JPH11309809A - Heat-resistant metallic foil laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate heat deterioration and yellowing caused by thermal melting of resin layers formed on both sides of a metallic foil, and prevent decolorization from a resin layer by forming a polyamide-imide resin on one side of a metallic foil having specified thickness and forming a polyamide-imide layer on the other side of the metallic foil. SOLUTION: A polyamide-imide resin layer A is formed on one side of a metallic foil of 10-50 μm thickness and a polyamide-imide resin layer B is formed on the other side of the metallic foil for manufacturing a heat-resistant metallic foil laminate. In this case, either or both of the resin layer A and B may be colored layers, and a metallic foil of broad continuous length may be used. A powdered heat-resistant laminate formed by powdering the metallic foil of broad continuous length, yarn shape, tape shape or the like can be used. Various metals such as AL, Cu, Ag, Au, Ni, Zn, In, Sn, Cr, Ni-Cr or the like or an alloy thereof can be used for the metallic foil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant metal foil laminate using a metal foil. More specifically, the present invention provides a Buddhist altar, a Buddhist utensil, a sliding door,
For decoration of lacquerware, ceramics, fans, artificial flowers, books, etc., or for decorative printing of confectionery, dairy products, other foods, medicines, cosmetics, tobacco, etc., and for printed circuits and electromagnetic shielding, etc. The present invention relates to a heat-resistant metal foil laminate particularly useful when used as a heat-resistant metal powder utilizing a metal foil used for a conductive ink, a conductive paint, and a conductive adhesive.

[0002]

2. Description of the Related Art Conventionally, as a metal powder used for the above-mentioned various applications, a metal thin film layer such as a resin layer or a metal vapor-deposited layer formed by a thin-film forming method such as vacuum vapor deposition is formed on a plastic film as a base film. And a resin layer which is obtained by peeling the resin layer integrally from the plastic film and thereafter cutting or crushing the peeled one. This is a metal powder in which a resin layer, an extremely thin metal thin film layer, and a resin layer are sequentially laminated.
The resin layer used for the conventional metal powder includes an acrylic resin, a butyral resin, a polyester resin, a polypropylene resin, a vinyl chloride resin, polyvinyl acetate, nitrocellulose, polyvinyl alcohol, casein, gelatin, and vinyl acetate-vinyl chloride. It is a resin layer made of a copolymer resin, a polyamide resin, an epoxy resin, or the like. In practice, specific resins such as an acrylic resin, a butyral resin, a polyester resin, a polypropylene resin, and a vinyl chloride resin are used.

However, conventional metal powders are all resin molded products, specifically, ABS resin, polycarbonate resin,
When used for decoration of a resin molded product such as a polystyrene resin, there are the following disadvantages. That is, a high temperature of 250 ° C. or more is required at the time of molding a resin molded product, and the residence time of the metal powder under that temperature condition is as long as 5 to 10 minutes. Therefore, the resin layers formed on both surfaces of the metal thin film layer are thermally degraded, melted and yellowed. And the beautiful metallic feeling is spoiled by yellowing of the resin layer. When the resin layer is colored, the resin layer is thermally degraded and melted, the color is removed from the colored resin layer, the resin molded product is colored, and a so-called color squeal phenomenon occurs. Then, the metallic sensation is blurred and reduced in appearance due to the color squeal phenomenon, and the beautiful metallic sensation is impaired. Also,
Conventional metal powders cannot maintain the shape of the metal powder due to poor shape stability, and the metal powder itself is easily broken. For example, when the metal powder is a thin and short thread-like metal powder,
The thread-like metal powder is finely cut during molding of the resin molded product. Furthermore, the conventional metal powder has a weak adhesion between the metal thin film layer and the resin layers formed on both surfaces thereof, and the resin layer is peeled off from the metal thin film layer during molding of the resin molded product. In this case, the color of the colored layer itself and the color of the metal thin film layer are mixed. For example, in the case of a metal powder in which a silver thin Al layer is used for the metal thin film layer and the resin layers on both sides are colored yellow by coloring the resin layers on both sides with gold, when the resin molded product is viewed with the naked eye, the gold and silver are observed. Colors appear mixed. Furthermore, in the conventional metal powder, usually, a resin layer, a metal thin film layer, and a resin layer sequentially formed on a plastic film, which is a base film, are integrally peeled off from the plastic film, and then the peeled one is cut or crushed. In order to peel off the resin layer, the metal thin film layer, and the resin layer integrally from the plastic film, it is necessary to previously form a release layer on the plastic film.

