JP2960173B2 - High-definition laminated metal sheet and decorative sheet used for it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-definition laminated metal sheet, particularly to a high-definition plastic laminated metal sheet used for appliances such as refrigerators and air conditioner covers, and a decorative sheet used therefor.

[0002]

2. Description of the Related Art Conventionally, decorative steel sheets having colored or patterned steel sheet surfaces have been widely used in electric appliances and various other fields. Examples of such a laminated metal plate include, for example, a metal plate in which a polyester film on which a pattern is printed is laminated on a metal substrate (Japanese Patent Publication No. 61-51988), a metal plate coated with a polyvinyl chloride film, Metal sheet laminated with a polyester film printed with
JP-A-174645), a high-definition laminated metal plate formed by laminating an adhesive layer, a basic thermoplastic resin layer, a printing ink layer, an adhesive layer, and a transparent surface thermoplastic resin layer in this order on a metal plate; A high-definition laminated metal sheet having a predetermined relationship between the melting temperature of the base thermoplastic resin and that of the surface thermoplastic resin and defining the visible light transmittance of the transparent surface thermoplastic resin layer within a predetermined range (Japanese Patent Laid-Open No. 280627).

However, the laminated metal sheet disclosed in Japanese Patent Publication No. Sho 61-51988 lacks a thermoplastic resin layer having good workability as an intermediate layer, and thus lacks bending properties. The laminated metal sheet disclosed in the official gazette has a step of coating the steel sheet with vinyl chloride and a step of coating the steel sheet with polyester, and the workability is not good because the heavy steel sheet is laminated twice. The laminated metal plate disclosed in JP-A-63-280627 regulates the visible light transmittance of the transparent surface thermoplastic resin layer within a predetermined range. It is not enough to specify only the transmittance.
In this laminated metal plate, color development is deteriorated due to the presence of the adhesive layer between the transparent surface thermoplastic resin layer and the printing ink layer. Further, when a vinyl chloride resin is used as the basic thermoplastic resin, printing is performed on the vinyl chloride resin, and foaming occurs at the time of lamination of the steel sheet due to a residual solvent at the time of printing on the vinyl chloride resin.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, improves the processability such as bendability, improves the coloration of the ink, and exhibits high sharpness. The purpose is to provide a board.

[0005]

According to the present invention, the order of layer formation on a metal plate and the haze and light transmittance of a thermoplastic resin used as a surface layer are required for obtaining high definition. It is necessary to limit to a predetermined range,
It was completed based on the findings.

That is, the high definition laminated metal sheet of the present invention comprises:
On the metal plate (1), the first thermoplastic resin layer (3), the printing ink layer (5), the haze degree is in the range of 1 to 8%, and the light transmittance is 70% or more (400 to 700 nm). ), Wherein a transparent second thermoplastic resin layer (6) is sequentially laminated in this order.

[0007] In a preferred embodiment of the present invention, between the metal plate (1) and the first thermoplastic resin layer (3) and / or the first thermoplastic resin layer (3) and the printing ink layer. Between (5) and (5), a first adhesive layer (2) and / or a second adhesive layer (4) can be further provided as necessary.

In another preferred embodiment of the present invention, the thermoplastic resin of the first thermoplastic resin layer (3) is made of a vinyl chloride resin, and the thermoplastic resin of the transparent second thermoplastic resin layer (6) is used. The resin may comprise a polyester resin.

[0009] DETAILED DESCRIPTION The following description of the invention are intended to further illustrate the present invention. The high definition laminated metal sheet of the present invention is a metal sheet (1).
A first thermoplastic resin layer (3) (hereinafter also referred to as an intermediate film (3)), a printing ink layer (5), and a haze degree of 1
８8% and a light transmittance of 70% or more (400
(700 nm) transparent second thermoplastic resin layer (6)
(Hereinafter, also referred to as a surface film (6)).

As the metal substrate, a mild steel plate, an electroformed iron foil, an aluminum plate, a copper plate, or a plate obtained by plating one or more of zinc, tin, lead, aluminum, copper, chromium, and nickel on them are used. Can be. Alternatively, those obtained by applying a polyvinyl chloride sol to these surfaces and gelling them may be used.

