JPH04238026A - Laminated metal plate with highly bright color and decorative sheet used therein - Google Patents

Abstract

PURPOSE:To provide a laminated metal plate improved in processability such as bending properties, improving the color development of ink and showing a highly bright color property. CONSTITUTION:The title laminated metal plate with a highly bright color is formed by successively laminating a first thermoplastic resin layer 3, a printing layer 5 and a second transparent resin layer 6 with haze of 1-8% and light transmittance of 70% or more within the wavelength range of 400-700nm to a metal plate in this order.

Description

[Detailed description of the invention]

0001

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

0002

2. Description of the Related Art Conventionally, decorative steel sheets whose surfaces are colored or patterned have been widely used in electrical products and other various fields. Such laminated metal plates include, for example, a metal plate in which a polyester film with a pattern printed on it is laminated on a metal substrate (Japanese Patent Publication No. 61-51988), a metal plate coated with a polyvinyl chloride film, and a pattern printed on the surface of the metal plate. A metal plate laminated with a polyester film printed with
-174645), a high-definition laminated metal plate in which an adhesive layer, a base thermoplastic resin layer, a printing ink layer, an adhesive layer, and a transparent surface thermoplastic resin layer are laminated in this order on a metal plate, A high-definition laminated metal plate in which the melting temperatures of the base thermoplastic resin and the surface thermoplastic resin have a predetermined relationship, and the visible light transmittance of the transparent surface thermoplastic resin layer is defined within a predetermined range.
JP-A-63-280627).

However, the laminated metal plate disclosed in Japanese Patent Publication No. 61-51988 lacks bendability because it does not have a thermoplastic resin layer with good workability as an intermediate layer. The laminated metal sheet disclosed in the publication involves a process of coating the steel plate with vinyl chloride and a process of coating the steel plate with polyester, and the heavy and bulky steel plates are laminated twice, resulting in poor workability. In the laminated metal plate disclosed in JP-A No. 63-280627, the visible light transmittance of the transparent surface thermoplastic resin layer is specified within a predetermined range, but in order to satisfy high definition,
It is not sufficient to simply specify the transmittance. In this laminated metal plate, the presence of an adhesive layer between the transparent surface thermoplastic resin layer and the printing ink layer causes poor color development. Furthermore, when vinyl chloride resin is used as the basic thermoplastic resin, printing is performed on the vinyl chloride resin, and the residual solvent from printing on the vinyl chloride resin causes foaming when laminating steel plates.

0004

[Problems to be Solved by the Invention] The present invention solves the drawbacks of the prior art, and provides a laminated metal that has good workability such as bendability, good color development of ink, and high image clarity. The purpose is to provide a board.

[0005]

[Means for Solving the Problems] The present invention provides the order of layer construction on a metal plate and the haze degree and light transmittance of a thermoplastic resin used as a surface layer as necessary conditions for obtaining high image clarity. It is necessary to limit the
It was completed based on the knowledge of

That is, the high-definition laminated metal plate of the present invention is
On the metal plate (1), a first thermoplastic resin layer (3), a printing ink layer (5), and a layer having a haze degree of 1 to 8% and a light transmittance of 70% or more (400 to 700 nm). ) are successively laminated in this order.

In a preferred embodiment of the present invention, there is a gap 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), 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 vinyl chloride resin, and the thermoplastic resin of the transparent second thermoplastic resin layer (6) is made of vinyl chloride resin.
) may be made of polyester resin.

DETAILED DESCRIPTION OF THE INVENTION The following description is provided to further explain the invention. The high-definition laminated metal plate of the present invention is a metal plate (1)
On top, there is a first thermoplastic resin layer (3) (hereinafter also referred to as intermediate film (3)), a printing ink layer (5), and a haze degree of 1.
~8% and has a light transmittance of 70% or more (400%
~700 nm) transparent second thermoplastic resin layer (6
) (hereinafter also referred to as surface film (6)) are sequentially laminated.