The present inventor has studied to develop a metal powder in which many of the above-mentioned disadvantages have been eliminated. As a result, a polyamide imide resin layer A, a metal thin film layer, a polyamide imide resin layer B, And a metal film having a polyamideimide resin layer A formed on one side of a metal thin film layer and a polyamideimide resin layer B formed on the other side. And succeeded in obtaining powder, and already filed a patent application (Japanese Patent Application No. 10-39747).

[0005] However, the above-mentioned film for producing metal powder and metal powder developed and filed by the present inventors have the following disadvantages. Since the metal thin film layer is formed by a thin film generation method such as vacuum deposition, it is extremely thin, so when it is cut or crushed to obtain metal powder, the so-called cutting is poor and it is difficult to cut cleanly, and the cross-section becomes white. . Since the metal thin film layer is extremely thin, a so-called interference pattern occurs when the polyamide imide resin layer A is formed on one side of the metal thin film layer and the polyamide imide resin layer B is formed on the other side. As in the case of the conventional metal powder, the polyamideimide resin layer A, the metal thin film layer, and the polyamideimide resin layer B sequentially formed on the plastic film as the base film are integrally peeled from the plastic film, and then the peeling is performed. Since the metal powder is obtained by cutting or crushing the crushed material, there are many processing steps. And since there are many processing steps, cost becomes high.

The present invention eliminates all the drawbacks of the above-mentioned metal powder-produced film and metal powder developed by the present inventor and of the above-mentioned conventional metal powder. It is.

[0007]

SUMMARY OF THE INVENTION The present invention has a thickness of 10 to 5 mm.
A heat-resistant metal foil laminate comprising a polyamide-imide resin layer A formed on one side of a 0-μm metal foil and a polyamide-imide resin layer B formed on the other side. In the heat-resistant metal foil laminate of the present invention, one or both of the polyamideimide resin layer A and the polyamideimide resin layer B may be colored. The present invention provides a wide and long heat-resistant metal foil when a polyamideimide resin layer A is formed on one side using a wide and long metal foil and a polyamideimide resin layer B is formed on the other side. Can be used as a laminate. In this case, if one or both of the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored, they can be used as a beautiful heat-resistant colored metal foil laminate. Further, the wide and long heat-resistant metal foil laminate can be cut into a vertically long shape into a thread or tape shape and used as a thread- or tape-like heat-resistant metal foil laminate. Furthermore, the wide and long heat-resistant metal foil laminate
It may be cut into an appropriate shape, such as cut into a rectangle such as a rectangle, and used as a heat-resistant metal foil laminate having an appropriate shape. Furthermore, the heat-resistant metal foil laminate of the present invention is a powdery heat-resistant metal foil that is made of a wide and long sheet, a thread or a tape, an appropriate shape such as a rectangle, or the like. It can also be used as a laminate. In this case, the heat-resistant metal foil laminate becomes a heat-resistant metal powder. The above heat-resistant metal powder can be used as a beautiful heat-resistant colored metal powder when one or both of the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the metal foil of the present invention, for example, Al, Cu, Ag, Au, Ni, Zn, In, S
Various metal or alloy metal foils composed of n, Cr, Ni-Cr, and the like can be used.

The thickness of the metal foil is 10 to 50 μm. When the thickness of the metal foil is thinner than 10 μm, it is too thin, and when the polyamideimide resin layer A or the polyamideimide resin layer B is formed on the surface of the metal foil, wrinkles are generated on the metal foil or the metal foil is easily cut. In some cases, it becomes difficult to perform coating processing smoothly. In addition, it is difficult to smoothly perform processing for cutting or crushing to obtain metal powder. If the thickness of the metal foil is more than 50 μm, it is too thick, so to speak, it is hard and thick like a plate, making it difficult to perform coating processing smoothly. Also, the processing when cutting or crushing to obtain metal powder is also smooth. It becomes difficult to do. Further, the thickness of the metal foil is 50 μm.
If the thickness is larger, when the polyamide-imide resin layer A or the polyamide-imide resin layer B is colored, the color of the metal foil itself appearing in the cut or crushed cross section becomes unnoticeable, which is not preferable.

A polyamide-imide resin layer A is formed on one side of the metal foil, and a polyamide-imide resin layer B is formed on the other side. Both the polyamide-imide resin layer A and the polyamide-imide resin layer B have transparency. The polyamide imide resin layer A and the polyamide imide resin layer B can be formed by a conventionally known coating method such as a reverse roll coating method, a die coating method, and a gravure coating method.