The first thermoplastic resin layer (3) laminated on the metal plate (1) has the function of absorbing the thickness of the printing layer provided on the surface film to eliminate irregularities, and has a good bending property. It is essential to obtain workability. As the plastic used for the layer (3), any resin can be used as long as it has such an effect, and among them, polyvinyl chloride is particularly typical. In addition, acrylic, ABS, polystyrene, and vinyl chloride-vinyl acetate copolymer resins can also be used. The thickness of this (3) layer is 10 to 200 μm
Is appropriate. If the thickness is less than 10 μm, the effect of absorbing the thickness of the printing layer provided on the surface film to eliminate irregularities is insufficient, and the bending property of a decorative board is not good. On the other hand, it is not preferable that the thickness is larger than 200 μm, on the contrary, for workability. However, when there is little bending or the like, the design can be improved by setting the thickness to 200 μm or more. Transparent first thermoplastic resin layer,
Two colored layers can also be used. In particular, in order to express the shine of the grain, kneading of pearl pigment and / or
As the embossing of the unevenness, a linear groove having a depth and a width of 0.1 to 100 μm is formed in a curve group obtained by translating a wavy curve such as a sine wave, a Bessel function, an elliptic function, or the like in parallel. Good. In particular, it is particularly preferable that the overall traveling direction of the grain is substantially orthogonal to the overall traveling direction of the line as shown in FIG. Here, "substantially orthogonal" means that both traveling directions need to intersect with each other so that the grain of wood can be sufficiently expressed. Further, a polyvinyl chloride film colored or embossed with a pearl pigment may be used.

The transparent second thermoplastic resin layer (6) forming the surface layer not only functions to make the printing of the printing ink layer stand out clearly, but also functions to protect the printing. In order to realize high sharpness, it is important that the haze of the thermoplastic resin used in the layer (6) is in the range of 1 to 8%, more preferably 3 to 8%.
~ 6%. If the haze is too small, the image will be too sharp, and even if there are slight scratches on the printed surface, they will be very noticeable. On the other hand, if the haze degree is larger than the predetermined value, the internal prints appear to be scattered and the sharpness is not sufficient.

Here, the haze degree (Haze degree) indicates the ratio of diffused light to transmitted light.
Shows the degree of haze when seeing an object through the sample,
The higher the haze, the more the image looks hazy. T is the total light transmittance
t, the diffuse transmittance is Td, and the haze (cloudiness) H
Is determined by H = (Td / Tt) × 100 (%).

In addition to defining the above haze degree in a predetermined range, it is important that the light transmittance is 70% or more (400 to 700 nm). When the light transmittance is less than 70%, high definition cannot be obtained, while the upper limit is not particularly limited.

The plastic film used for the transparent second thermoplastic resin layer (6) forming the surface layer is not particularly limited as long as it has a predetermined range of haze and light transmittance. Polyester film,
In particular, a biaxially stretched polyethylene terephthalate film having high dimensional stability is preferable. In addition, cellulose triacetate, acrylic, and polycarbonate can also be used. The thickness of this surface film is suitably in the range of 5 to 200 μm. A thin film having a thickness of less than 5 μm has poor print depth and lacks sharpness.
Thicknesses exceeding m are difficult to bend and are disadvantageous in terms of cost. In order to improve printability and facilitate lamination with the layer (3), the surface film may be subjected to a corona treatment or an easy adhesion treatment. Further, a transparent pigment, dye, or the like may be added within a range that does not cause the haze and the light transmittance to deviate from the above ranges.

A printing ink layer (5) is provided between the first thermoplastic resin layer (3) and the transparent second thermoplastic resin layer (6). As the ink used for forming the printing ink layer (5), a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like were appropriately mixed with the vehicle as needed. Use something.

Here, the vehicle is a thermoplastic resin,
Use from thermosetting resin, ionizing radiation curable resin, etc.
It is appropriately selected according to necessary 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; (b) styrene resins such as polystyrene and poly α-methylstyrene; Styrene copolymer, (c) acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc., (d) polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer And a vinyl polymer such as polyvinyl butyral.

The thermosetting resin includes phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine / urea cocondensation. There are resins, silicon resins, polysiloxane resins, etc., if necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier,
Add extenders and the like. As a curing agent, isocyanate is usually an unsaturated polyester resin or polyurethane resin, amine is an epoxy resin, peroxide such as methyl ethyl ketone peroxide, or radical initiator such as azobisisobutyronitrile is an unsaturated polyester resin. Often used for.

