JP2008221802A - Resin product and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin product which is equipped with a photoluminescent metal film with a discontinuous structure, and a holding coated film therefor, and a manufacturing method for the resin product. <P>SOLUTION: The method comprises the steps of: forming the metal film 32, having photoluminescence and the discontinuous structure, on a resin base material 31; thereon, applying a high-Tg coating material which is solidified by activated energy rays and which has a glass-transition temperature (Tg) not lower than a temperature lower than a molding temperature of a resin backside material 34 by 10°C, after solidification; forming a high-Tg coated film 21 by solidifying the high-Tg coating material by means of the activated energy rays; thereon, applying a low-Tg coating material having a glass-transition temperature (Tg) not higher than a temperature lower than the molding temperature of the resin backside material 34 by 110°C, after solidification; forming a low-Tg coated film 22 by solidifying the low-Tg coating material, so as to compose the holding coated film 20 for the metal film of the high-Tg coated film and the low-Tg coated film; and molding the resin backside material on the low-Tg coated film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin product provided with a metallic film having a brilliant and discontinuous structure and a pressing coating film thereof, and a method for producing the same.

  Today, millimeter-wave radar devices for distance measurement can be installed behind various parts of the vehicle, such as radiator grills, side moldings, back panels, etc., to warn the driver that the vehicle has approached nearby objects. is there. However, when these radiator grilles and the like are provided with glitter by a metal film, the metal film blocks or greatly attenuates the millimeter wave. Therefore, it is necessary to cover the millimeter wave path of the radar device with a radar device cover that is brilliant and millimeter wave transmissive. In order for the metal film to have millimeter wave permeability, it is a discontinuous structure, that is, the metal film is not continuous on one side, and a large number of fine metal particles are slightly separated from each other or are in partial contact with each other. It is necessary to make a structure (sea island structure) that is spread by

For the presser coating film formed on such a metal film, the corrosion resistance of this metal film is improved, the adhesion with the resin backing material formed above the metal film in a later process, and the resin backing material It is required to protect the metal film from stress during molding.
Here, a coating film having a low glass transition temperature (Tg) is preferred in order to improve the adhesion with the resin backing material formed in the subsequent step. On the other hand, a coating film having a high glass transition temperature is preferable in order to protect the metal film when a resin backing material is formed on the upper surface of the metal film in a subsequent step.
As described above, since the presser coating film is preferred to have a contradictory glass transition temperature, the presser coating film needs to have the target glass transition temperature uniformly throughout the coating film.

  Based on this, the coating process for forming a presser film is currently applied using a paint obtained by diluting a two-component acrylic urethane resin consisting of a main agent and a curing agent with a diluent, and then in the coating film. The diluent is evaporated and heat drying is performed until the reaction components of the resin are completely crosslinked and cured.

However, in order for the reaction components of the resin in the coating film to completely crosslink, it is necessary to heat dry for a long time at 100 ° C. or higher, so that the production process and manufacturing cost cannot be optimized.
Accordingly, in order to shorten the curing time of the presser coating film, a coating material that cures the coating film by irradiating light as described in Patent Document 1 was used for painting the presser coating film.
JP 2005-68384 A

  However, using a coating that cures the film when exposed to light, the curing time of the coating could be shortened, but those with a high glass transition temperature were adhesive to the resin backing material that was molded in the subsequent process. However, when a film having a low glass transition temperature was used, the metal film was affected during molding of the resin backing material, resulting in poor appearance. For this reason, it was not possible to use a paint whose coating film is cured by light irradiation for the application of the presser coating film.

  Then, an object of this invention is to provide the resin product provided with the metallic film of the glittering and discontinuous structure, and its presser film, and the manufacturing method of this resin product.

A. Resin product In order to achieve the above object, the resin product of the present invention is provided with a metallic film having a brilliant and discontinuous structure on a resin base material and against the heat during molding of a resin backing material to be molded in a subsequent process. A high Tg coating film having a glass transition temperature (Tg) that can protect the metal film, and a glass transition temperature (Tg) that is softened so that adhesion to the resin backing material can be obtained by heat during molding of the resin backing material. A low Tg coating is laminated in this order, and the metal coating presser coating is composed of a high Tg coating and a low Tg coating, and a resin backing material is molded on the low Tg coating. It is.