The thickness of each of the polyamideimide resin layer A and the polyamideimide resin layer B is 0.1 to 100 μm.
m, preferably 1.0 to 50 μm, more preferably 2.
0 to 30 μm is appropriate. Polyamideimide resin layer A
When the thickness of the polyamide-imide resin layer B is smaller than 0.1 μm, it is not easy to form a continuous resin coating film. Also,
When the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored, they are hardly colored. The thickness of the polyamide-imide resin layer A and the polyamide-imide resin layer B is 100
If the thickness is larger than μm, the proportion of the resin in the metal powder increases, and the proportion of the metal decreases, so that the overall metallic luster tends to be insufficient. In addition, when used in conductive inks, conductive paints, conductive adhesives, and the like that require electrical conductivity, it is difficult to obtain sufficient electrical conductivity. Further, it becomes difficult to obtain fine metal powder easily. Furthermore, it becomes difficult to cut or crush the heat-resistant metal foil laminate smoothly. From these, the thickness of the polyamide-imide resin layer A and the polyamide-imide resin layer B is particularly preferably 2.0 to 30.
μm is optimal.

One or both of the polyamide imide resin layer A and the polyamide imide resin layer B may be colored, or both may not be colored. In order to color the polyamide-imide resin layer A and the polyamide-imide resin layer B, a dye may be mixed into these resins. If the pigment is a transparent pigment, it can be mixed with these resins and colored.

When the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored, when viewed from the colored resin layer side, the color of the metal or alloy used for the metal foil is colored and appears. . That is, a beautiful colored metallic feeling is exhibited. When these resin layers are not colored, the colors of the metals and alloys used for the metal foil appear as they are when viewed from the uncolored resin layer side. That is, a beautiful metallic feeling appears.

When both the polyamide imide resin layer A and the polyamide imide resin layer B are colored, the polyamide imide resin layer A and the polyamide imide resin layer B may be colored in the same color, or may be colored in different colors. Is also good. If different colors or one color is used, the metal powder etc. will appear different colors on the front and back, so when using metal powder etc., use two types of metal powder etc. of different colors. Looks like

In the present invention, first, a polyamideimide resin layer A is formed on one surface of a wide and long metal foil, for example. Next, a polyamide-imide resin layer B is formed on the other side of the metal foil.
To form As described above, the polyamide imide resin layer A and the polyamide imide resin layer B can be formed by a conventionally known coating method such as a reverse roll coating method, a die coating method, and a gravure coating method.

Prior to forming the polyamide-imide resin layer A and the polyamide-imide resin layer B, a polyamide-imide clear layer is provided on a metal foil, and the polyamide-imide resin layer A and the polyamide-imide resin layer B Of the present invention, and a polyamideimide clear layer is interposed between the metal foil and the polyamideimide resin layer A or the polyamideimide resin layer B. When the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored, a dye or a pigment is mixed in the resin layer, so that the adhesion between the resin and the metal foil tends to be weak. To prevent this, it is effective to interpose a polyamide imide clear layer. Further, it is highly preferable that the polyamideimide clear layer is provided from above the colored polyamideimide resin layer A or the colored polyamideimide resin layer B, since it effectively functions as protection of the dye or the pigment. Including those that did. Prior to forming the polyamide-imide resin layer A or the polyamide-imide resin layer B, a polyamide-imide clear layer is provided on the metal foil, or the polyamide-imide clear layer is formed by coloring the polyamide-imide resin layer A or the colored polyamide-imide resin. When provided from above the layer B, or further, when the polyamideimide clear layer is provided on both sides of the colored polyamideimide resin layer A or the colored polyamideimide resin layer B, the colored polyamideimide resin layer A and The total thickness of the contacted polyamideimide clear layer and the total thickness of the colored polyamideimide resin layer B and the contacted polyamideimide clear layer are all 0.3 to 1
It is suitable to be 00 μm, preferably 1.0 to 50 μm, more preferably 2.0 to 30 μm.

As described above, the polyamide-imide resin layer A is formed on one side of the heat-resistant metal foil laminate of the present invention, that is, the metal foil having a thickness of 10 to 50 μm, and the polyamide-imide resin layer B is formed on the other side. Can be obtained. In this case, the heat-resistant metal foil laminate is wide and long.

