JPH0874037A - Composite material having metallic vapor-deposited layer and production thereof - Google Patents

Abstract

PURPOSE: To easily and inexpensively form a high-grade uniform metallic vapor- deposited layer even on a rigid transparent resin sheet with good productivity by applying a winding up type vapor deposition device and to provide a composite material having the metallic vapor-deposited layer excellent in weatherability and durability since the quality of the transparent resin sheet is not selected. CONSTITUTION: Weatherproof transparent resin layers 5 and 5' are stuck on both sides of a metallic vapor-deposited layer 3 through adhesive layers 4 and 4' to constitute a composite material having a metallic vapor-deposited layer consisting of five layers. Alternately, a releasable layer is formed on one side of a plastic film capable of being easily vapor-deposited with a winding-up vapor deposition device, a metal is vapor-deposited on the releasable layer to form a metallic vapor-deposited layer, the metallic vapor-deposited layer is stuck to a weatherproof transparent layer through an adhesive layer by dry lamination, the metallic vapor-deposited layer is released at the interface of the releasable layer and the metallic vapor-deposited layer to form a three-layer structure consisting of the metallic vapor-deposited layer, adhesive layer and weatherproof transparent resin layer, and then a weatherproof transparent resin layer is stuck to the metallic vapor-deposited layer of the three-layer structure through the adhesive layer by dry lamination.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material having a metal vapor deposition layer and a method for producing the same, and more particularly to a composite material having a metal vapor deposition layer having improved weather resistance and durability and a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, as a metal vapor deposition processing method on a transparent resin plate, there have been known a method of directly vapor depositing on a transparent resin plate and a method of adhering a metal vapor deposition film which has been subjected to an adhesive process onto the transparent resin plate.

[0003]

However, in the direct vapor deposition method on the transparent resin plate, it is difficult to control the film thickness of the metal vapor deposition layer because of the batch method, and it is easy to cause the vapor deposition unevenness, and it cannot be applied to a large surface. In addition, in the batch method, since the productivity is low, the vapor deposition cost becomes very high, and its use is limited. On the other hand, in the method of adhering the metallized film with adhesive processed to the transparent resin plate, the adhesive processing on the metallized film is an off-line process, and the appearance quality may be degraded by the protrusion of the adhesive. , Was ugly in practice. That is, the conventional technique has many problems.

The present invention has been made in view of the above problems, and it is a metal having no vapor deposition unevenness, excellent productivity, low cost, good appearance, and excellent weather resistance and durability. It is an object of the present invention to provide a composite material having a vapor deposition layer and a method for producing the same.

[0005]

As a result of research to improve the above various problems, the present invention has no vapor deposition unevenness, can be applied to a large surface, has high productivity, is low in cost, We have developed a composite material having a metal vapor-deposited layer that has no adhesive sticking out and is excellent in appearance and has excellent weather resistance and durability, and a method for producing the same.

That is, according to the present invention, a weather resistant transparent resin layer (5, 5 ') is laminated on both surfaces of a metal vapor deposition layer (3) via adhesive layers (4, 4'). As a result, there is no vapor deposition unevenness, it can be applied to a large surface, it has good productivity, it is low cost, there is no sticking out of the adhesive, and the appearance is high quality. Especially excellent weather resistance and durability are improved. A composite material having the deposited metal vapor deposition layer was obtained.

Furthermore, a release treatment layer (2) is formed on one surface of a plastic film (1) which can be easily vapor-deposited by a roll-up type vapor deposition device, and a metal is vapor-deposited on the release treatment layer (2). To form a metal vapor deposition layer (3), and the surface of the metal vapor deposition layer (3) and the weather resistant transparent resin layer (5) are bonded to the adhesive layer (4).
After being laminated by a dry laminating method via a layer, the release treatment layer (2) and the metal vapor deposition layer (3) are peeled and separated at the interface, and the metal vapor deposition layer (3) / adhesive layer (4) / weather resistance A three-layer structure comprising a transparent resin layer (5) is prepared, and thereafter, a weather resistant transparent resin layer (5 ') is formed on the metal vapor deposition layer (3) surface of the three-layer structure.
By a dry laminating method in which the adhesive layer (4 ') is bonded to the both sides of the metal vapor-deposited layer (3) with the adhesive layer (4, 4') being interposed between them and the weather-resistant transparent layer. A composite material having a metal vapor deposition layer having a five-layer structure in which the resin layers (5, 5 ′) were laminated was obtained.

