JP4918454B2 - Resin base material provided with metal decorative film protected by protective film, and method for laminating metal decorative film on resin base material - Google Patents

Description

  The present invention relates to a resin base material provided with a metal decorative film protected by a protective film, and a method for laminating the metal decorative film on the resin base material.

Conventionally, a metal decorative film is formed by wet plating, sputtering or vacuum deposition to give a metallic luster to the surface of resin substrates used in electronic equipment, home appliances, automotive exteriors and interiors, etc. I have to.
When the metal decoration film is formed by a wet plating method, the film thickness is relatively large, such as several tens of μm. Therefore, even if a protective film is coated on the metal decoration film using an organic solvent, The substrate is not attacked by the organic solvent.
However, in the metal decorative film formed by sputtering method or vacuum vapor deposition method, the film thickness is relatively thin such as several tens to several hundreds nm, so that the protective film is made of an organic solvent in the same manner as the wet plating method. When applied, the organic solvent penetrates into the metal decorative film, and further, there is a problem that the resin base material under the organic solvent is invaded and the metal decorative film is peeled off.
In order to solve this problem, a method of forming a protective film for preventing the penetration of an organic solvent on a resin base material by a wet method or a coating method is conceivable. If there is a fine uneven surface formed by embossing, this protective film is not laminated well along the uneven surface, and even if a metal decorative film is formed on it, the desired design property can be obtained There was no problem.

  Therefore, the present invention provides a resinous substrate and a resinous substrate provided with a metal decorative film protected by a protective film that does not attack the resinous substrate even if a protective film is formed using an organic solvent. An object of the present invention is to provide a method for laminating a metal decorative film.

In order to solve the above problems, the present inventors have found that, as a result of intensive studies, a thin film made of a polymer that does not penetrate an organic solvent on a resin substrate is formed by a vapor deposition polymerization method. The solution was found as follows.
That is, the method for laminating a metal decorative film according to the present invention is a method for laminating a metal decorative film protected by a protective film on a resin base material as described in claim 1, wherein the metal decorative film is formed on the resin base material. A polymer film formed by vapor deposition polymerization and a metal decoration film are laminated, and then a protective film is laminated using an organic solvent.
According to a second aspect of the present invention, in the metal decorative film laminating method according to the first aspect, the metal decorative film is formed by a dry process.
According to a third aspect of the present invention, in the metal decorative film laminating method according to the first or second aspect, the polymer film is a polyurea film.
The resin member according to the present invention is a resin base material provided with a metal decorative film protected by a protective film formed using an organic solvent, as defined in claim 4, wherein the resin base The metal decoration film is provided on the surface of the material through a polymer film obtained by vapor deposition polymerization.
The present invention according to claim 5 is the resin substrate according to claim 4, wherein the polymer film is a polyurea film.

According to the method for laminating a metal decorative film on a resinous base material of the present invention, even if a protective film is laminated using an organic solvent on the metal decorative film, the resinous base material may be attacked by the organic solvent. Absent. As a result, peeling of the metal decorative film can be prevented.
Further, according to the resin base material of the present invention, the metal decorative film is suppressed from peeling, and the shape of the uneven surface formed on the resin base material surface by embossing or hairline processing is impaired. Therefore, it can have excellent design properties.

Next, an embodiment of the present invention will be described.
In the method for laminating a metal decorative film according to the present invention, a polymer film is first laminated on a resin substrate by vapor deposition polymerization.
The film formation rate of the polymer film is not particularly limited, but is preferably 0.5 μm / min or less. This is because the film forming conditions are controlled by the monomer reaction rate, and the film is formed along the surface shape.
The material for forming the polymer film is not particularly limited as long as it is a polymer material capable of vapor deposition polymerization such as polyurea film, polyimide, polyamide, polyoxadiazole, polyurethane, and polyazomethine. A film is preferred. It is because it is excellent in the characteristic which protects the resin-made base materials.
The polyurea film can be obtained by vapor deposition polymerization of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer.
As the diisocyanate of the raw material monomer, for example, an aromatic alkyl diisocyanate represented by Chemical Formula 1, such as an alicyclic diisocyanate represented by Chemical Formula 2, or an aliphatic diisocyanate represented by Chemical Formula 3, for example, can be used.