The printing ink layer (5) is usually formed by printing on the surface film (6), but may be formed by other methods. The printing of the picture on the surface film may be performed by a known method such as a gravure method or a screen method using the above-described ink.
Here, the printing of the pattern includes printing of the ink and printing of the pattern using metal deposition. The formation of a pattern using a metal vapor deposition film is performed, for example, by providing a water-soluble ink layer of a desired pattern on a surface film, vapor-depositing a metal thereon, and then rinsing the water-soluble ink layer and a vapor-deposited layer thereon. Removal can be performed, and such a technique is also included in the printing of a pattern according to the present invention.

It should be noted that an intervening layer should not be provided between the printing ink layer (5) and the surface film (6), but an intervening layer should be provided as long as the coloring properties and high definition of the ink are not impaired. Is possible.

As described above, the first substrate is placed on the metal substrate (1).
The thermoplastic resin layer (3), the printing ink layer (5), and the transparent second thermoplastic resin layer (6) are sequentially laminated in this order, so that processability, ink coloring property, High clarity can be satisfied at the same time.

As the ink pigment, carbon black,
Known color pigments such as cyanine blue, pearl pigments such as titanium dioxide-coated mica, etc., as the pattern or pattern, wood grain pattern, natural products such as stone pattern, polka dots, abstract patterns such as stripes, the whole surface solid or Any combination of these is optional.

If no picture or pattern is required, the printing ink layer (5) can be omitted. Further, instead of the printing ink layer, a metal thin film layer made of aluminum, chromium, or the like, which is provided on the entire surface or in a partial pattern, may be provided.

[0025] Between the metal plate (1) and the first thermoplastic resin layer (3) and / or between the first thermoplastic resin layer (3) and the printing ink layer (5). And optionally further a first adhesive layer (2) and / or a second
May be provided. By providing such an adhesive layer, the adhesiveness between the respective layers is further ensured.

There are various types of adhesives that can be used here.
(A) phenolic resin, furan resin, urea resin,
Melamine resin, polyester resin, polyurethane resin, epoxy resin, or other thermosetting resin, if necessary, crosslinking agent such as isocyanate and amine, methyl ethyl ketone peroxide, hydroperoxide, azobisisobuty Polymerization initiators such as lonitrile, polymerization accelerators such as cobalt naphthenate and dimethylaniline, etc., (b) polyvinyl acetate, polyvinyl chloride, polyvinyl acetate / vinyl chloride copolymer, ethylene / vinyl alcohol Copolymer, ethylene / vinyl acetate copolymer, polyvinyl polymer such as polyvinyl alcohol, polyvinyl butyral, polyolefin resin such as polyethylene and polypropylene, polyacrylate resin, poly (meth) acrylate resin, nitric acid fiber Element, cellulose acetate, poly Mid, ionomer or other thermoplastic resin, (c) butadiene-acrylonitrile rubber, neoprene rubber, natural rubber or other rubber, or (d) natural resin such as glue, casein, dextrin, starch, arabic gum, rosin, Use one or a mixture of two or more of these as a main component, and add a known filler, pigment, dye, stabilizer, solvent, plasticizer, etc. to the adhesive, if necessary. Can be.

As a method of curing these adhesives, an appropriate method such as a solvent drying type, an emulsion type, a hot-melt solidification type, and a thermosetting type can be selected.

Surface film (6) and intermediate film (3)
And the lamination of both laminated films and a metal substrate may be performed according to a known method. For example, there are a heat fusion method, a dry lamination method, a wet lamination method, and a hot melt lamination method using various kinds of adhesives such as urethane, phenol and vinyl adhesives as described above.

Various known hard coat layers may be provided on the surface of the transparent second thermoplastic resin layer of the laminated metal sheet and decorative sheet of the present invention within the range of the haze degree and light transmittance described above. It may be provided. For example, a hard coat paint such as an electron beam or ultraviolet curable polyester acrylate or urethane acrylate is used.

FIG. 1 is an enlarged sectional view of a main part showing an example of the laminated metal plate of the present invention. A first adhesive layer (2), a first thermoplastic resin layer (3), a second adhesive layer (4), a printing ink layer (5), a transparent second layer on a metal substrate (1). Shows a state in which the thermoplastic resin layers (6) are sequentially laminated.