[0008]

The structure of the composite material having the metal vapor deposition layer of the present invention and the manufacturing method thereof will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a composite material having a metal vapor deposition layer of the present invention, and FIG. 2 is a schematic cross-sectional view in the order of steps until the composite material having a metal vapor deposition layer shown in FIG. 1 is produced.

FIG. 1 shows a metal vapor deposition layer of the present invention in which a weather resistant transparent resin layer (5, 5 ') is attached to both sides of a metal vapor deposition layer (3) via adhesive layers (4, 4'). A schematic cross-sectional view of a composite material having The thickness of each layer in the drawings is conceptual and different from the actual thickness, and the ratio of the thickness of each layer is not limited to this. Figure 2
(A, B, C, D, E) are schematic cross-sectional views for explaining a process for producing a composite material having a metal vapor deposition layer of the present invention.

FIG. 2A shows a plastic film (1).
Is a two-layer structure having a release treatment layer (2) formed on one surface thereof. FIG. 2B shows a three-layer structure in which a release treatment layer (2) is formed on one side of a plastic film (1), and a metal deposition layer (3) is further formed on the release treatment layer (2). is there. Figure 2
In (C), a release treatment layer (2) and a metal vapor deposition layer (3) are sequentially formed on one side of a plastic film (1), and an adhesive layer (4) is provided on the metal vapor deposition layer (3). It is a five-layer structure in which a weather resistant transparent resin layer (5) is laminated. 2D is a metal vapor deposition layer 3 and an adhesive layer 4 in which the plastic film 1 and the release treatment layer 2 are removed from the five-layer structure of FIG. 2C. Weatherproof transparent resin layer (5)
It is a three-layer structure consisting of. FIG. 2 (E) shows an adhesive layer (4 ′) on the surface of the metal vapor deposition layer (3) of the three-layer structure of FIG. 2 (D).
It is a composite material having a metal vapor deposition layer of the present invention having a five-layer structure in which the weather resistant transparent resin layer (5 ′) is bonded via the.

The above-mentioned plastic film (1) used in the present invention is not particularly limited, and usually commercially available cellulose resins such as cellulose triacetate and acetate, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and poly resins. Acrylic resins such as methyl methacrylate, polycarbonate resins, polyether sulfone resins, polynorbornene resins, polyolefin fin resins such as polypropylene and polyethylene, polytetrafluoroethylene,
An artificial resin film or a synthetic resin film such as a fluororesin such as polyvinyl fluoride can be used. The thickness is not particularly limited, and is usually 4 to 300 μm.
Is preferred. If the thickness is less than 4 μm, the strength is insufficient, and wrinkles or vapor deposition burns occur in the metal vapor deposition process or the step of forming the release treatment layer (2), which is not preferable because workability is poor. On the other hand, if the thickness exceeds 300 μm, the strength is too strong and the winding property in a roll-up type vacuum vapor deposition device is poor, and the loading amount (length) per time becomes small, which increases the vacuum vapor deposition cost and material cost. From the point of view, it is not economical and is not practical except in special cases, which is not preferable. Above all, the thickness is 9 ~
The 100 μm biaxially oriented polyethylene terephthalate film has excellent mechanical suitability, is relatively inexpensive, and is easily available. In addition, it does not cause wrinkles, thermal deformation, or whitening in the roll-up type vapor deposition device, and emits little gas, resulting in extremely high vapor deposition. It is preferable because it is easy.

The release treatment layer (2) used in the present invention is not particularly limited, and those used in ordinary release treatment layers such as urethane acrylate resin, silicone resin, fluorine resin, Waxes, surfactants, metal oxides, polypropylene resins, polyethylene resins and the like can be used. These are, for example, as a solvent solution, applied on one side of the plastic film (1), dried, and cured for a curable resin, or formed by a vacuum deposition method. The thickness is not particularly limited, and is usually appropriately selected from several molecular layers to about 5 μm capable of exhibiting a function as a release treatment layer.

