JP3273756B2 - Highly decorative metal base laminate with paper laminated - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite metal plate in which paper is laminated on a metal plate, and more particularly to a composite metal plate such as an inner wall material, a floor material, a ceiling material, an interior material, a panel, and a door in a house or a structure. The present invention relates to a high-design composite metal sheet applicable to various fields such as building materials, various furniture, exterior members and containers of home electric appliances, interior materials of automobiles and vehicles, and the like.

[0002]

2. Description of the Related Art Various techniques have been developed for the purpose of imparting a design property to a metal plate. For example, by applying a resin coating on the surface of a plated metal plate or a non-plated metal plate, or by printing a beautiful color or pattern after the resin coating, a method of obtaining a beautiful painted metal plate, or hot rolling of a metal plate Sometimes a black oxide film naturally formed on the surface is used, or an oxide film having a dark blue color or other colors is artificially formed on the metal surface, so that a steel plate coated with decorative coating of various colors or A method for obtaining a titanium alloy plate has been put to practical use. According to these prior arts, a metal plate having a beautiful appearance and design can be obtained, but the feel such as touch and coldness does not go beyond the metal plate.

On the other hand, for example, laminated metal plates on which films of polyvinyl chloride, polyolefin, acrylic resin and the like are laminated are known, but these laminated plates have a main purpose of improving corrosion resistance and scratch resistance. Few are excellent in design. Further, in the case of a laminate plate in which processability is regarded as important, since a thermoplastic film is used, it is weak to heat. Further, a so-called "PVC steel sheet" which is particularly frequently used among laminated steel sheets is problematic because a polyvinyl chloride film which generates toxic gas by combustion and causes pollution is laminated.

[0004]

In order to solve the above-mentioned problems of the prior art, a new laminated metal plate has been studied. For example, Japanese Patent Application Laid-Open No. 7-256822 discloses a paper laminated metal plate in which paper is adhered to a metal plate via an adhesive. It is considered that the feature of the present invention lies in a processing method for preventing the occurrence of cracks in paper by bending a processed portion after being wetted with water when performing the bending process. However, it is complicated in the process to wet each processed part with water at the time of bending, and the productivity is deteriorated. Further, when the paper is wet, it becomes easy to bend, but on the other hand, the strength of the paper is reduced, so that there is a disadvantage that the paper is damaged or broken by processing. Furthermore, when the paper is wet,
Since the adhesion to the metal plate is deteriorated, there is a problem that the paper is separated depending on the degree of processing.

In view of the above, an object of the present invention is to provide a highly-designed metal substrate laminate which can be processed without wetting with water despite paper being laminated.

[0006]

According to the present invention, at least one sheet of paper is laminated on at least one side of a metal plate via a pressure-sensitive adhesive layer or an adhesive layer, and the outermost layer of the paper laminated surface is protected. The gist lies in that it is a high-design metal laminate having a layer formed thereon. With this configuration, it was possible to provide a metal base laminate capable of giving a soft and warm texture peculiar to paper while eliminating the inorganic texture and cold feel peculiar to metal. Further, the presence of the protective layer can prevent breakage of the paper during processing or during use as a product. The use of printed paper can further enhance the design. For example, when wood-grained printing paper is used, it can be applied to various fields as a high-quality new material.

The protective layer includes a resin film having water repellency,
In particular, it is preferable to be formed of a resin film having a contact angle of water of 60 ° or more measured at 23 ° C. by a droplet method.
Since the protective layer has water repellency, the paper can be prevented from being damaged while being used as a product, and the metal plate as the base material is not corroded by moisture penetrating through the paper.

The laminate of the present invention further has a 180-degree peel strength between the laminated paper and the metal plate of 0.01 to 5.0 k.
gf / 10 mm width and the peel strength must be smaller than the breaking strength of the paper itself. The paper used has a breaking elongation of 2% or more.
By satisfying the above embodiments, it is possible to improve the processability of the laminated board of the present invention without employing a complicated and difficult processing method of protecting the paper, such as processing the paper wet with water. it can.

