JPH0789010A - Moldable highly sharp laminated metal panel and decorative sheet used therein - Google Patents

Abstract

PURPOSE:To obtain excellent moldability and high sharpness by constituting a first thermoplastic resin layer of a specific vinyl chloride resin film and constituting a second thermoplastic resin layer of a specific polyester film composed of a specific copolyester resin. CONSTITUTION:A decorative sheet is formed by laminating a first thermoplastic resin layer 3, an adhesive layer 4, a printing ink layer 5 and a second thermoplastic resin layer 6 in this order from below. The first thermoplastic resin layer 3 adsorbs the unevenness of the printing ink layer 5 together with the adhesive layer 4 to prevent the generation of unevenness on the surface of the first thermoplastic resin layer 3 to obtain good moldability and is composed of a vinyl chloride resin film containing 5-50 pts.wt. of a plasticizer with respect to 100 pts.wt. of a resin. The second thermoplasric resin layer 6 forms a surface layer and has function making a printing pattern sharp and imparting moldability and is composed of a polyester film formed from a co-polyester resin wherein the difference between cold crystallizing temp. and glass transition temp. is 60 deg.C or less and having quasi-crystal melting peak temp. between cold crystallizing temp. and an m.p. and having tensile elastic modulus of 1-500MPa.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-image-quality laminated metal sheet having a high moldability, and in particular, it has a high moldability and is used for household appliances such as refrigerators, fan heaters (stoves) and audio equipment. TECHNICAL FIELD The present invention relates to a plastic laminated metal plate of Shinei and a decorative sheet used for the same.

[0002]

2. Description of the Related Art Conventionally, decorative steel sheets having a steel sheet surface colored or patterned have been widely used in various fields such as electrical appliances. Examples of such decorative steel sheets include (a)
As described in Japanese Examined Patent Publication No. 61-51988,
A laminated metal plate in which a polyester film on which a pattern is printed is laminated on a metal plate to form a polyester film / printing ink layer / metal plate from the surface side, (b) JP-B-63-1
As described in Japanese Patent No. 3838, a polyester film on which a pattern is printed is laminated on the surface of a metal plate coated with a polyvinyl chloride film, and a polyester film / printing ink layer / vinyl chloride resin layer / from the surface side. Laminated metal plate composed of metal plate, (C) Surface thermoplastic resin layer / adhesive layer / printing ink layer / basic thermoplastic layer which is transparent from the surface side as described in JP-B-63-280627 As a constitution laminated on the constitution of resin layer / adhesive layer / metal plate,
The basic thermoplastic resin and the surface thermoplastic resin layer have a predetermined melting temperature, and the visible light transmittance of the transparent surface thermoplastic resin layer is regulated within a predetermined range to achieve high-definition high-definition lamination. Metal plate, (d) A transparent polyester film on which a pattern is printed as described in JP-A-4-238026 and another thermoplastic resin film via an adhesive with the printing ink layer as the inner surface. It is laminated and laminated on a metal plate with a polyester film as a surface layer via an adhesive, and a polyester film / printing ink layer / adhesive layer / thermoplastic resin layer / adhesive layer / metal plate which is transparent from the surface side is formed. As a constitution, there is a high-definition image laminated metal plate which has a high-definition image by defining the haze value and the visible light transmittance of the polyester film in a predetermined range.

However, in each of the above-mentioned conventional laminated metal sheets, in practice, a polyester film is used on the outermost surface, and a biaxially stretched film is also used. Therefore, since the film has poor flexibility and elongation characteristics,
There is a problem in formability, especially deep drawability and suitability for 90 ° bending, and thus it has been widely used in home electric appliances and the like, but it has become a major bottleneck in the design development of these products. Because it is preferable to be able to perform deep drawing in order to support the rounded shape of home appliances,
For conventional home appliances and parts using metal plates with poor formability, such as refrigerator doors, plastic parts are used for parts that cannot be applied, and laminated metal plates are used for surface parts that are relatively easy to adapt. I used it, and responded with a combination of both. For this reason, the use of conventional laminated metal sheets increases the number of parts and increases the cost, and there are restrictions in terms of shape and design, and it is not possible to design freely. It was

[0004]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a laminated metal plate which solves the restriction on the design development due to the poor moldability of the above-mentioned conventional laminated metal plate and exhibits a high image clarity. To aim.