The method for forming the metal vapor deposition layer (3) used in the present invention is not particularly limited, and examples thereof include a vacuum vapor deposition method, a sputtering method, an ion plating method,
It is formed by a usual method for forming a metal thin film, a metal compound thin film, or an alloy thin film, such as a reactive vacuum deposition method, a reactive sputtering method, or a reactive ion plating method. Therefore, the vapor deposition method referred to in the specification of the present invention includes the above-mentioned vacuum vapor deposition method, sputtering method, ion plating method, reactive vacuum vapor deposition method, reactive sputtering method, and reactive ion plating method. The metal used in the metal vapor deposition layer (3) of the present invention is not particularly limited, and for example, simple metals such as silver, aluminum, platinum, titanium, chromium, nickel, tin, iron and cobalt, and zinc sulfide, bismuth oxide, etc. And a metal compound such as a nickel-chromium alloy, stainless steel, Inconel, or a silver-gold-copper alloy can be used. Therefore, the metal vapor deposition layer (3) referred to in the specification of the present invention includes the above-mentioned single metal vapor deposition layer, metal compound vapor deposition layer, and alloy vapor deposition layer.
The thickness of the metal vapor deposition layer (3) is not particularly limited, but is usually 5n.
It is appropriately selected from the range of about m to 200 nm. If the thickness is less than 5 nm, the metal vapor-deposited layer does not have a common function, that is, light selective transmission and light selective reflection, which is not preferable. For the purpose of reflecting the metal vapor-deposited layer, the thickness is usually preferably about 30 nm or more. On the other hand, if the thickness exceeds 200 nm, the reflectance is not further improved, which is not preferable. Moreover,
As the amount of heat received by the plastic film (1) and the release treatment layer (2) during metal deposition processing increases, the plastic film (1) and the release treatment layer (2) are thermally damaged, so that expansion and contraction and wrinkles may occur. This is not preferable because it causes the workability to be lowered and the amount of metal used is increased, resulting in poor economic efficiency.

The metal vapor deposition layer (3) used in the present invention is not limited to a uniform and continuous one, and may have a gradient in film thickness and may have a pattern of an arbitrary shape. There is no particular limitation on the method of forming a pattern of the metal vapor deposition layer (3) in an arbitrary shape, and for example, a mask vapor deposition method in which a pattern is formed simultaneously with vapor deposition by using a mask during the formation of the metal thin film, and a metal is previously formed on the entire surface. Ordinary patterns such as an opal processing method (a kind of etching method), a celite processing method (cleaning method), a lift-off method, a photoresist method, etc., which removes an unnecessary metal vapor deposition layer (3) portion after forming the vapor deposition layer (3) A forming method can be used. Among them, the opal processing method and the sealite processing method are preferably used.

Here, the opal processing method and the sealite processing method will be briefly described. The opal processing method uses a plastic film (1) with a release treatment layer (2) formed on one side.
A three-layer structure having a metal deposition layer (3) formed on the entire surface of the release treatment layer (2) is prepared, and a necessary part of the metal deposition layer (3) (metal deposition formed in a discontinuous pattern later) is prepared. A method in which a printed layer having an arbitrary pattern is formed by printing on a layer (3) to be left as a layer (3) with a corrosion-resistant printing ink, and then the metal deposition layer (3) on the exposed portion is removed by etching by immersing the printed layer in a metal-corrosive solution. Is. The sealite processing method is a plastic film (1) having a release treatment layer (2) formed on one side.
An unnecessary portion of the metal vapor deposition layer (3) (portion to be a gap between the metal vapor deposition layers (3) formed in a discontinuous pattern later) is previously formed on the release treatment layer (2) of the above-mentioned water-soluble paint or solvent. After forming a printed coating film of an arbitrary pattern with a soluble paint, form a metal vapor deposition layer (3) on the entire surface, and then dip it in water or a solvent to form a printed film with a pattern of a water-soluble paint or a solvent-soluble paint. This is a method of dissolving and removing the upper metal vapor deposition layer (3). Therefore, the metal vapor deposition layer (3) pattern having an arbitrary shape can be easily obtained by the ordinary printing method, the ordinary vapor deposition method, and the ordinary pattern forming method.

The metal vapor deposition layer (3) used in the present invention is not limited to one layer. For example, if silver is vapor-deposited first and gold is then vapor-deposited, a vapor-deposited film with a gold-colored front surface and a silver-colored back surface can be obtained, and this color can be expressed even in the case of a composite material to enhance decorativeness. . In addition, first, a semi-transparent metal is vapor-deposited, and then a transparent metal compound is added to the optical thickness (n
d) is a vapor-deposited film having an odd number of quarter wavelengths, which is semi-transparent or a metal having a normal thickness having a metallic luster is vapor-deposited. This interference iris color is exhibited even when it is obtained as a composite material, and the decorative property can be enhanced.