FIG. 2 is an explanatory view showing a preferred example of a case where wood grain pattern printing is performed, and shows the overall running of a parallel curve group line embossing (7) formed on the upper surface side of the first thermoplastic resin layer. The direction (H direction) and the overall traveling direction (V direction) of the grain pattern printing are substantially orthogonal to each other. FIG. 3 is a cross-sectional view taken along line AA ′ of FIG. 2. The layer configuration is the same as that shown in FIG. 1, but the upper surface side of the first thermoplastic resin layer (3) has It shows a state in which a line emboss (7) has been applied, and a grain pattern print has been applied to the printing ink layer (5).

Manufacturing Method One example of the manufacturing method of the laminated metal sheet of the present invention is to use a plastic film excellent in heat resistance and solvent resistance as a surface film (6) and print a pattern thereon to form a printing ink layer (5). ), A plastic film having good workability is laminated as an intermediate film (3) on the printing surface (5) side of the surface film (6), and the obtained laminated film is formed on a metal substrate by an intermediate film. (3) is laminated in contact with the metal surface side to obtain a laminated metal plate. In this laminating, by applying a constant pressure uniformly from the surface, the unevenness of the printing ink layer (5) is embedded in the intermediate film (3) layer, and a laminated metal plate having a flat surface is obtained.

[0033]

The following examples are provided to further illustrate the present invention. The present invention is not limited in scope by these examples.

Example 1 A surface film having a thickness of 2 with a corona discharge treatment on one side was used.
Using a biaxially oriented polyethylene terephthalate (PET) film “Lumirror S-50” (manufactured by Toray Industries, Inc.) having a haze of 5 μm and a haze of 5%, the two-part curable ink “N”
The pattern was gravure printed with "L-ALFA" (manufactured by Morohoshi Ink Co., Ltd.).

A polyester urethane two-part adhesive "DLU-1000" (manufactured by Morohoshi Ink Co., Ltd.) is applied to the printing layer side of the surface film by a reverse roll coater so that the thickness when dried becomes 10 g / m ^2. Then, an intermediate film of colored polyvinyl chloride having a thickness of 100 μm was dry-laminated thereon.

On a degreased mild steel sheet having a thickness of 0.5 mm,
The modified acrylic resin-based two-part adhesive “Y-6067” (manufactured by Yokohama Rubber Co., Ltd.) was roll-coated so that the thickness when dried was 8 g / m ² . Heat the mild steel plate to a temperature of 200 ° C,
The above laminated film was adhered using a metal press roll heated to 200 ° C., and cooled with water to obtain a laminated metal plate.

COMPARATIVE EXAMPLE 1 A surface film having a thickness of 1 with a corona discharge treatment on one side was used.
Biaxially-stretched polyethylene terephthalate film "Tetron CS" with 2 μm and haze degree of 14.5% (manufactured by Teijin Limited)
The same procedure as in Example 1 was carried out except for using, to obtain a laminated metal plate.

Comparative Example 2 A surface film having a thickness of 5 with a corona discharge treatment on one side
Laminated metal plate treated in the same manner as in Example 1 except that a biaxially stretched polyethylene terephthalate film “Tetron O type” (manufactured by Teijin Limited) having a thickness of 0 μm, a haze of 0.4% and a visible light transmittance of 90% was used. I got

COMPARATIVE EXAMPLE 3 Using a gravure print on a colored polyvinyl chloride having a thickness of 100 μm, a vinyl chloride vinyl acetate copolymer / acryl
1/1 (weight ratio) based ink "Kake X" (manufactured by Showa Ink Co., Ltd.)
After forming a pattern, a biaxially stretched polyethylene terephthalate film “Lumirror S-50” (manufactured by Toray Industries, Inc.) having a thickness of 25 μm and a haze of 5% on the pattern side, and a polyester urethane two-part adhesive “DLU” -1000 "(manufactured by Morohoshi Ink Co., Ltd.) using a reverse roll coater at 10 g / m ^2.
It was dry-coated and laminated with the above-mentioned vinyl chloride film.

On a degreased mild steel sheet having a thickness of 0.5 mm,
The modified acrylic resin-based two-part adhesive “Y-6067” (manufactured by Yokohama Rubber Co., Ltd.) was roll-coated so that the thickness when dried was 8 g / m ² . Heat the mild steel plate to a temperature of 200 ° C,
The above laminated film was adhered using a metal press roll heated to 200 ° C., and cooled with water to obtain a laminated metal plate.