[0005]

In order to solve the above-mentioned problems and to achieve the object, in the formable high-definition image laminated metal plate of the present invention, in order to solve the above-mentioned problems, a first thermoplastic resin layer, an adhesive layer, In a decorative sheet in which a printing ink layer and a second thermoplastic resin layer are laminated in the order described, the first thermoplastic resin layer contains 5 to 50 parts by weight of a plasticizer with respect to 100 parts by weight of the resin. Made of vinyl chloride resin film
The thermoplastic resin layer comprises a copolyester resin having a difference between the cold crystallization temperature and the glass transition temperature of 60 ° C. or less,
A decorative sheet for a formable high-definition laminated metal sheet, which is a polyester film having a quasi-crystal melting peak temperature between a cold crystallization temperature and a melting point and a tensile elastic modulus of 1 to 500 MPa. is there. Further, in the layer structure of, the first thermoplastic resin layer is made of a vinyl chloride resin film containing 5 to 50 parts by weight of a plasticizer with respect to 100 parts by weight of the resin, and the second thermoplastic resin layer is used together. Made of polymerized polyester resin and has a melting point of 2
A decorative sheet for formable high-definition laminated metal sheet, which is a polyester film having a glass transition temperature of 70 ° C or lower at 10 to 245 ° C. Further, in the layer structure of 1, the first thermoplastic resin layer is made of a vinyl chloride resin film containing 5 to 50 parts by weight of a plasticizer with respect to 100 parts by weight of the resin, and the second thermoplastic resin layer is 2 A laminated film in which two layers of axially stretched polyester film are laminated, and the melting point of the inner layer closer to the back side is 17
0-220 ℃, the melting point of the surface layer farther to the back side is 220-
It is also a decorative sheet for a moldable high-definition laminated metal plate, which is a laminated polyester film having a two-layer structure at 255 ° C.

Further, in the formable high-definition laminated metal plate, the decorative sheet and the above-mentioned decorative sheet and the metal plate are laminated via an adhesive between the back surface of the decorative sheet and the metal plate. is there.

The present invention will be described in detail below with reference to the drawings. FIG. 1 is an enlarged vertical sectional view of a main part of a formable high-definition image laminated metal plate according to the present invention. The layer structure is such that the first adhesive layer 2, the first thermoplastic resin layer 3, the second adhesive layer 4, the printing ink layer 5, and the second thermoplastic resin layer 6 are sequentially formed on the metal plate 1. It is laminated.

As the metal plate 1, mild steel plate, electroformed iron foil, aluminum plate, copper plate, etc., or zinc, tin, lead,
It is possible to use a material obtained by plating one kind or two kinds of aluminum, copper, chromium, nickel and the like. Alternatively, those obtained by coating the surface of these with a sol of vinyl chloride resin and gelling them can be used.

As the first thermoplastic resin layer 3 laminated on the metal plate 1 via the first adhesive layer, the unevenness of the printing ink layer 5 and the printing ink layer 5 and the first thermoplastic resin layer 3 are formed. Along with the second adhesive layer 4 which is interposed between the resin layer 3 and the resin layer 3, it has a function of absorbing irregularities of the printing ink layer 5 and preventing irregularities from being generated on the surface of the first thermoplastic resin layer. With
It is essential to obtain good moldability. The resin used in the first thermoplastic resin layer 3 may be any resin that exhibits such an action, and examples thereof include vinyl chloride resin, acrylic resin, ABS resin, styrene resin, vinyl chloride / vinyl acetate. Examples thereof include polymers. Among them, a vinyl chloride resin is used in an amount of 5 to 100 parts by weight of the plasticizer.
Those containing 50 parts by weight are preferable. The plasticizer content is particularly preferably 5 to 30 parts by weight. When it is less than 5 parts by weight, moldability is deteriorated, while when it is more than 50 parts by weight, dusts and the like are easily visible and aesthetic defects are conspicuous.

