation of the undercoat layer, fluorine resin paint, polyester resin paint, epoxy resin paint, melamine resin paint, silicon resin paint, acrylic silicon resin paint, acrylic urethane resin paint, etc. may be used. It is preferable to use an acrylic urethane resin paint. The acrylic silicone resin paint has excellent adhesion to the substrate, 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. These resin paints may be used alone or in combination of two or more.

The thickness of the undercoat layer is not particularly limited, and is preferably about 5 to 25 μm from the viewpoint of securing a smooth surface.

In order to improve the adhesion between the undercoat layer and the substrate, a primer layer may be provided between the undercoat layer and the substrate.

<Silver mirror layer>
The silver mirror layer is a layer formed by a silver mirror reaction. As a method for forming a silver mirror layer by a silver mirror reaction, a conventionally known method can be appropriately employed.
The thickness of the silver mirror layer is not particularly limited, and is preferably about 50 nm to 200 nm. When the thickness of the silver mirror layer is 50 nm or more, a metallic decoration effect tends to be easily obtained, and when it is 200 nm or less, silver discoloration tends to be suppressed.
The molded product of the present disclosure can be used, for example, for manufacturing a half mirror, and by adjusting the thickness of the silver mirror layer, transmission visibility when the molded product is used as a half mirror can be adjusted.

<Topcoat layer>
The top coat layer is a layer provided on the outermost surface, and the silver mirror layer is easily protected by the top coat layer. The top coat layer preferably has transparency that does not mask the silver mirror layer, and may be colorless clear (colorless and transparent) or colored color clear (colored and transparent).

For forming the topcoat layer, a resin paint can be used, and a thermosetting resin may be used. Examples of the thermosetting resin include fluorine resin paint, polyester resin paint, epoxy resin paint, melamine resin paint, silicone resin paint, acrylic silicone resin paint, acrylic urethane resin paint, acrylic silicone resin paint, and acrylic urethane paint. Is preferably used. The acrylic silicone resin paint is excellent in adhesion to the substrate, gloss retention, color retention, 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. These resin paints may be used alone or in combination of two or more.

The thickness of the top coat layer is not particularly limited, and is preferably about 20 μm to 40 μm. If the thickness of the topcoat layer is 20 μm or more, the silver mirror layer tends to be sufficiently protected, and if it is 40 μm or less, cracks, peeling, poor adhesion and the like due to changes with time tend not to occur.

<Filler>
The material of the filler is not particularly limited, and may be an inorganic material or an organic material. Examples of inorganic substances include calcium carbonate, silicon dioxide (silica), silicate minerals (talc, mica, etc.), aluminum silicate (clay), aluminum oxide (alumina), ceramic (titanium oxide, etc.), and the like. Examples of the organic material include polyimide, polytetrafluoroethylene (PTFE), nylon, acrylic acid ester, and styrene. As the filler, one kind may be used alone, or two or more kinds may be used in combination.

The filler may be colorless or colored, and is preferably colorless and transparent or cloudy from the viewpoint of utilizing the silver mirror layer present inside the resin layer containing the filler as a design. By making the filler colorless and transparent or cloudy, the filler can be prevented from being seen through from the viewing side.
In addition, when using a colored filler, it is preferable that the resin layer containing a filler is the same color system color clear (colored transparent) as a filler. Further, when a layer is further provided on the resin layer containing the filler, this layer may be a color clear of the same color as the filler.
As described above, the molded article of the present disclosure can change the color of the resin layer, for example, can match the color of the automobile body.

The size of the filler is not particularly limited. From the viewpoint of effectively suppressing the appearance of rainbow colors on the surface of the molded article, the average particle size is preferably 0.3 μm to 50 μm, more preferably 0.5 μm to 35 μm, and 3 μm to 30 μm. More preferably.
The average particle diameter of the filler can be adjusted by fine pulverization, granulation or the like.

In the present disclosure, the average particle size is determined by measuring the volume cumulative distribution curve by irradiating the filler with laser light using a laser diffraction / scattering particle size distribution measuring device, and measuring 50% particle size (cumulative 50% from the small diameter side) Median diameter).

The content rate of the filler in the resin layer containing the filler is not particularly limited, and can be appropriately designed according to the intended design.
From the viewpoint of effectively suppressing the appearance of rainbow colors on the surface of the molded product, the content of the filler in the undercoat layer or the topcoat layer 40 is preferably 0.001% by mass or more. The content is more preferably 05% by mass or more, and further preferably 0.15% by mass or more. The content of the filler in the top coat layer is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

Moreover, from the viewpoint of ensuring the light transmittance of the molded product, the content of the filler is preferably 50% or less, and preferably 30% or less with respect to the area (100%) when observed from the viewing side. It is more preferable that it is 20% or less.

In addition, when an undercoat layer or a topcoat layer is a multiple layer, the said content rate means the content rate of the filler in 1 layer.
When the undercoat layer or the topcoat layer is a plurality of layers, it is sufficient that at least one layer contains a filler, and an undercoat layer and a topcoat layer that do not contain a filler may be further provided. .

[Display device]
The display device of the present disclosure includes the molded product of the present disclosure described above and a backlight.
As shown in FIG. 3, when a backlight that is a light source 60 is disposed on the side opposite to the viewing side with respect to a molded product having the light-shielding image layer 50, the light emitted from the backlight causes the light-shielding image layer 50 to pass. To the viewing side. Therefore, when the molded product 120 is observed from the viewing side, an image formed by the non-light-shielding portion of the light-shielding image layer 50 is displayed on the surface of the molded product 120. The light-shielded image in the light-shielded image layer 50 can be changed in design and is excellent in design.
The type of backlight is not limited, and an LED or the like may be used.