[0010] As the metal substrate, a mild steel plate, an electroformed iron foil, an aluminum plate, a copper plate, or a plate plated with one or more of zinc, tin, lead, aluminum, copper, chromium, and nickel may be used. I can do it. Alternatively, a polyvinyl chloride sol may be applied to these surfaces and gelled.

The first thermoplastic resin layer (3) laminated on the metal plate (1) has the function of absorbing the thickness of the printed layer provided on the surface film to eliminate unevenness, and also has good bending properties. It is essential to obtain processability. The plastic used for this layer (3) may be any resin as long as it has the above-mentioned effect, but polyvinyl chloride is particularly representative. In addition, acrylic, ABS, polystyrene, vinyl chloride vinyl acetate copolymer resins can also be used. The thickness of this (3) layer is 10 to 200 μm
A range of is appropriate. If it is thinner than 10 μm, the effect of absorbing the thickness of the printed layer provided on the surface film and eliminating unevenness is insufficient, and the bending workability when used as a decorative board is not good. On the other hand, making it thicker than 200 μm is also not preferable in terms of workability. However, if there is little bending, etc., the thickness can be set to 200 μm or more to improve the design. The first thermoplastic resin layer is transparent;
It can also be colored in two layers. In particular, in order to express the shine of the wood grain, it is necessary to knead pearl pigments and/or
For embossing of unevenness, we form line-shaped grooves with a depth and width of 0.1 to 100 μm in the shape of a group of curves obtained by parallelly moving a wavy curve such as a sine wave, Bessel function, elliptic function, etc. Good. In particular, it is particularly good if the overall running direction of the wood grain and the overall running direction of the parallel lines are substantially perpendicular to each other as shown in FIG. Here, "substantially orthogonal" means that the two running directions should just intersect to the extent that the luster of the wood grain can be sufficiently expressed. Alternatively, a polyvinyl chloride film colored or embossed with pearl pigments may be used.

The transparent second thermoplastic resin layer (6) forming the surface layer has the function of making the print of the printing ink layer stand out clearly, and also has the function of protecting the print. In order to achieve high image clarity, it is important that the thermoplastic resin used for this layer (6) has a haze degree in the range of 1 to 8%, and a more preferable range is 3.
~6%. If the haze level is too low, the image will be too sharp and even small scratches on the printed surface will become very noticeable. On the other hand, if the degree of haze is greater than a predetermined value, the internal printing will appear scattered and the sharpness of the image will not be sufficient.

[0013] Here, the haze degree indicates the ratio of diffused light to the transmitted light.
Indicates the degree of haziness when looking at an object through the sample,
The higher the haze level, the hazier the image appears. Total light transmittance is Tt
, when the diffuse transmittance is Td, the haze degree (cloudiness) H is,
The value is determined by H=(Td/Tt)×100(%).

[0014] In addition to regulating the above haze degree within a predetermined range, it is important that the light transmittance is 70% or more (400 to 700 nm). If the light transmittance is less than 70%, high image clarity cannot be obtained, but the upper limit is not particularly limited.

The plastic film used for the transparent second thermoplastic resin layer (6) forming this surface layer is not particularly limited as long as it has a haze degree and light transmittance within a predetermined range. polyester film,
In particular, a biaxially stretched polyethylene terephthalate film with high dimensional stability is suitable. 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. If the thickness is less than 5 μm, the printing depth will be poor and the sharpness will be insufficient.
If it is thicker than m, it will be difficult to bend it and it will be disadvantageous in terms of cost. In order to improve printability and facilitate lamination with the layer (3), the surface film may be subjected to corona treatment or adhesion treatment. Further, transparent pigments, dyes, etc. may be added within a range that does not cause the haze degree and 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). The ink used to form this printing ink layer (5) is prepared by mixing pigments, coloring agents such as dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. in a vehicle as necessary. use something

[0017] Here, the vehicle is a thermoplastic resin,
Applications from thermosetting resins, ionizing radiation curable resins, etc.
It is selected as appropriate depending on the required physical properties, printing suitability, etc.