The thickness of the first thermoplastic resin layer 3 is 10 to 10.
The range of 200 μm is preferable. If less than 10 μm,
Since the unevenness of the printing ink layer 5 in contact with the back surface of the thermoplastic resin layer can not be absorbed, the formability such as deep drawing formability and bending workability is poor. On the other hand, a thickness of more than 200 μm is not preferable for moldability. However, if the molding process is small, 20
A thickness of 0 μm or more can improve the design. The first thermoplastic resin layer 3 may have a two-layer structure of transparent and colored. In particular, for the purpose of expressing the luster of wood grain, a pearl pigment is kneaded, and / or a sine wave, a Bessel function, an elliptic function, etc., as a concavo-convex embossing. When a fine line-shaped groove having a depth and an opening width of about 0.1 to 100 μm is formed, a design expression expressing a feeling of shinyness can be obtained. In the design expression of wood grain, it is effective that the overall running direction of the wood grain and the overall running direction of the lines are substantially orthogonal to each other. Since both the wood grain and the lines are curved, it is not necessary that the straight lines are exactly orthogonal to each other, and if the average running directions of both of the entire design surface are approximately orthogonal, or vice versa It suffices if the traveling directions cross to the extent that can be expressed as. The first thermoplastic resin layer 3 has an important meaning in terms of moldability and high image clarity, but also has an important meaning in terms of design expression as described above. The coloring described above may be formed by forming the colored layer of the first thermoplastic resin layer on the entire surface,
It may be kneaded with a colorant.

The second thermoplastic resin layer 6 forms the surface layer of the moldable high-definition laminated metal plate, is transparent, and makes the printed pattern of the underlying printing ink layer 5 stand out clearly. In addition, it serves to protect the printing ink layer 5. Further, the second thermoplastic resin layer 6 has a formability which is an important factor in the present invention, that is, deep drawing,
It is a layer that allows the high-image-quality laminated metal sheet having moldability to have a property capable of withstanding a bending process of up to 180 °. This second
The resin layer having moldability capable of forming the thermoplastic resin layer 6 is made of a copolyester having a difference between the cold crystallization temperature and the glass transition temperature of 60 ° C. or less, and has a quasi-crystal structure between the cold crystallization temperature and the melting point Has a melting peak temperature and a tensile modulus of 1-5
Polyester film of 00 MPa, melting point of 210-245 ° C, glass transition temperature of 70 ° C
A polyester film made of the following copolyester, a laminated film in which two biaxially stretched polyester films are laminated, and the melting point of the inner layer closer to the metal plate is 170 to 2
At 20 ° C, the melting point of the surface layer farther from the metal plate is 220 to 255.
It is possible to use a laminated polyester film having a two-layer structure at a temperature of 0 ° C. The thickness of the film that becomes the second thermoplastic resin layer is in the range of 5 to 200 μm, preferably 12 to 120 μm.
About m is optimal in terms of moldability, sharpness and cost. Then, in order to improve the printability and facilitate the stacking property with the first thermoplastic resin layer, the surface to be the lower layer of the film,
It is preferable to perform an easy adhesion treatment such as a corona discharge treatment. It is also possible to add transparent pigments, dyes, etc. for coloring.

Here, the cold crystallization temperature and the quasi-crystal melting peak temperature are types of temperatures at which the crystalline state of the material obtained by measurement with a differential scanning thermal analyzer changes. That is, first, the sample was melted in a nitrogen stream for 5 minutes at 280 ° C. and then cooled to liquid nitrogen temperature, and this was cooled to 10 ° C.
The specific heat and endothermic heat of the sample are measured while heating at a heating rate of / min. The glass transition temperature is obtained from the change in the specific heat, and the cold crystallization temperature is obtained from the peak temperature of the heat generated by crystallization.
Further, the melting point can be obtained from the heat absorption due to melting. The quasi-crystallization melting peak temperature is also a kind of temperature at which the crystalline state of the material obtained by measurement with a differential scanning thermal analyzer changes. That is, the endothermic heat generation of the sample is measured while increasing the temperature of the sample from room temperature under a nitrogen stream at a rate of 10 ° C./min. The crystal melting temperature is obtained from the endothermic peak due to the crystal melting, and the quasi-crystal melting peak temperature corresponds to the melting of the quasi-crystal obtained as a temperature lower than the peak temperature due to the crystal melting.