The adhesive layer (4,
Although 4 ') is not particularly limited, various adhesives such as emulsion type adhesives and solvent type adhesives can be used. For example, urethane resin adhesives, polyester resin adhesives, acrylic resin adhesives, ethylene-vinyl acetate copolymer adhesives, chlorinated polypropylene adhesives, vinyl chloride-vinyl acetate copolymer adhesives, acrylic chlorides Adhesives such as vinyl-vinyl acetate copolymer-based adhesives may be used alone or as a mixture. These are applied, for example, as a solvent solution on the surface of the metal vapor deposition layer (3),
It is formed by drying, coating on one side of the weather-resistant transparent resin layer (5, 5 ') and drying, or coating on both sides and drying.

The thickness of the adhesive layer (4, 4 ') is not particularly limited, as long as the desired adhesive force can be obtained, and it is usually 0.
It is appropriately selected from the range of about 3 to 10 μm, preferably about 0.5 to 5 μm. If the thickness is less than 0.3 μm, it is difficult to obtain a sufficient adhesive force, while if it exceeds 10 μm, the adhesive force is not further improved, and the transparency of the adhesive layer decreases, or It is not preferable because complete removal of the solvent becomes difficult and swelling occurs in the dry lamination process. The components and thickness of the adhesive layer (4) and the adhesive layer (4 ′) may be different.

The weather resistant transparent resin layer (5, 5 ') used in the present invention is not particularly limited, but a plastic resin having high transparency, weather resistance and durability is used in consideration of its application. Preferably, for example, acrylic resin, polycarbonate resin, polyester resin,
It is preferable to use a synthetic resin such as a polyether sulfone resin, a polynorbornene resin, a fluorine resin, a cellulose resin or an artificial resin. Further, these resins may be added with known additives such as lubricants, plasticizers, ultraviolet absorbers, various hillers, matting agents, dyes and pigments to the extent that transparency is not lost. Further, a wire mesh and a glass cloth may be laminated on the weather resistant transparent resin layer (5, 5 ').

The thickness of the weather resistant transparent resin layer (5, 5 ') is
There is no particular limitation, but for the purpose of the present invention, it is usually 50
A plate-like object is targeted from a sheet-like object having a size of μm or more. However, it can be said that it is an effective and preferable object to apply a film-like material having a thickness of 50 μm or less, which has poor vapor deposition suitability. The weather resistant transparent resin layer (5) and the weather resistant transparent resin layer (5 ′) may have different thicknesses from each other.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0022]

【Example】

Example 1 A urethane acrylate UV-curable resin coating (Dainippon Ink and Chemicals Co., Ltd., Unidec) was applied to one surface of a polyethylene terephthalate film (1) having a thickness of 24 μm by a gravure coating method, and the thickness when dried and cured. A coating layer of 3 μm is formed and 160 W / cm
The ultraviolet ray irradiation lamp of the high pressure mercury lamp is used to cure at a moving speed of 15 m / min to form a release treatment layer (2), and a roll-up type vapor deposition device is formed on the release treatment layer (2). Aluminum metal is vapor-deposited by using to form a metal vapor deposition layer (3) having a thickness of 50 nm, and a polyester adhesive (Takelac A-310 manufactured by Takeda Pharmaceutical Co., Ltd.) is formed on the metal vapor deposition layer (3). 24%, hardener (Takeda A-3, Takenate A-3) 10%, ethyl acetate 40
%, Methyl ethyl ketone 20%, cyclohexanone 6%
Is applied by a gravure coating method to form a coating layer having a thickness of 3 μm when dry and cured, and the solvent component is removed by passing through a 90 ° C. hot air drying oven at a moving speed of 15 m / min. A cured adhesive layer (4) is formed, and a thickness of 3 mm is formed on the adhesive layer (4).
Of the acrylic resin plate (weather resistant transparent resin layer (5)) are laminated, pressure-bonded to each other, and then held at 40 ° C. for 24 hours to accelerate and cure the adhesive, and polyethylene terephthalate film (1) / release treatment A five-layer structure consisting of layer (2) / metal vapor deposition layer (3) / adhesive layer (4) / weather resistant transparent resin layer (5) was obtained.