Examples of thermoplastic resins include (a) cellulose derivatives such as ethylcellulose, cellulose nitrate, cellulose acetate, ethylhydroxyethylcellulose, and cellulose acetate propionate; (b) styrene resins such as polystyrene and polyα-methylstyrene; Styrene copolymer, (c) Acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, (d) Polyvinyl chloride, polyvinyl acetate, vinyl chloride/vinyl acetate copolymer Examples include vinyl polymers such as polyvinyl butyral and polyvinyl butyral.

[0019] Examples of thermosetting resins include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine/urea cocondensation resin. There are resins, silicone resins, polysiloxane resins, etc., and to these, crosslinking agents, curing agents such as polymerization initiators, polymerization accelerators, solvents, viscosity modifiers, extender pigments, etc. are added as necessary. As curing agents, isocyanates are usually used in unsaturated polyester resins and polyurethane resins, amines are used in epoxy resins, peroxides such as methyl ethyl ketone peroxide, and radical initiators such as azobisisobutyronitrile are used in unsaturated polyester resins. often used in

[0020] This printing ink layer (5) is usually formed by printing on the surface film (6), but it may be formed by other methods. The pattern may be printed on the surface film by a known method such as a gravure method or a screen method using the above-mentioned ink. Here, the printing of a pattern includes not only ink printing but also the provision of a pattern using metal vapor deposition. To form a pattern using a metal vapor deposition film, for example, a water-soluble ink layer with a desired pattern is provided on a surface film, a metal is vapor-deposited on top of the water-soluble ink layer, and then the metal is washed with water to remove the water-soluble ink layer and the vapor-deposited layer above it. This can be done by removing the pattern, and such a method is also included in the printing of a pattern in the present invention.

[0021] Although no intervening layer should be provided between the printing ink layer (5) and the surface film (6), an intervening layer may be provided as long as it does not impair the color development and high image clarity of the ink. is possible.

As described above, the first
The thermoplastic resin layer (3), the printing ink layer (5), and the transparent second thermoplastic resin layer (6) are sequentially laminated in this order, thereby improving processability, ink color development, High image clarity can be achieved at the same time.

[0023] As the ink pigment, carbon black,
Known coloring pigments such as cyanine blue, pearl pigments such as titanium dioxide-coated mica, etc. are used, and the designs and patterns include natural materials such as wood grain patterns and stone grain patterns, abstract patterns such as polka dots and stripes, and solid or solid patterns. Any combination of these may be used.

[0024] Note that if a picture or pattern is not required, the printing ink layer (5) may be omitted. Also,
Instead of the printing ink layer, a metal thin film layer of aluminum, chromium, etc. may be provided over the entire surface or in a partial pattern.

[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); , if necessary further the first adhesive layer (2) and/or the second adhesive layer (2)
It is also possible to provide an adhesive layer (4). By providing such an adhesive layer, the adhesion between each layer becomes more reliable.

There are various types of adhesives that can be used here, but resin-based adhesives include (a) phenolic resins, furan-based resins, urea-based resins, melamine-based resins, and polyester-based resins. resin, polyurethane resin, epoxy resin, or other thermosetting resin,
If necessary, crosslinking agents such as isocyanates and amines, polymerization initiators such as methyl ethyl ketone peroxide, hydroperoxide, and azobisisobutyronitrile, and polymerization accelerators such as cobalt naphthenate and dimethylaniline are added, (b) Vinyl polymers such as polyvinyl acetate, polyvinyl chloride, polyvinyl acetate/vinyl chloride copolymer, ethylene/vinyl alcohol copolymer, ethylene/vinyl acetate copolymer, polyvinyl alcohol, polyvinyl butyral, polyethylene, Polyolefin resin such as polypropylene, polyacrylic ester resin, poly(meth)acrylic ester resin, cellulose nitrate, cellulose acetate, polyamide, ionomer or other thermoplastic resin, (iii) butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, or other rubber,
or (d) The main component is one or a mixture of two or more of natural resins such as glue, casein, dextrin, starch, gum arabic, and rosin, and if necessary, known fillers, pigments, etc. A material to which dyes, stabilizers, solvents, plasticizers, etc. are added can be used as an adhesive.