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 polycarbonate substrate with length: 70 mm, width: 150 mm, thickness: 3 mm, and degrease and clean the surface of the substrate with a waste cloth containing IPA (isopropyl alcohol) to remove oil film, dirt, and dust. Thereafter, the substrate was dried.
Also, 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 (part by mass), and the filler a (Sekisui Plastics Co., Ltd.) Company: MBX-30, average particle size 30 μm, approximately spherical shape) was added in an amount of 0.3 part by mass, and this was stirred to prepare an undercoat layer composition.
The prepared undercoat layer composition was sprayed onto the substrate with a spray gun and dried in a drying oven set at 80 ° C. for 1 hour to form an undercoat layer having an average 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. After sufficient spray cleaning with pure water, Mitsubishi Paper Industries Co., Ltd. MSPS-Sa2A (trade name) manufactured by the company was applied to activate silver mirror deposition. Then, two liquids of MSPS-Ag (trade name) and MSPS-Do (trade name) manufactured by Mitsubishi Paper Industries Co., Ltd. were applied with a two-head spray gun to form a silver mirror layer by silver mirror reaction. Thereafter, spray cleaning was performed with pure water, MSPS-R1A manufactured by Mitsubishi Paper Industries Co., Ltd. was applied, and further spray cleaning with pure water was performed. And in order to remove the water | moisture content of a silver mirror layer, after blowing compressed air (air blow), it dried for 30 minutes in the drying furnace set to 45 degreeC.

(Formation of top coat layer)
MSPS top coat clear M, MSPS top coat thinner P-7, MSPS top coat curing agent W, and MSPS color black produced by Ohashi Chemical Co., Ltd., 20: 20: 5: 0. 4 (based on parts by mass) and stirred to prepare a composition for the topcoat layer.

After the silver mirror layer was dried, it was naturally cooled, and after confirming that the temperature of the molded product was room temperature (25 ° C.), the prepared composition for the top coat layer was sprayed with a spray gun and set to 80 ° C. It dried for 45 minutes in the drying furnace, and formed the topcoat layer with an average thickness of 25 micrometers.

<Example 2>
A molded product was obtained in the same manner as in Example 1 except that the filler a was replaced with the filler b (manufactured by Maruo Calcium Co., Ltd .: R heavy coal, average particle diameter 20 μm, amorphous).

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

<Example 4>
(Formation of undercoat layer)
In the formation of the undercoat layer in Example 1, an undercoat layer was formed in the same manner as in Example 1 except that the composition for an undercoat layer was prepared without adding the filler a.

(Formation of silver mirror layer)
In the same manner as the formation of the silver mirror layer in Example 1, a silver mirror layer was formed on the undercoat layer.

(Formation of top coat layer)
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 (based on parts by mass), and 0.3 parts by mass of a filler (manufactured by Sekisui Plastics Kogyo Co., Ltd .: MBX-30, average particle size of 30 μm, substantially spherical shape) is added and stirred. A composition was prepared.
The prepared composition was sprayed with a spray gun and dried in a drying furnace set at 80 ° C. for 45 minutes to form a topcoat layer having an average thickness of 25 μm.

(Comparative Example 1)
A molded product was obtained in the same manner as in Example 1 except that the composition for an undercoat layer was prepared without adding the filler a.

[Evaluation]
<Light transmission (half mirror property)>
For the molded products of Examples and Comparative Examples, the transmittance of visible light having a wavelength of 400 nm was measured by an ultraviolet-visible absorption spectrum method using an ultraviolet-visible spectrophotometer (Hitachi High-Tech Science Co., Ltd., U-3310 Spectrophotometer).

<Expression of interference fringes (rainbow colors)>
About the molded product of an Example and a comparative example, the presence or absence of generation | occurrence | production of an interference fringe (rainbow color) was confirmed visually by 50 test subjects, and the following evaluation criteria evaluated. The evaluation results are shown in Table 1.
A: 40 or more people are judged not to occur B: 30 to 39 people are judged not to occur C: 20 to 29 people are judged not to occur D: 19 people or less are judged not to occur

<Evaluation of metal texture>
About the molded product of an Example and a comparative example, the presence or absence of the metal texture was confirmed visually by 50 test subjects, and the following evaluation criteria evaluated. The evaluation results are shown in Table 1.
A: More than 40 people are judged to have metal texture B: 30 to 39 people judged to have metal texture C: 20 to 29 people judged to have metal texture D: 19 people or less judged to have metal texture

From the results of Table 1, in Comparative Example 1, expression of rainbow colors due to interference fringes was confirmed in many subjects.
On the other hand, in Examples 1 to 4, it was confirmed that the expression of rainbow colors due to interference fringes can be suppressed. Moreover, it has light transmittance, and it was confirmed that it can be used as a half mirror.

All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

Silver mirror layer,
A resin layer provided on both sides of the silver mirror layer;
A substrate provided on the outer surface of at least one of the resin layers,
A molded product in which at least one of the resin layers contains a filler and has light transmittance.
The molded article according to claim 1, wherein the silver mirror layer has a thickness of 100 nm or less.
The molded article according to claim 1 or 2, wherein the resin layer containing the filler is provided on the viewing side with respect to the silver mirror layer.
The molded article according to any one of claims 1 to 3, wherein the base material is provided on the outer surface on the viewing side.
The molded article according to any one of claims 1 to 4, wherein a light-shielding image layer is further provided on a side farther from the viewing side than the silver mirror layer.
The molded article according to any one of claims 1 to 5,
With backlight,
A display device.