Next, when the obtained wide and long heat-resistant metal foil laminate is cut vertically into a thread or tape shape, a thread- or tape-shaped heat-resistant metal foil laminate is obtained. Further, the wide and long heat-resistant metal foil laminate can be cut into an appropriate shape such as a rectangular shape to obtain a heat-resistant metal foil laminate having an appropriate shape. Furthermore, the heat-resistant metal foil laminate of the present invention may be a wide and long one, a thread-like or tape-like one, an appropriate shape such as a rectangle, or the like cut into an appropriate size according to the application. It can also be crushed or made into a powder form, and used as a powdery heat-resistant metal foil laminate. In this case, the heat-resistant metal foil laminate becomes a heat-resistant metal powder. As described above, if any one or both of the polyamideimide resin layer A and the polyamideimide resin layer B are colored, the heat resistant metal powder can be used as a beautiful heat resistant colored metal powder.

In the present invention, since the polyamideimide resin layer is used as the resin layer, the heat-resistant metal foil laminate has very good shape stability. Therefore, the heat-resistant metal foil laminate does not easily shatter, and the processability for obtaining a powdery heat-resistant metal foil laminate, that is, a heat-resistant metal powder, is very good.

The heat-resistant metal powder of the present invention thus obtained is, of course, a polyamide-imide resin layer A having a thickness of 10 to 5 mm.
Since the 0 μm metal foil and the polyamideimide resin layer B are integrated, the shape stability is very good, the shape can be maintained well, and the heat-resistant metal powder is easily broken. Nothing. In particular, since the shape stability is very good even during the molding process of the resin molded product, the shape of the heat-resistant metal powder obtained by cutting or crushing to an appropriate size can be maintained as it is. it can.

When the heat-resistant metal foil laminate is cut or crushed, any cutting method or crushing method may be used. For example, it is slit into a width of 0.05 mm (50 μm) to 1.5 mm and made into a thread-like shape.
An appropriate crushing method such as a method of cutting to (100 μm) to 20 mm, a crushing method using a hammer mill, a ball mill, a kneader or the like can be adopted.

In the present invention, the use of a polyamide-imide resin for the resin layer and the use of a metal foil having a thickness of 10 to 50 μm have resulted in a number of special effects described below.

[0023]

EXAMPLE 1 A transparent inorganic pigment was applied to a polyamideimide resin (Toyobo Co., Ltd.) on one side of a wide and long 12 mm thick Al foil (manufactured by Nippon Foil Co., Ltd .: 12 μm thick, 600 mm wide, 1000 m long). (Yellow disazo organic pigment) mixed resin,
A colored polyamideimide resin layer A having a thickness of about 10 μm and colored yellow by a gravure coating method is formed on another surface of the Al foil in the same manner as described above. Form layer B,
A wide and long heat-resistant metal foil laminate of the present invention was obtained. The obtained heat-resistant metal foil laminate was cut into the size of an A4 plate, and 300 heat-resistant metal foil laminates (about 1 cm thick) of the A4 plate obtained by cutting were stacked, It is slit into a width of about 0.2 mm with a metal blade to form a thread, and this thread is cut into a length of about 0.3 mm to obtain a powdery heat-resistant metal foil laminate of the present invention. Was. The obtained powdery heat-resistant metal foil laminate is a heat-resistant metal powder,
It had a beautiful gold metallic feeling. next,
The obtained heat-resistant metal powder was added to an ABS resin melted at about 250 ° C. or higher at a rate of about 10% by weight, and about 1% by weight was added.
A screw pressure is applied for 0 minute to uniformly disperse the heat-resistant metal powder in the ABS resin, and then the ABS resin is cooled, and a beautiful gold-colored heat-resistant metal powder having a metallic feeling is dispersed in a dish-shaped ABS resin. A molded product was obtained. Obtained ABS
With respect to the resin molded product, yellowing, color squealing phenomenon, metallic feeling, shape stability, adhesion between the Al foil and the resin layer, whitening of the cross section, and interference pattern of the heat-resistant metal powder were visually observed.
The observation was as follows. "Yellowness" The presence or absence of beautiful gold discoloration from brown to red was observed with the naked eye. "Color squeal phenomenon" The presence or absence of the color squeal phenomenon was visually observed. “Metallic sensation” Whether or not the metallic sensation was reduced was observed based on whether or not the transparency and the sharpness of the beautiful gold color were visually observed. "Shape stability" It was observed with the naked eye whether or not a thread shape was maintained. "Adhesive force" It was observed with the naked eye whether it was a metallic feeling of gold only or a metallic feeling of a mixture of gold and silver. "Whitening of cross-section" The presence or absence of whitening of the cross-section was visually observed. "Interference pattern" The presence or absence of the interference pattern was observed with the naked eye.