Examples of the copolyester capable of obtaining the above-mentioned characteristics include, for example, polyoxyalkylene glycols such as polyethylene glycol and polytetramethylene glycol as diol components, aliphatic diols such as butanediol and hexanediol, and cyclohexanediene. Alicyclic diols such as methanol are used, and dicarboxylic acid components are adipic acid, azelaic acid sebacic acid,
Aliphatic dicanrubonic acid such as dimer acid, alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, isophthalic acid,
An aromatic dicarboxylic acid such as terephthalic acid or naphthalene dicarboxylic acid, or an aliphatic diol or an aliphatic dicarboxylic acid obtained by ring-opening polymerization of ε-caprolactone in the presence of a diol or dicarboxylic acid is used. The polyesters obtained by copolycondensation using one kind or two or more kinds are used. The aliphatic, alicyclic and aromatic units are used for forming a hard segment having an alicyclic or aromatic skeleton, and the aliphatic unit is used for forming a soft segment having an aliphatic skeleton.

The printing ink layer 5 is provided as a lower layer in contact with the above-mentioned second thermoplastic resin layer 6. As the ink used for forming the printing ink layer 5, a vehicle is mixed with a coloring agent such as a pigment or a dye, an extender pigment, a stabilizer, a plasticizer, a catalyst, a curing agent, etc., if necessary.

The vehicle is appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin and the like according to the application, required physical properties, printability and the like.

Examples of the thermoplastic resin include (a) cellulose derivatives such as ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose and cellulose acetate propionate, and (b) styrene resins such as polystyrene and poly-α-methylstyrene. Or styrene copolymers, (c) acrylic resins such as poly (methyl methacrylate), poly (ethyl methacrylate), poly (ethyl acrylate) and poly (butyl acrylate), (d) polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers Examples thereof include polymers and vinyl polymers such as polyvinyl butyral.

Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanazine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine / urea resin. There are condensation resins, silicone resins, polysiloxane resins, and the like, and if necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender pigment, etc. are added. As the curing agent, isocyanate is usually unsaturated polyester resin, polyurethane resin, amine is epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azobisisobutyronitrile is unsaturated polyester resin. Often used in resins.

Known coloring pigments such as carbon black and cyanine blue, pearl pigments such as titanium dioxide-coated mica, etc. are used as the coloring agent to be mixed with the vehicle, and the patterns and patterns include wood grain pattern and stone grain pattern. Natural products, polka dots, abstract patterns such as striped patterns, full-face solids, or combinations thereof are optional.

The printing ink layer 5 is formed by gravure printing on the back surface of the film which is the second thermoplastic resin layer 6,
It is provided by a known printing means such as offset printing or silk screen printing.

An intervening layer should not be provided between the printing ink layer 5 and the second thermoplastic resin layer 6 serving as the surface layer, but the intervening layer should not be provided as long as the coloring property and high image clarity of the ink are not impaired. It is possible to provide layers.

Further, the printing ink layer 5 can be omitted when a picture or pattern is not required. Further, instead of the printing ink layer 5, a solid pattern or a partially patterned pattern is formed on the surface of the first thermoplastic resin layer 1 and / or the lower surface of the second thermoplastic resin layer with aluminum, chromium or the like. It may be provided by a metal thin film layer.

Although the metal plate 1, the first thermoplastic resin layer 3, the printing ink layer 5 and the second thermoplastic resin layer 6 have been described above, the metal plate 1 and the first thermoplastic resin layer 6 serve as adhesive layers. The first adhesive layer 2 is interposed between the thermoplastic resin layer 3 and the second adhesive layer 4 between the first thermoplastic resin layer 3 and the printing ink layer 5. When there is no printed pattern on the entire surface of the printing ink layer 5, or when the printing ink layer 5 is omitted,
The surface of the second thermoplastic resin layer 6 is the first thermoplastic resin layer 2
There is also a case where they face each other via the adhesive layer 4. The first and second adhesive layers serve to secure the adhesion between the layers.