B. Manufacturing method of resin product In order to achieve the above object, the manufacturing method of the resin product of the present invention is a method for forming a glittering and discontinuous metal film on a resin substrate, and after solidifying on the metal film. Applying a high Tg paint that becomes a high Tg paint film having a glass transition temperature (Tg) that can protect the metal film against the heat during molding of the resin backing material to be molded in a subsequent process, and solidifying the high Tg paint A low Tg having a glass transition temperature (Tg) that forms a high Tg coating film and softens on the high Tg coating film so that adhesion to the resin backing material can be obtained by heat during molding of the resin backing material after solidification. A low Tg coating is applied, and the low Tg coating is solidified to form a low Tg coating. The metal coating presser coating is composed of a high Tg coating and a low Tg coating. A resin backing material is formed on the Tg coating film.

  The aspect of each element in the present invention is exemplified below.

1. Resin base material The form of the resin base material is not particularly limited, and examples thereof include a plate material, a sheet material, and a film material. Further, the resin of the resin base material is not particularly limited except that it is transparent in order to make use of the glitter of the metal film formed thereon, but is preferably a thermoplastic resin, such as polycarbonate (PC), acrylic. Examples thereof include resin, polystyrene (PS), polyvinyl chloride (PVC), and polyurethane. In addition, the transparency may be not only colorless and transparent but also colored and transparent.

2. The metallic film having a brilliant and discontinuous structure The metallic film having a brilliant and discontinuous structure is not particularly limited, but includes indium (In), tin (Sn) or aluminum (Al) and indium (In). Examples of the film include an alloy. Moreover, you may have a corrosion-resistant protective film which improves the corrosion resistance of a metal membrane | film | coat on or under or above and below a metal membrane | film | coat.
Although it does not specifically limit as a film thickness, 10-100 nm is preferable. If the thickness is less than 10 nm, the glitter tends to decrease, and if it exceeds 100 nm, a discontinuous structure is unlikely to occur.
Although it does not specifically limit as a film-forming method, Physical vapor deposition, such as vacuum evaporation, molecular beam evaporation, ion plating, ion beam evaporation, sputtering, can be illustrated.
The corrosion-resistant protective film is not particularly limited, silicon oxynitride _{(SiO x N} y), aluminum oxynitride _{(AlO x N} y), chromium oxide _{(Cr 2 O} 3), inorganic compounds such as titanium oxide can be exemplified .

3. Presser coating film The presser coating film is composed of a high Tg coating film having a relatively high glass transition temperature and a low Tg coating film having a relatively low glass transition temperature for the reason described later. One or two or more other coating films may or may not be present between the low Tg coating film and the low Tg coating film.

3-1. High Tg coating film The high Tg coating film is not particularly limited as long as it has a glass transition temperature (Tg) capable of protecting the metal film against heat during molding of the resin backing material to be molded in a subsequent process. However, an acrylic resin type, a polyester resin type, an epoxy resin type coating film, etc. can be illustrated. The film thickness of the high Tg coating film is preferably 5 to 50 μm. If the film thickness is thicker than this, sagging occurs at the time of coating, the cost increases, and uniform curing cannot be obtained in the coating film depth direction. Moreover, even if it hardens | cures completely, it is because the internal stress of a coating film becomes high and the coating film itself will be cracked. On the other hand, if the film thickness is thinner than this, the function of protecting the metal film cannot be obtained sufficiently.
Moreover, since the production process time can be shortened, it is a coating film (photocured coating film) in which the coating is solidified and cured with active energy rays, and the coating film is preferably cured by irradiation with active energy rays. Furthermore, the glass transition temperature (Tg) is preferably equal to or higher than the temperature lower by 10 ° C. than the molding temperature of the resin backing material because the metal film can be better protected from the heat during molding of the resin backing material. .

3-1-1. Active energy ray Although it does not specifically limit as an active energy ray, An ultraviolet-ray, visible light, an electron beam etc. can be illustrated. Moreover, the irradiation method of the active energy ray is not particularly limited, and examples thereof include a high pressure mercury lamp and a metal halide lamp.

3-2. Low Tg coating film The low Tg coating film is not particularly limited as long as it has a glass transition temperature (Tg) that is softened so that adhesion to the resin backing material can be obtained by heat during molding of the resin backing material. However, examples include acrylic resin-based, polyester resin-based, epoxy resin-based, acrylic urethane-based coating films, and the like. The film thickness of the low Tg coating film is preferably 5 to 50 μm. If the film thickness is thicker than this, sagging occurs at the time of coating, the cost increases, and uniform curing cannot be obtained in the coating film depth direction. On the other hand, if the film thickness is thinner than this, sufficient adhesion with the resin backing material cannot be obtained.
Moreover, the coating film (photocuring coating film) which hardens and hardens the paint with active energy rays, etc., or the paint film hardens and hardens by mixing the main agent and the curing agent (2 (Liquid cured coating film). Further, since the adhesion with the resin backing material is further improved, the glass transition temperature (Tg) is preferably equal to or lower than this temperature with respect to a temperature 110 ° C. lower than the molding temperature of the resin backing material.