The results of comparison of the laminated metal sheets obtained in Example 1 and Comparative Examples 1 to 3 are as follows. Example 1
Of the laminated metal plate had high sharpness and good bending workability. In the laminated metal plate of Comparative Example 1, since the haze of the surface film was high, the internal ink appeared to be scattered, and the sharpness was insufficient. In the laminated metal plate of Comparative Example 2, the surface of the printed surface was scratched at the time of pattern ink printing, and the haze of the surface film was low, so that the scratch was very conspicuous. The laminated metal plate of Comparative Example 3 had an adhesive layer between the ink layer and the polyethylene terephthalate (PET) film constituting the surface film, so that the color of the ink was not good. The residual solvent in the vinyl developed color and bubbles were generated.

Example 2 Printed PET film and colored vinyl chloride film (5
0μ), when a transparent vinyl chloride film (150μ) was inserted, a three-dimensional design was obtained due to the difference in distance between the printing ink on the back of the PET film and the colored vinyl chloride viewed through the transparent film. .

Example 3 The vinyl chloride film of Example 1 was kneaded with pearl pigment, and parallel sine waves were moved in parallel and embossed into a group of curved grooves. Also, the embossed surface side and the embossed surface side are set so that the PET back side printing is a wood grain pattern and the overall running direction of the wood grain is substantially perpendicular to the overall running direction of the line as shown in FIG.
When the printed surface of the ET film was laminated, the luster of the pearl pigment moved depending on the viewing angle due to the line embossing effect, and a woodgrain-like metal plate faithfully reproducing the shine of natural wood was obtained.

[0044]

According to the laminated metal plate of the present invention, the first thermoplastic resin layer, the printing ink layer, and the haze degree are 1 to 8 on the metal plate.
% And the light transmittance is in the wavelength range of 400 nm to 700 nm.
In the range of 70% or more, the transparent second thermoplastic resin layer is sequentially laminated in this order, and the printing ink layer is provided substantially immediately below the surface film. In addition, a plastic laminate having good ink coloring and high sharpness can be obtained.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view of a main part showing an example of a laminated metal plate of the present invention.

FIG. 2 is an explanatory diagram showing a preferred example of a case where wood grain printing is performed.

FIG. 3 is a sectional view taken along line AA ′ of FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal plate 2 1st adhesive layer 3 1st thermoplastic resin layer 4 2nd adhesive layer 5 Printing ink layer 6 Transparent 2nd thermoplastic resin layer 7 Ten thousand line emboss H Overall of ten thousand line emboss Running direction V Overall running direction of wood grain pattern

Claims (7)

(57) [Claims] A first thermoplastic resin layer, a printing ink layer, a haze degree in a range of 1 to 8% and a light transmittance of 70% in a wavelength range of 400 nm to 700 nm on a metal plate;
A highly vivid laminated metal sheet, wherein the transparent second thermoplastic resin layer described above is sequentially laminated in this order. 2. A first adhesive, if necessary, between the metal plate and the first thermoplastic resin layer and / or between the first thermoplastic resin layer and the printing ink layer. The high-definition laminated metal sheet according to claim 1, further comprising an agent layer and / or a second adhesive layer. 3. The thermoplastic resin of the first thermoplastic resin layer comprises a vinyl chloride resin, and the thermoplastic resin of the transparent second thermoplastic resin layer comprises a polyester resin. Item 3. The highly vivid laminated metal sheet according to item 1 or 2. 4. A hard surface is formed on the surface of the second thermoplastic resin layer.
The method according to claim 1, further comprising a coat layer.
High definition laminated metal plate. 5. A first thermoplastic resin layer, a printing ink layer and a transparent second layer having a haze of 1 to 8% and a light transmittance of 70% or more in a wavelength range of 400 to 700 nm. A decorative sheet for a high-definition laminated metal sheet in which the thermoplastic resin layers of the above are laminated in this order. 6. A hard surface is formed on the surface of the second thermoplastic resin layer.
6. The high definition laminated metal sheet according to claim 5, which has a coat layer.
Makeup sheet. 7. A line-shaped unevenness formed of a group of wavy parallel curves having a depth and a width of 0.1 to 100 μm on the surface of the first thermoplastic resin layer, and the printing ink layer has
At least partially transparent wood pattern, and
The general running direction of the grain pattern and the general running direction of the line-shaped irregularities are substantially orthogonal to each other.
5. The high-definition laminated metal sheet according to any one of 4 .