Various kinds of adhesives can be used as the adhesive used for the first adhesive layer 2 and the second adhesive layer 4, and examples of the resin system of the adhesive include (a) phenol resin , Furan-based resin, urea-based resin, melamine-based resin, polyester-based resin, polyurethane-based resin, epoxy-based resin, or other thermosetting resin, if necessary, a crosslinking agent such as isocyanate or amine, methyl ethyl ketone peroxide, Addition of polymerization initiators such as hydroperoxide, azobisisobutyronitrile, etc., polymerization accelerators such as cobalt naphthenate, dimethylaniline, etc. (b) Polyvinyl acetate, polyvinyl chloride, vinyl acetate / vinyl chloride Polymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer, polyvinyl alur, polyvinyl Vinyl polymers such as polyvinylbutyral, polyolefin resins such as polyethylene and polypropylene, polyacrylic ester resins, polymethacrylic acid ester resins, cellulose nitrate, cellulose acetate, polyamide, ionomer, or other thermoplastic resin, (c)
Butadiene / acrylonitrile rubber, neoprene rubber,
Natural rubber, or other rubber, or (d) one or a mixture of two or more of natural resins such as glue, casein, dextrin, starch, gum arabic, rosin, etc. as a main component, and if necessary, A known filler, pigment, dye, stabilizer, solvent, plasticizer or the like may be used as the adhesive.

As a solidifying method for these adhesives, an appropriate method such as a solvent drying type, an emulsion type, a hot melt solidifying type, or a thermosetting type can be selected.

As a method of laminating each layer described above, a film which forms the second thermoplastic resin layer 6 on which the printing ink layer 5 is formed and a film which forms the second thermoplastic resin layer 3 are laminated. The resulting decorative sheet for a high-definition image-forming laminated metal plate according to the present invention and the metal plate 1 may be laminated by a conventionally known laminating means using the above-mentioned adhesive. For example, using an adhesive whose main component is urethane resin, phenol resin, vinyl resin,
Means such as a dry laminating method, a wet laminating method and a hot melt laminating method can be used.

As described above, the adhesive layer, the first thermoplastic resin layer, the adhesive layer, the printing ink layer, and the transparent second thermoplastic resin layer are laminated in this order on the metal plate 1. With such a constitution, it is possible to obtain the moldable high-definition image laminated metal plate according to the present invention and the decorative sheet used therefor, which simultaneously satisfy the moldability, the ink coloring property, and the high-visibility property.

Further, the formable high-definition laminated metal plate of the present invention,
Also, various known hard coat layers may be provided on the surface of the second thermoplastic resin layer 6 which is transparent in the decorative sheet used for the same and within the range not departing from the moldability. For example, a hard coat paint containing an ionizing radiation curable resin such as electron beam or ultraviolet ray curable polyester acrylate or urethane acrylate as a main component is used.

An example of the method for producing a high-definition image-forming laminated metal sheet and a decorative sheet used therefor according to the present invention is excellent in formability such as deep-drawing workability and bending workability, and has excellent heat resistance and solvent resistance. An excellent plastic film (front surface film) is used as the second thermoplastic resin layer 6, a pattern is printed on the back surface thereof to form the printing ink layer 5, and the printing ink layer 5 is further formed.
The second adhesive layer 4 is formed by applying an adhesive on the surface on which the
A plastic film (intermediate film) having good moldability is used as the first thermoplastic resin layer 2, and this is laminated with the surface film with the above-mentioned adhesive intervening to obtain the decorative sheet according to the present invention. Next, an adhesive is applied to the metal plate 1 to form a first adhesive layer 2, and the decorative sheet is laminated thereon with the intermediate film side facing the metal surface side, and the formability according to the present invention is obtained. Obtain a high-definition laminated metal plate. By uniformly applying a constant pressure from the surface during the lamination, when the printing ink layer 5 has irregularities, the irregularities are embedded in the intermediate film side to obtain a laminated metal plate having a flat surface.