4). Resin backing material The resin backing material is not particularly limited, but is preferably a thermoplastic resin, polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer (AES), Examples include polypropylene (PP), acrylic resin, polystyrene (PS), and polyurethane. In addition, the method of molding the resin backing material is not particularly limited, and examples thereof include injection molding and insert molding.

5. Application of resin product The application of this resin product is not particularly limited, but it may have radio wave transparency while having brilliant properties, such as a cover for a millimeter wave radar device or a housing of a communication device. What is preferred can be exemplified.

  ADVANTAGE OF THE INVENTION According to this invention, the resin product provided with the metallic film of the glittering and discontinuous structure and its presser film, and the manufacturing method of this resin product can be provided.

A metallic film with a glittering and discontinuous structure is formed on a resin substrate,
It is a coating film cured by irradiation with active energy rays on a metal film, and has a glass transition temperature (Tg) equal to or higher than this temperature with respect to a temperature 10 ° C. lower than the molding temperature of the resin backing material after solidification. Apply a high Tg paint to become a high Tg coating, solidify the high Tg paint by irradiation of active energy rays, and form a high Tg coating.
On the high Tg coating film, after solidification, a low Tg coating material that becomes a low Tg coating film having a glass transition temperature (Tg) below this temperature with respect to a temperature lower by 110 ° C. than the molding temperature of the resin backing material, A low Tg coating is solidified to form a low Tg coating film,
The metal coating presser coating is composed of a high Tg coating and a low Tg coating,
A resin backing material is molded on the low Tg coating film.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, first, preliminary tests conducted up to the present invention will be described.

  What is shown in the following Table 1 is a result of evaluation of cracking of the metal film by heating.

(1) Evaluation of cracking of metal film by heating (simple reproduction test of AES molding)
Under heating, the influence on the metal film due to the difference in the glass transition temperature (Tg) of the presser film was examined under the following conditions.
As heating conditions, heating was performed at 200 ° C. for 3 minutes.
As a presser coating film, a coating film having a glass transition temperature of 80 ° C. (a two-component cured coating film that is cured by mixing two components of a main agent and a curing agent, acrylic urethane type), a coating film having a glass transition temperature of 100 ° C. Film (photocured film cured by UV, acrylic resin, polyester resin, epoxy resin) or film having glass transition temperature of 200 ° C. or higher (photocured film cured by UV, acrylic resin, polyester resin) System, epoxy resin system).
In addition, in order to measure the glass transition temperature (Tg) of the presser coating film in all the tests including those described below, a rigid pendulum type physical property tester (model of A & D Corporation: RPT-3000) is used. Using.
As a resin base material, a polycarbonate (PC, thickness: 5 mm) having dimensions of 30 mm × 40 mm was used.
As the metal film, indium (In, film thickness: 400 mm) or an alloy of aluminum (Al) and indium (Al / In alloy, film thickness: 300 mm) was used. When indium was used as the metal film, an anticorrosion protective film (lower anticorrosion protective film) made of silicon oxynitride (SiO _x N _y , film thickness: 100 mm) was formed on the lower side of the metal film. .
As a test method, as shown in FIG. 2 (a), a metal film was formed on a resin substrate, and a press film was formed thereon, after heating under the above conditions, The state of the metal film (presence of cracks) was evaluated visually. “No” indicates that the crack is present, and “X” indicates that the crack is present.

From this test,
In Tests 1-1 and 2-1, which did not have a presser coating film, the polycarbonate as the resin base material was deformed by heat, and the metal film was cracked.
Tests 1-2 and 2-2 in which the glass transition temperature of the presser coating film is 80 ° C., and tests 1-3 and 2-3 in which the glass transition temperature of the presser coating film is 100 ° C. Both the polycarbonate which is the resin base material and the presser coating film were deformed, and the metal film was cracked.
In Tests 1-4 and 2-4, in which the glass transition temperature of the presser coating film is 200 ° C. or higher, the presser coating film that is highly cross-linked holds the metal film firmly, so that the polycarbonate serving as the resin substrate moves. However, the metal film did not crack.

  What is shown in the following Table 2 is a result of evaluation of cracking of the metal film by the film thickness of the presser film.