Moreover, as a diamine of a raw material monomer, the aromatic alkyldiamine shown by Chemical formula 4, For example, the alicyclic diamine shown by Chemical formula 5, For example, the aliphatic diamine shown by Chemical formula 6 can be used.

A polyurea film can be obtained by evaporating these raw material monomers in a vacuum and polymerizing them on a resin substrate. The vacuum pressure is not particularly limited, but can be about 10 ^{−3 to} 100 Pa.

Specific examples of the raw material monomer are as follows.
<Diisocyanate>
Aromatic alkyl: 1,3-bis (isocyanatemethyl) benzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene, etc. Alicyclic: 1,3-bis (isocyanatemethyl) cyclohexane, 3-isocyanatemethyl −3,5,5-trimethylhexyl isocyanate, methylenebis (4-cyclohexylisocyanate), 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2,2,1] heptane, etc. Aliphatic: 1,6- Diisocyanate hexane, 1,5-diisocyanate-2-methylpentane, 1,8-diisocyanate octane, 1,12-diisocyanate dodecane, tetraisocyanate silane, monomethyltriisocyanate silane, etc. <diamine>
Aromatic alkyl: 1,3-bis (aminomethyl) benzene, 1,4-bis (aminomethyl) benzene, isophthalic acid dihydrazide, etc. Alicyclic: 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( (Aminomethyl) cyclohexane, 3-aminomethyl-3,5,5-trimethylhexylamine, 1,2-diaminecyclohexane, 1,4-diaminocyclohexane, methylenebis (4-cyclohexylamine), piperazine, 2-piperazine, 2, 5-dimethylpiperazine, 2,6-dimethylpiperazine, N, N′-bis (3-aminopropyl) piperazine, 1,3-di (4-piperidyl) propane, hydantoin, hexahydro-1H-1,4-diazepine, Aliphatic acids such as barbituric acid: 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminodo Can, bis (2-aminoethyl) amine, bis (3-aminopropyl) amine, N, N′-bis (aminopropyl) methylamine, N- (3-aminopropyl) -1,4-butanediamine, N N '-(3-aminopropyl) -1,4-butanediamine, adipic acid dihydrazide, dodecanedioic acid dihydrazide, sebacic acid dihydrazide, etc.

  The film thickness of the polymer film is preferably 1 μm to 50 μm, more preferably 5 μm. This is because if it is less than 1 μm, the organic solvent cannot be prevented from penetrating into the resin base material, and if it exceeds 50 μm, the surface design may be lost.

Next, a metal decorative film is laminated on the resin base material on which the polymer film is formed as described above by sputtering, vacuum deposition, ion plating, or the like.
The thickness of the metal decorative film is not particularly limited, but is preferably about 10 nm to 1000 nm. If the thickness is less than 10 nm, the metallic luster does not appear, and if it exceeds 1000 nm, defects such as cracks occur in the film. Moreover, although it does not restrict | limit especially about the material which comprises a metal decoration film, For example, Cr, Al, SUS, etc. can be used.
The metal decorative film is preferably formed by a dry process such as sputtering, vacuum deposition, or ion plating. This is because the generation of environmentally hazardous substances such as waste liquid can be reduced.

Then, a protective film is laminated on the metal decorative film using an organic solvent. Specifically, acrylic, urethane, acrylurethane, or the like can be used as the material for the protective film. In addition, as an organic solvent, alcohol type, acetone type etc. can be used, for example.
The thickness of the protective film can be set to about 20 μm, for example.

  As described above, if a metal decorative film is laminated on the polymer film formed by the vapor deposition polymerization method, even when the organic solvent permeates the metal decorative film when the protective film is laminated using an organic solvent. The resin substrate is not attacked by the polymer film formed by the vapor deposition polymerization method.

  The resin substrate in the present invention is not particularly limited as long as it is a resin. For example, ABS (acrylonitrile / butadiene / styrene), PC (polycarbonate), PBT (polybutylene terephthalate), or the like is used. Can do. The resin substrate is not particularly limited to a planar shape, and may be a complicated three-dimensional shape.