[0029]

In the moldable high-definition laminated metal sheet and the decorative sheet used for the same according to the present invention, the second thermoplastic resin layer serving as the surface film is a polyester resin film having specific thermal and mechanical characteristics. And using a vinyl chloride resin film having a specific plasticizer content in the first thermoplastic resin layer serving as an intermediate film, a laminated metal plate having moldability suitable for deep drawing and bending, and It becomes a decorative sheet. In addition, a laminated metal sheet and a decorative sheet having various physical properties such as moldability, heat resistance, and processability by using a laminated polyester film having a two-layer structure in which specific thermal characteristics are defined as the second thermoplastic resin layer. Becomes Furthermore, a transparent, excellent heat-resistant and solvent-resistant film is used for the second thermoplastic resin layer, and a printing ink layer is formed directly on the back surface of the film, resulting in ink coloring, high image clarity, And a laminated metal plate and decorative sheet having excellent surface properties such as chemical resistance. In addition, by providing the adhesive layer and the first thermoplastic resin layer having moldability on the inner surface side of the printing ink layer, even if the printing ink layer has irregularities due to the printed pattern, Unevenness on the surface of the first thermoplastic resin layer, which becomes the surface film, due to the flattening of the unevenness of the first thermoplastic resin layer and the absorption effect of the first thermoplastic resin layer due to the pressure applied when the decorative sheet is laminated on the metal plate. It is possible to obtain a laminated metal plate having a flat and clean surface.

[0030]

【Example】

Example 1 As a surface film to be the second thermoplastic resin layer 6, a biaxially stretched polyester film having a corona discharge treatment on one side, having a melting point of 210 to 245 ° C. and a glass transition temperature of 70 ° C. or less ( Teijin Ltd. D type, thickness 25 μm, melting point 230 ° C., glass transition temperature 55 ° C.) is used, and urethane resin-based two-component curable ink (NL-ALFA manufactured by The Inktech Co., Ltd.) is used on the treated surface. Was subjected to gravure printing to form a printing ink layer 5. A polyester urethane two-component curable adhesive (DLU-1000 manufactured by The Inktech Co., Ltd.) was applied to the printing ink layer 5 side of this surface film with a reverse roll coater to a dry thickness of 5 g / m ^2. Thus, the second adhesive layer 4 was applied, and an intermediate film made of colored polyvinyl chloride to be the first resin layer was laminated thereon by dry lamination. As described above, a decorative sheet according to the present invention to be used for a moldable high-definition image laminated metal plate was obtained.

The metal plate 1 is degreased and has a thickness of 0.5 mm.
On one surface of the mild steel plate of No. 3, a modified acrylic resin-based two-component curable adhesive (Y-6 manufactured by Yokohama Rubber Co., Ltd.) to be the first adhesive layer 2 is formed.
067) was applied by a roll coater so that the thickness when dried was 8 g / m ² . Then, the mild steel plate is heated to a temperature of 200 ° C., the decorative sheet is attached using a metal pressure roll heated to 200 ° C., and then water-cooled to form a high-definition imageable laminated metal plate according to the present invention. Got

Example 2 Instead of the surface film used in Example 1, a copolymerized polyester having a difference between the cold crystallization temperature and the glass transition temperature of 60 ° C. or less was used. As a polyester film having a quasicrystal melting peak temperature between them and a tensile elastic modulus of 1 to 500 MPa, a soft polyester film (Lumirror Type N manufactured by Toray Industries, Inc., thickness 50 μm, cold crystallization temperature 35
C., melting point 185.degree. C., quasicrystal melting peak temperature 120.degree. C., tensile elastic modulus 190 MPa) to obtain a decorative sheet in the same manner as in Example 1, and using this decorative sheet, the moldability according to the present invention is obtained. A high-definition laminated metal plate was obtained.

Example 3 Instead of the surface film used in Example 1, a biaxially stretched polyester film was used.
A laminated polyester film having a two-layer structure in which the melting point of the inner layer closer to the back surface side is 170 to 220 ° C. and the melting point of the surface layer farther to the back surface side is 220 to 255 ° C. in the laminated film (total thickness 25 μm Inner layer side: melting point 200 ° C., thickness 20 μm, surface layer side: melting point 235 ° C., thickness 5 μm) A decorative sheet was obtained in the same manner as in Example 1, and the decorative sheet was used to apply the present invention. A moldable high-definition laminated metal plate was obtained.