(2) Evaluation of cracking of metal film due to film thickness of presser film The effect on the metal film due to the difference in film thickness of the presser film was examined under the following conditions.
As a presser coating, a two-component cured coating (acrylic urethane) that cures by mixing two components of a main agent having a glass transition temperature of 80 ° C. and a curing agent, has a film thickness of 30 μm (standard) or 60 μm. Alternatively, three levels of film thickness 10 μm (standard), 20 μm, or 30 μm were used for a photo-curing coating film (acrylic resin-based, polyester resin-based, epoxy resin-based) that is cured with ultraviolet rays having the same glass transition temperature of 80 ° C.
As the resin base material, polycarbonate (PC, thickness: about 4 to 6 mm) was used.
As the metal film, indium (In, film thickness: 400 mm) or an alloy of aluminum (Al) and indium (Al / In alloy, film thickness: 300 mm) was used. When indium was used as the metal film, an anticorrosion protective film (lower anticorrosion protective film) made of silicon oxynitride (SiO _x N _y , film thickness: 100 mm) was formed on the lower side of the metal film. .
As the resin backing, acrylonitrile / ethylene / styrene copolymer (AES, thickness: about 2 to 4 mm) was used.
As a test method, as shown in FIG. 2 (b), a metal film is formed on a resin substrate, and after a press coat film is formed thereon, a resin backing material is insert-molded to form a metal film. The state (presence of cracks) and the adhesion between the presser coating film and the resin backing material were evaluated visually. “No” indicates that the crack is present, and “X” indicates that the crack is present. Further, good adhesion is indicated by ◯, and poor adhesion is indicated by ×.

  From this test, even when the press coating film having a glass transition temperature of 80 ° C. was thickened, the metal film was attacked when AES as the resin backing material was insert-molded (cracking of the metal film occurred).

  What is shown in the following Table 3 is a result of evaluation of adhesion between the cracks of the metal film and the resin backing material in the examples (6 types) and comparative examples (9 types) of the present invention.

The influence on the metal film was examined in the same manner as the evaluation of cracking of the metal film by the thickness of the presser film.
As shown in FIG. 1, the resin product 10 of the present example is made of indium (In) or an alloy of aluminum (Al) and indium (Al / In alloy) on a polycarbonate (PC) resin base material 31. A metal film 32 made of was formed. When indium was used as the metal film, an anticorrosion protective film 33 (lower anticorrosion protective film) made of silicon oxynitride (SiO _x N _y ) was formed below the metal film 32. On the metal film 32, a presser film 20 comprising a high Tg coating film 21 cured with ultraviolet rays and having a glass transition temperature of 200 ° C or higher and a low Tg coating film 22 having a glass transition temperature of 70 ° C, 80 ° C or 90 ° C. After that, a resin backing material 34 of acrylonitrile / ethylene / styrene copolymer (AES) is insert-molded thereon.
Moreover, as a test method and test conditions, except for the presser coating film, it is the same as the crack evaluation of the metal film by the film thickness of the presser coating film.
Each presser film is as follows. The two-part cured coating film (acrylic urethane type) in which the coating film is solidified by mixing the two liquids of the main agent and the curing agent, and the coating film is cured, is 30 μm, and the film thickness of the presser coating film is The photocured coating film (acrylic resin type, polyester resin type, epoxy resin type) in which the coating was solidified by irradiation and the coating film was cured was 10 to 15 μm.

In Examples 1-1, 1-2, and 1-3, the presser coating film is formed in two layers, a photocuring coating film having a glass transition temperature of 200 ° C. or higher is used as the lower layer, and the glass transition temperature is 70 ° C. or 80 in the upper layer. A two-component cured coating film at 90 ° C. or 90 ° C. was used.
In Examples 2-1, 2-2, and 2-3, the upper layer was changed to a photocured coating film having a glass transition temperature of 70 ° C, 80 ° C, or 90 ° C as compared with Example 1-1.

In Comparative Examples 1-4 and 2-4, the upper layer was changed to a two-component cured film or a photocured film having a glass transition temperature of 100 ° C. as compared with Example 1-1.
In Comparative Example 1-5, as compared with Example 1-1, the lower layer was changed to a two-component cured coating film having a glass transition temperature of 80 ° C, and the upper layer was changed to a photocurable coating film having a glass transition temperature of 200 ° C or higher. .

In Comparative Example 3-1, a two-part cured coating film having a presser coating film and a glass transition temperature of 80 ° C. was used.
Comparative Examples 3-2, 3-3, 3-4, 3-5, and 3-6 have glass transition temperatures of 80 ° C., 100 ° C., 180 ° C., 190 ° C., and 200 compared with Comparative Example 3-1. It changed into the photocuring coating film more than degreeC.