Typical applications of the highly-designed metal substrate laminate of the present invention include building materials, furniture materials, and exterior members of home electric appliances, but are not limited thereto, and can be used.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly designed metal substrate laminate (hereinafter simply referred to as a laminate) in which a paper is adhered to at least one side of a metal plate and a protective layer is provided on the outermost layer on the lamination side of the paper. That is). It has a warm touch as a natural material of paper, and also has good processability and strength, which are advantages of a metal plate. Since the paper itself has a design property, the laminate of the present invention has a high design property. In addition, if a paper that has been subjected to printing, embossing, or other processing, such as a printed decorative paper used for makeup of building materials and furniture, is used, the material will have a much higher design. Furthermore, since a protective layer is provided on the outermost layer,
The design and aesthetics of paper can be maintained semipermanently.

The laminate of the present invention has the following features by this configuration. 1. While a metal plate as it is has an inorganic cold touch, it has a soft and warm texture, and the feeling (“look”) is calming. 2. Excellent design. It can be used as a new material with a sense of quality that does not seem to be metal. 3. On the contrary, the corrosion resistance is improved by the anticorrosion effect of the protective layer and the paper without impairing the workability and strength of the metal plate. 4. Even if a cigarette or the like is pressed, the metal plate absorbs heat, so that it is superior in fire resistance and flame spread to paper itself. Also, even if it burns, no toxic gas is generated as in the case of a PVC steel sheet. 5. The strength is remarkably improved as compared with the paper itself. 6. Due to the presence of the protective layer, the paper is not damaged or contaminated, and its design is maintained semipermanently.

Hereinafter, an embodiment of the highly designable metal substrate laminate of the present invention will be described in detail. The laminate of the present invention has a metal plate as a base material. Examples of the type of the metal plate include a steel plate, a copper plate, an Al plate, a titanium plate, and various alloy plates. A well-known anticorrosion surface treatment may be applied. Further, a metal foil can be used as the metal plate.

[0013] Paper is produced by entanglement of plant fibers and other fibers. The thickness and basis weight are appropriately selected depending on the application, but usually, the basis weight is 15 to 200 g /
m ² of the paper is preferably used. It is also possible to use patterned paper to which a pattern has been added at the manufacturing stage, or paper to which physical processing such as embossing, creping, corrugating, and calendaring has been performed. In the present invention, the paper itself may be printed such as printed decorative paper used for makeup of building materials and furniture, and in addition to woodgrain, artificial leather paper, and the like, a known printing process may be used. The various decorative papers obtained can be used. In various types of processed paper, those in which a protective layer is formed on the entire surface of the outermost layer can be formed by simply laminating the metal substrate laminate of the present invention without providing another protective layer again. Obtainable.

As for the properties of the paper, the maximum elongation must be 2% or more in consideration of the workability of the laminate. 2%
If it is less than 1, the paper tends to break during processing. The breaking strength of the paper must be greater than the 180-degree peel strength between the paper and the metal plate described below. In the present invention, the breaking strength (kgf / 10 mm width) and the maximum elongation (%) of the paper are as follows: atmosphere temperature: 23 ° C., humidity: 80%, sample: speed 1 mm / m
It is the maximum value of breaking strength and elongation when pulled in.

In the present invention, a protective layer must be formed on the outermost surface of the surface of the metal base paper on which the paper is laminated. Protective layer, before or after laminating paper on metal substrate,
It is formed directly on paper, indirectly through other layers or without intervening. The other layers at this time are not particularly limited. The thickness of the protective layer is preferably 5 μm or more because the protection of the paper can be surely performed. Since it is not necessary to make it too thick, it is usually 10 to 30 μm.

The protective layer is formed of a resin film having water repellency. In particular, it is preferably formed of a resin film having a contact angle of water of 60 ° or more measured at 23 ° C. by a liquid method. Since the protective layer has water repellency, the paper is not damaged while being used as a product, and is not contaminated by other aqueous liquids. Further, the metal plate as the base material does not corrode due to moisture or the like penetrating through the paper.

In the present invention, the contact angle is determined by forming a water droplet on the protective layer sample at an ambient temperature of 23 ° C. using a contact angle meter CD-DT · A manufactured by Kyowa Interface Chemical Co., Ltd. The measured value by the droplet method for measuring was adopted.

As the material of the protective layer, polyolefin resin, silicone resin, fluorine resin, polyurethane resin,
Epoxy resins, alkyd resins, acrylic resins, polyester resins, vinyl acetate resins and the like can be used. Chlorine atom-containing resins such as polyvinyl chloride and polyvinylidene chloride are not suitable for the present invention because toxic gases are generated during combustion. In addition, "resin" means, if necessary, water or an organic solvent, or a known additive, for example, a curing agent, a curing catalyst, a thickener,
The meaning includes those containing a wettability improver, a plasticizer, a filler, and the like.