<< Comparative Example >> As a comparative example, a product currently in practice was also manufactured in the following manner. Instead of the surface film used in Example 1, a biaxially stretched polyethylene terephthalate film having a melting point of 263 ° C., a glass transition temperature of 70 ° C. and a corona discharge treatment on one side (Lumirror S type manufactured by Toray Industries, thickness 25 μm) A decorative sheet was obtained in the same manner as in Example 1 except that was used, and a high-definition laminated metal plate was obtained using this decorative sheet.

As shown in Table 1, the laminated metal sheets of Examples and Comparative Examples obtained as described above exhibited excellent performance in terms of moldability and the like.

[0036]

[Table 1]

[0037]

[Effect] According to the formable high-definition image laminated metal plate and the decorative sheet used for the same according to the present invention, since it has a pattern such as a printed pattern with high-definition image and a rich design feeling and is excellent in formability, It enables deep drawing and bending that were possible,
Conventionally, it is possible to manufacture a product using a metal plate, which is usually composed of 2 to 3 parts or more, with a smaller number of parts such as 1 part depending on the shape, which leads to cost reduction and further design development in terms of design. It can greatly contribute to the expansion.

[Brief description of drawings]

FIG. 1 is an enlarged sectional view of an essential part of a formable high-definition image laminated metal plate according to the present invention.

[Explanation of symbols]

 1 Metal Plate 2 1st Adhesive Layer 3 1st Thermoplastic Resin Layer 4 2nd Adhesive Layer 5 Printing Ink Layer 6 2nd Thermoplastic Resin Layer

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B29K 33:04

Claims (6)

[Claims] 1. A decorative sheet in which a first thermoplastic resin layer, an adhesive layer, a printing ink layer, and a second thermoplastic resin layer are laminated in this order from the back side, The plastic resin layer contains 5 parts of plasticizer per 100 parts by weight of the resin.
To 50 parts by weight of a vinyl chloride resin film, and the second thermoplastic resin layer is made of a copolyester resin having a difference between the cold crystallization temperature and the glass transition temperature of 60 ° C. or less. A decorative sheet for formable high-definition laminated metal sheet, comprising a polyester film having a quasicrystal melting peak temperature between the melting point and the melting point and having a tensile elastic modulus of 1 to 500 MPa. 2. A decorative sheet in which a first thermoplastic resin layer, an adhesive layer, a printing ink layer, and a second thermoplastic resin layer are laminated in this order from the back side, and the first heat The plastic resin layer contains the plasticizer in an amount of 5 to 100 parts by weight of the resin.
Made of vinyl chloride resin film containing 50 parts by weight,
The second thermoplastic resin layer is made of a copolyester resin and has a melting point of 210 to 245 ° C. and a glass transition temperature of 7
A decorative sheet for a high-definition imageable laminated metal sheet, which comprises a polyester film having a temperature of 0 ° C. or lower. 3. A decorative sheet in which a first thermoplastic resin layer, an adhesive layer, a printing ink layer, and a second thermoplastic resin layer are laminated in this order from the back surface side. The plastic resin layer contains 5 to 5 parts of the plasticizer with respect to 100 parts by weight of the resin.
A laminated film comprising a vinyl chloride resin film containing 0 part by weight, and the second thermoplastic resin layer having two biaxially stretched polyester films laminated, wherein the melting point of the inner layer closer to the back side is 170 to 220 ° C. A decorative sheet for a formable high-definition laminated metal sheet, comprising a laminated polyester film having a two-layered structure in which the melting point of the surface layer farther to the back side is 220 to 255 ° C. 4. A formable high-definition laminated metal plate, characterized in that the decorative sheet according to claim 1 and the metal plate are laminated via an adhesive between the back surface of the decorative sheet and the metal plate. . 5. A formable, high-definition laminated metal plate comprising the decorative sheet according to claim 2 and the metal plate laminated between the back surface of the decorative sheet and the metal plate via an adhesive. . 6. A moldable high-definition laminated metal plate, characterized in that the decorative sheet according to claim 3 and the metal plate are laminated via an adhesive between the back surface of the decorative sheet and the metal plate. .