As shown in Table 3, an example using a two-layer presser film in which the lower layer is a coating film having a glass transition temperature of 200 ° C. or more and the upper layer is a coating film having a glass transition temperature of 90 ° C. or less is a metal coating. No cracking occurred, and adhesion with AES as the resin backing material was also good.
On the other hand, the comparative example which made the upper layer into the coating film whose glass transition temperature is 100 degreeC, the lower layer into the coating film whose glass transition temperature is 80 degreeC, and the comparative example which made the upper layer into the coating film whose glass transition temperature is 200 degreeC or more, and one layer In the comparative example using the presser coating film, the metal film was cracked or the adhesion with AES was not good.

  As shown in FIG. 3B, the mechanism for cracking the metal film is 200 ° C. at the time of insert molding of AES as the resin backing material. PC which is is softened. And the softened presser film and the resin base material are deformed by the stress when AES flows in the mold, and the metal film undergoes motion cracks.

  However, as shown in FIG. 3A, when the presser coating film 20 is composed of two layers of a high Tg coating film 21 and a low Tg coating film 22, the low Tg coating is caused by heat during AES insert molding. Although the film 22 and the PC as the resin base material 31 are softened, the high Tg coating film 21 is not softened, and the high Tg coating film 21 is also formed in the gap between the metal particles of the metal film having a discontinuous structure. Therefore, even if AES flows in the mold, the metal film does not move and cracks do not occur.

  As shown in FIG. 4, the photograph which peeled at the interface of a metal film and a presser film, and observed the state of the metal film from the top is attached. The photograph shown in FIG. 5 is a photograph in a state where no crack is generated in the metal film, and the photograph shown in FIG. 6 is a photograph in a state where a crack is generated in the metal film.

  Regarding the process time of the presser coating film, the presser coating film is made into two layers, the coating film cured by ultraviolet rays is used in the lower layer, and the coating film cured by mixing two liquids of the main agent and the curing agent in the upper layer is used. The curing time for forming the presser coating film was shortened to about 1/16 compared with the current time. In addition, by using a coating film that is cured by ultraviolet rays in both the lower layer and the upper layer, the curing time for forming the presser coating film was shortened to about 1/95 compared to the current level.

  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.

It is a schematic diagram of the resin product of the Example of this invention. It is a schematic diagram of the test piece for preliminary tests. It is a schematic diagram at the time of resin backing material molding. It is a schematic diagram which shows the metal film observation method. It is a microscope picture of a favorable metal film. It is a microscope picture of the metal film which the crack produced.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Resin product 20 Presser coating 21 High Tg coating 22 Low Tg coating 31 Resin base material 32 Metal coating 34 Resin backing material

Claims (5)

  A high Tg having a glass transition temperature (Tg) capable of protecting the metallic film against the heat during molding of a metallic film having a brilliant and discontinuous structure and a resin backing material molded in a subsequent process on the resin substrate. A coating film and a low Tg coating film having a glass transition temperature (Tg) that is softened so that adhesion to the resin backing material can be obtained by heat during molding of the resin backing material are laminated in this order, and the metal A resin product in which a presser coating film of the film is composed of the high Tg coating film and the low Tg coating film, and the resin backing material is molded on the low Tg coating film. A metallic film with a glittering and discontinuous structure is formed on a resin substrate,
On the metal film, a high Tg paint that becomes a high Tg paint film having a glass transition temperature (Tg) capable of protecting the metal film against heat at the time of molding of a resin backing material to be molded in a subsequent process after solidification is applied. , Solidify the high Tg paint to form a high Tg coating film,
On the high Tg coating film, a low Tg coating film having a glass transition temperature (Tg) that is softened so that adhesion to the resin backing material can be obtained by heat during molding of the resin backing material after solidification. Apply a paint, solidify the low Tg paint to form a low Tg coating film,
Therefore, the press coating film of the metal film is composed of the high Tg coating film and the low Tg coating film,
A method for producing a resin product, comprising molding a resin backing material on the low Tg coating film.   The manufacturing method of Claim 2 which solidifies the said high Tg coating material by irradiation of an active energy ray.   The resin product according to claim 1, wherein a glass transition temperature (Tg) of the high Tg coating film is equal to or higher than a temperature lower by 10 ° C than a molding temperature of the resin backing material.   The resin product according to claim 1 or 4, wherein a glass transition temperature (Tg) of the low Tg coating film is equal to or lower than the temperature lower than a molding temperature of the resin backing material by 110 ° C.