COMPARATIVE EXAMPLE 1 In place of the Al foil, an Al vapor-deposited layer having a thickness of 600 ° was formed on both sides of a 25 μm-thick polyester film.
The procedure was the same as in Example 1, except that a vapor deposition film was used. Comparative Example 2 The procedure of Example 1 was repeated except that an acryl-melamine resin was used instead of the polyamideimide resin. Comparative Example 3 On one surface of a long polyester film having a thickness of 25 μm and a width of 1020 mm, a colored polyamideimide resin layer A colored yellow by adding a transparent inorganic pigment (a yellow disazo-based organic pigment) by a die coating method. An Al thin film layer having a thickness of about 600 ° is formed on the colored polyamide-imide resin layer A by vacuum evaporation.
(1) A colored polyamideimide resin layer B colored yellow by adding a transparent inorganic pigment (a yellow disazo organic pigment) to a thickness of about 10 μm by a die coating method on the thin film layer, and forming a film for metal powder production. I got Next, a metal powder laminate in which the colored polyamide-imide resin layer A, the Al thin film layer, and the colored polyamide-imide resin layer B are integrated is peeled from the polyester film of the film for metal powder production while being rolled, and the metal is peeled off. A laminate for powder was obtained. further,
The obtained laminate for metal powder is cut to the size of an A4 plate, and the cut laminate of A4 plate for metal powder obtained by cutting is cut into 30 pieces.
In a state where 0 sheets (about 1 cm thick) are superimposed, a metal blade is used to slit them into a width of about 0.2 mm to form a thread, and this thread is cut into a length of about 0.3 mm. A metal powder was obtained. The obtained metal powder had a beautiful gold metallic feeling. About 10% by weight of the obtained metal powder is added to an ABS resin melted at about 250 ° C. or higher.
And apply screw pressure for about 10 minutes to add A
After uniformly dispersing the metal powder in the BS resin, the ABS resin was cooled to obtain a dish-shaped ABS resin molded product in which a beautiful metallic metal powder having a metallic feeling was dispersed. The resulting ABS resin molded product was visually observed for yellowing, color squealing phenomenon, metallic feeling, shape stability, adhesion between the Al thin film layer and the resin layer, whitening of the cross section, and interference pattern of the metal powder. The observation was the same as in Example 1.

The results observed in Example 1 and Comparative Examples 1 to 3 are shown in Tables 1, 2 and 3 below. Table 2 “Shape stability” “Adhesion force” Example 1 Retaining thread-like color Gold only Comparative example 1 Retaining thread-like color Gold only Comparative example 2 Filament cut and shattered Coloured color and silvery color mixed Comparative example 3 Filament Holding gold color only

[0026]

Since the present invention is constructed as described above, it has the following effects when used as a heat-resistant metal powder, particularly when used for decoration of a resin molded product. The resin layers formed on both sides of the metal foil do not deteriorate due to heat and are not melted and yellowed. The so-called color squeal phenomenon does not occur because the color is not removed from the resin layer and the resin molded product is colored. The beautiful metallic feeling is not impaired by the yellowing or squealing phenomenon of the resin layer. Since the shape stability of the metal powder is very good, the shape can be maintained well, and the metal powder itself does not easily shatter. The adhesion between the metal foil of the metal powder and the resin layers formed on both surfaces thereof is very good. There is no need to previously form a release layer on the plastic film. Since the metal foil is used when cutting or crushing to obtain the metal powder, so-called cutting is poor and it is difficult to cut cleanly, so that the cross-section does not whiten. That is, there is no whitening of the cross section. No so-called interference pattern is generated because the metal foil is used. Since the number of processing steps is small, the cost is reduced.

Claims (3)

[Claims] 1. A heat-resistant metal foil laminate comprising a polyamide-imide resin layer A formed on one side of a metal foil having a thickness of 10 to 50 μm and a polyamide-imide resin layer B formed on the other side. 2. The heat-resistant metal foil laminate according to claim 1, wherein the heat-resistant metal foil laminate is in a powder form. 3. The heat-resistant metal foil laminate according to claim 1, wherein one or both of the polyamide-imide resin layer A and the polyamide-imide resin layer B are colored.