From the thus obtained five-layer structure, the polyethylene terephthalate film (1) / release treatment layer (2) is peeled off, and a metal vapor deposition layer (3) / adhesive layer (4) is obtained.
A three-layer structure comprising the weather resistant transparent resin layer (5) was obtained.
Then, 24% of a polyester adhesive (Takeda Pharmaceutical Co., Ltd., Takelac A-310), a curing agent (Takeda Pharmaceutical Co., Takenate A-) was formed on the metal vapor deposition layer (3) of the three-layer structure. 3) An adhesive solution consisting of 10%, ethyl acetate 40%, methyl ethyl ketone 20%, and cyclohexanone 6% was applied by a gravure coating method to form a coating layer having a thickness of 3 μm at the time of drying and curing at 90 ° C.
The solvent component is removed by passing through a hot air drying oven at a moving speed of 15 m / min to form an uncured adhesive layer (4 '), and a 3 mm thick adhesive layer (4') is formed on the adhesive layer (4 '). Acrylic resin plates (weather-resistant transparent resin layer (5 ')) are overlaid, pressure-bonded and bonded together, and then held at 40 ° C. for 24 hours to accelerate and cure the adhesive to give weather-resistant transparent resin layer (5') / A composite material having a metal vapor deposition layer of the present invention consisting of 5 layers of an adhesive layer (4 ′) / a metal vapor deposition layer (3) / an adhesive layer (4) / a weather resistant transparent resin layer (5).

Comparative Example 1 Aluminum metal was vapor-deposited on the acrylic resin plate having a thickness of 3 mm used in Example 1 by using a roll-up type vapor deposition apparatus, but the acrylic resin plate cannot be rolled up and vapor-deposited. I couldn't do that.

[0025]

According to the present invention, even a rigid transparent resin plate
It is possible to apply a roll-up type vapor deposition device easily, at low cost, with good productivity, and it is possible to provide a high-quality metal vapor deposition layer with no vapor deposition unevenness, and because it does not select the material of the transparent resin plate, it has excellent weather resistance. And a composite material having a durable metal vapor deposition layer can be provided.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a composite material having a metal vapor deposition layer of the present invention.

2A to 2D are schematic cross-sectional views in the order of steps until a composite material having a metal vapor deposition layer shown in FIG. 1 is produced.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Plastic film 2 Release treatment layer 3 Metal vapor deposition layer 4 Adhesive layer 4'Adhesive layer 5 Weather resistant transparent resin layer 5'Weather resistant transparent resin layer

Claims (5)

[Claims] 1. A metal vapor deposition having a five-layer structure in which a weather resistant transparent resin layer (5, 5 ′) is bonded to both sides of a metal vapor deposition layer (3) via adhesive layers (4, 4 ′). Composite material with layers. 2. A composite material having a metal vapor deposition layer according to claim 1, wherein the metal vapor deposition layer (3) is an aluminum vapor deposition layer. 3. The composite material having a metal vapor deposition layer according to claim 1, wherein the weather resistant transparent resin layer (5, 5 ′) is an acrylic resin. 4. A release treatment layer (2) is formed on one surface of a plastic film (1) which can be easily vapor-deposited by a roll-up type vapor deposition device, and a metal is vapor-deposited on the release treatment layer (2). After forming a metal vapor deposition layer (3) and bonding the surface of the metal vapor deposition layer (3) and the weather resistant transparent resin layer (5) via the adhesive layer (4) by a dry lamination method, a release treatment layer At the interface between (2) and the metal vapor deposition layer (3), the metal vapor deposition layer (3) /
A three-layer structure comprising an adhesive layer (4) / a weather resistant transparent resin layer (5) is prepared, and then a weather resistant transparent resin layer (5 ′) is formed on the metal vapor deposition layer (3) side of the three layer structure. The weather-resistant transparent resin layer (5) / adhesive layer (4) / metal vapor deposition layer (3) / adhesive layer (4 ′) / which is adhered by a dry laminating method via the adhesive layer (4 ′) Weatherproof transparent resin layer (5 ')
And a method for producing a composite material having a metal vapor deposition layer having a five-layer structure. 5. The method for producing a composite material having a metal vapor deposition layer according to claim 4, wherein the plastic film (1) is a polyethylene terephthalate film.