[0027] As the curing method for these adhesives, an appropriate method such as a solvent drying type, an emulsion type, a heat melting type, a thermosetting type, etc. can be selected.

Surface film (6) and intermediate film (3)
The lamination with the metal substrate and the lamination of both laminated films and the metal substrate may be performed according to known methods. Examples include a heat fusion method, a dry lamination method, a wet lamination method, and a hot melt lamination method using various adhesives such as urethane-based, phenol-based, and vinyl-based adhesives as described above.

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

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

FIG. 2 is an explanatory diagram showing a preferable example of wood grain pattern printing, and shows the overall running of the 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 running direction (V direction) of the wood grain pattern printing are shown to be approximately perpendicular to each other. 3 is a cross-sectional view taken along the line A-A' in FIG. 2, and the layer structure is the same as that shown in FIG. A line embossing (7) is applied, and a printing ink layer (5) is applied.
) shows wood grain pattern printing.

Manufacturing method An example of the method for manufacturing the laminated metal plate of the present invention is to use a plastic film with excellent heat resistance and solvent resistance as a surface film (6
), a pattern is printed on it to form a printing ink layer (5), and a plastic film with good processability is used as an intermediate film (3) to form a printing surface (
5) side, the obtained laminated film is laminated on a metal substrate, and the intermediate film (3) is laminated in contact with the metal surface side,
Obtain a laminated metal plate. During this lamination, by uniformly applying a constant pressure from the surface, the unevenness of the printing ink layer (5) is embedded in the intermediate film (3) layer, resulting in a laminated metal plate with a flat surface.

[0033]

EXAMPLES The following examples are intended to explain the present invention more specifically. The scope of the present invention is not limited by these Examples.

Example 1 As a surface film, a thickness of 2 with corona discharge treatment on one side was used.
A biaxially oriented polyethylene terephthalate (PET) film "Lumirror S-50" (manufactured by Toray Industries, Inc.) with a thickness of 5 μm and a haze degree of 5% was used, and the two-component curing ink "N" was applied to the treated surface.
The pattern was gravure printed using "L-ALFA" (manufactured by Moroboshi Ink Co., Ltd.).

[0035] Apply a polyester urethane two-component adhesive to the printed layer side of this surface film using a reverse roll coater.
"DLU-1000" (manufactured by Moroboshi Ink Co., Ltd.) was applied to a dry thickness of 10 g/m 2 , and an intermediate film of colored polyvinyl chloride having a thickness of 100 μm was dry laminated thereon.

[0036] A modified acrylic resin two-component adhesive "Y-6067" (
(manufactured by Yokohama Rubber Co., Ltd.) was roll coated to a dry thickness of 8 g/m2. A mild steel plate was heated to a temperature of 200°C, the above-mentioned laminated film was adhered using a metal pressure roll heated to 200°C, and water-cooled to obtain a laminated metal plate.

Comparative Example 1 As a surface film, a thickness of 1 with corona discharge treatment on one side was used.
Biaxially oriented polyethylene terephthalate film “Tetron CS” (manufactured by Teijin) with a thickness of 2 μm and a haze degree of 14.5%
A laminated metal plate was obtained in the same manner as in Example 1 except that .

Comparative Example 2 As a surface film, one side was treated with corona discharge and the thickness was 5.
A laminated metal plate was prepared in the same manner as in Example 1, except that a biaxially stretched polyethylene terephthalate film "Tetron O type" (manufactured by Teijin) with a diameter of 0 μm, a haze degree of 0.4%, and a visible light transmittance of 90% was used. I got it.

Comparative Example 3 Vinyl chloride vinyl acetate copolymer/acrylic =
1/1 (weight ratio) ink “KaX” (manufactured by Showa Ink Co., Ltd.)
After forming a pattern, a polyester urethane two-component adhesive "DLU" was applied to a biaxially stretched polyethylene terephthalate film "Lumirror S-50" (manufactured by Toray Industries, Inc.) with a thickness of 25 μm and a haze degree of 5% on the pattern side. -1000'' (Moroboshi Ink Co., Ltd.) using a reverse roll coater at 10g/m2.
It was dry coated and laminated with the above vinyl chloride film.