  Moreover, this invention is especially effective when the uneven surface of about 100 nm-1 mm in height is formed in the said resin-made base materials by embossing or hairline processing. This is because, since the polymer film is formed into a thin film along the shape of the uneven surface, the metal decorative film laminated thereon can also conform to the shape of the uneven surface.

An embodiment of the present invention will be described below with reference to the drawings.
FIG. 1 shows an example of an apparatus for carrying out the method of the present invention. In FIG. 1, reference numeral 1 denotes a processing chamber, and a PC resin base material 2 on which a polyurea film is to be formed in the processing chamber 1 is a holder. 3 was supported rotatably. Further, the processing chamber 1 was connected to an external vacuum pump or other evacuation system 4 and containers 7 and 8 filled with raw material monomers via flow paths 5 and 6. Methylene bis (4-cyclohexylamine) and 1,3-bis (isocyanatomethyl) cyclohexane were used as raw material monomers. In the figure, reference numeral 9 denotes a valve in which the PC resin substrate 2 and the evaporation containers 7 and 8 are interposed.

  Next, methylenebis (4-cyclohexylamine) in the container 7 is heated to 84 ° C., and 1,3-bis (isocyanatomethyl) cyclohexane in the glass container 8 is heated to 76 ° C. The pressure in the chamber is evacuated by the evacuation system 4 until the temperature in the chamber is 20 ° C. and the temperature of the PC resin substrate 2 is 20 ° C., and then each raw material monomer is introduced into the processing chamber 1. A polyurea film was laminated on the PC resin substrate 2 at a film formation rate of 0.4 μm / min by the vapor deposition polymerization reaction shown in Chemical Formula 7 below. The pressure in the processing chamber 1 after the introduction of the raw material monomer was 5 Pa.

  Next, as shown in FIG. 2, a metal decorative film 11 made of Cr having a film thickness of 0.1 μm is laminated on the polyurea film 10 by sputtering, and acrylic urethane is applied thereon using an organic solvent. By doing so, the protective film 12 was laminated | stacked and it was set as the resin-made base materials of an Example.

  For comparison, a resin substrate was prepared as a comparative example in the same manner as in the example except that the polyurea film was not laminated by vapor deposition polymerization.

When the metal decorative film of each of the examples and comparative examples was cut from the protective film so as to be 1 mm square, and a peel test was performed according to JIS H8504, in the example, peeling was observed for 100 pieces. In contrast, almost all peeled off in the comparative example.
From this result, in the comparative example, the resin base material was attacked by the organic solvent and the adhesion to the metal decorative film was lost, whereas in the example, the resin base material was attacked by the organic solvent. It was found that the adhesion to the metal decorative film could be secured.

  The present invention is widely applicable to resinous substrates such as electronic devices (for example, mobile phone exteriors), home appliances (for example, refrigerator handles), automotive exteriors (for example, front grills), interior parts (for example, center consoles), and the like. Can be used.

Explanatory drawing of the apparatus structure used for one Example of this invention Explanatory drawing of the laminated structure of the resin-made base materials of one Example of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Processing chamber 2 Resin base material 3 Holder 4 Vacuum exhaust system 5 Channel 6 Channel 7 Container 8 Container 9 Valve 10 Polyurea membrane (polymer membrane)
11 Metal decorative film 12 Protective film

Claims (5)

  A method of laminating a metal decorative film protected by a protective film on a resin base material, wherein a polymer film by vapor deposition polymerization and a metal decorative film are laminated on the resin base material, and then an organic solvent A method for laminating a metal decorative film on a resin substrate, comprising laminating a protective film using   The method for laminating a metal decorative film on a resin base material according to claim 1, wherein the metal decorative film is formed by a dry process.   The method for laminating a metal decorative film on a resin substrate according to claim 1 or 2, wherein the polymer film is a polyurea film. A resin base material provided with a metal decorative film protected by a protective film formed using an organic solvent, wherein the metal is interposed on the surface of the resin base material through a polymer film obtained by vapor deposition polymerization. A resin base material provided with a decorative film.   The resin base material according to claim 4, wherein the polymer film is a polyurea film.

Images