[0040] A modified acrylic resin two-component adhesive "Y-6067" (
(manufactured by Yokohama Rubber Co., Ltd.) was roll coated to a dry thickness of 8 g/m2. A mild steel plate was heated to a temperature of 200°C, the above-mentioned laminated film was adhered using a metal pressure roll heated to 200°C, and water-cooled to obtain a laminated metal plate.

The results of comparing the laminated metal plates obtained in Example 1 and Comparative Examples 1 to 3 are as follows. Example 1
The laminated metal plate had high image clarity and good bending workability. In the laminated metal plate of Comparative Example 1, the surface film had a high haze, so the internal ink appeared scattered and the image lacked sharpness. The printed surface of the laminated metal plate of Comparative Example 2 was scratched during pattern ink printing, and the scratches were very noticeable because the haze of the surface film was low. The laminated metal sheet of Comparative Example 3 has an adhesive layer between the ink layer and the polyethylene terephthalate (PET) film constituting the surface film, so the color development of the ink is not good. The residual solvent in the vinyl developed color and created bubbles.

Example 2 Printed PET film and colored vinyl chloride film (5
When a transparent vinyl chloride film (150μ) was sandwiched between 0μ), 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 seen through the transparent film. .

Example 3 The vinyl chloride film of Example 1 mixed with a pearl pigment was moved in parallel with a parallel sinusoidal wave to perform embossing in the form of grooves in the form of a group of curves. In addition, the PET back side is printed with a wood grain pattern, and the embossed side and P
When the printed surface of the ET film was laminated, the luster of the pearl pigment shifted depending on the viewing angle due to the linear embossing effect, resulting in a wood-grained metal plate that faithfully reproduced the shine of natural wood.

[0044]

[Effect] 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 has a light transmittance of wavelength 400 nm to 700 nm.
The transparent second thermoplastic resin layer having a content of 70% or more in the nanometer range is laminated in this order, and the layer structure has a printing ink layer substantially directly under the surface film, so bendability is improved. A plastic laminate with good ink color development and high image clarity can be obtained.

[Brief explanation of the drawing]

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

FIG. 2 is an explanatory diagram showing a preferred example of wood grain pattern printing.

FIG. 3 is a sectional view taken along the line AA' in FIG. 2;

[Explanation of symbols]

1 Metal plate 2 First adhesive layer 3 First thermoplastic resin layer 4 Second adhesive layer 5 Printing ink layer 6 Transparent second thermoplastic resin layer 7 Line emboss H　Overall running direction of line embossing V Overall running direction of wood grain pattern

Claims (5)

[Claims] [Claim 1] A first thermoplastic resin layer, a printing ink layer, a haze degree in the range of 1 to 8%, and a light transmittance of 70% in the wavelength range of 400 nm to 700 nm, on a metal plate.
A high-definition laminated metal plate characterized in that the transparent second thermoplastic resin layers described above are sequentially laminated in this order. 2. If necessary, further a first adhesive is provided 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 plate according to claim 1, further comprising an adhesive layer and/or a second adhesive layer. 3. The thermoplastic resin of the first thermoplastic resin layer is made of vinyl chloride resin, and the thermoplastic resin of the transparent second thermoplastic resin layer is made of polyester resin. The high-definition laminated metal plate according to item 1 or 2. 4. A first thermoplastic resin layer, a printing ink layer, and a transparent second layer having a haze degree in the range of 1 to 8% and a light transmittance of 70% or more in the wavelength range of 400 nm to 700 nm. A decorative sheet for high-definition laminated metal plates in which thermoplastic resin layers are laminated in this order. 5. Line-shaped unevenness consisting of a group of wavy parallel curves with a depth and width of 0.1 to 100 μm is formed on the surface of the first thermoplastic resin layer, and the printing ink layer has:
at least partially has a transparent grain pattern, and
Claims 1 to 3, characterized in that the overall running direction of the wood grain pattern and the overall running direction of the linear unevenness are substantially orthogonal.
3. The high-definition laminated metal plate according to any one of 3.