The method for forming the protective layer is not particularly limited, but these resins may be roll-coated, spray-coated, nozzle-coated, dip-coated, bar-coated, etc., on paper, through another layer or through another layer. Instead, a method of forming a film by coating and heating and drying is mentioned as an example.
The resin at this time may be any of an aqueous type (emulsion type), a solvent type, and a non-solvent type. As another method, a film (film) of these resins is laminated by dry lamination, wet lamination, hot melt lamination, or the like using an adhesive (to be described later) as necessary, or the resin is melted. A method of extruding from a die and directly laminating can be adopted.

[0020] The paper is made of a metal plate with an adhesive or an adhesive
Both are represented by "adhesives". ).
The adhesive can be supplied onto the metal plate by directly coating the metal plate or laminating a film made of the adhesive on the metal plate. The coating method is not particularly limited, and the above-described methods and the like can be employed. Examples of the type of the adhesive include polyvinyl acetate resins such as polyvinyl acetate and vinyl acetate-ethylene copolymer (EVA); poly (meth) acrylic acid and / or an ester thereof, and (meth) acrylic acid and / or an ester thereof. And acrylic resins such as copolymers with other monomers such as styrene and vinyl acetate; polyurethane resins; polyester resins; polyolefin resins; styrene resins such as SBS and SIBS; rubbers such as natural rubber and synthetic rubber; An adhesive can be used. In addition, these adhesives may be any of an emulsion type, a solvent type, and a non-solvent type.

The amount of the adhesive is determined after drying per unit area.
Usually 0.5 to 40 g / m as weight^Two And 0.5
g / m^Two If less, the adhesion between paper and metal substrate will be poor.
You. 40g / m^Two If it exceeds, the paper may wrinkle
In addition, the effect of improving the adhesion is saturated. More preferred use
The lower limit of the amount is 3.0 g / m^Two And the upper limit is 15 g / m ^Two 
It is.

After applying the adhesive, the paper is laminated. If the adhesive contains solvents, before drying,
Alternatively, it is preferable to laminate the paper before it is cured. This is because the adhesive is impregnated into the voids of the paper, so that the effect of improving the adhesive strength is obtained. However, the paper is thin,
When the basis weight is small, the adhesive may ooze onto the paper surface (the surface opposite to the metal surface) due to excessive impregnation,
The timing for laminating the paper may be appropriately determined in consideration of the drying / curing speed of the adhesive. After laminating the paper, it is preferable to heat the adhesive by a method such as passing through a hot air drying oven so that the adhesive is completely dried and cured. It is preferable that such considerations be made when forming the protective layer.

The laminate of the present invention has a 180-degree peel strength between the paper and the metal plate laminated via the adhesive layer of 0.01 to 0.01.
It must be within the range of 5.0 kgf / 10 mm width and the peel strength must be smaller than the breaking strength of the paper itself. Laminates that meet this requirement can be processed without breaking the paper without wetting the paper during processing. It is recommended to select an adhesive or paper to meet the above requirements.

The 180 degree peel strength is 0.01 kgf
If it is smaller than / 10 mm, the paper may be peeled off with time because of poor adhesion of the paper. In addition, 5.0kgf / 1
If it is larger than 0 mm, the adhesion of the paper is too strong, and the paper is not able to withstand deformation due to processing and is damaged, which is not preferable. More preferable 180 degree peel strength is 0.1 to 0.1.
The range is 5 kgf / 10 mm. Note that the 180-degree peel strength referred to in the present invention is “180 ° peel strength” in JIS Z 0237.
This is a value measured at a peeling speed of 200 mm / min in an atmosphere of 23 ° C. and a humidity of 80% according to the “peeling method”.

In the present invention, not only one sheet of paper,
Two or more sheets may be stacked. When laminating two or more sheets, an adhesive is supplied again after laminating the paper. The paper laminated on the front side (the side opposite to the metal surface) may be partially cut away. In the case of such a cut-out paper, the lower layer paper can be seen, so that the design property is further enhanced when a plurality of papers of different colors are used.

The highly designable metal substrate laminate of the present invention is applicable to various uses. Typical applications and the effects in those applications are shown below.

(1) Building material applications In this field, building materials used for houses and other structures,
Specifically, it can be used as a partition unit, an inner wall material, a ceiling material, a floor material, a door, a frame material of a sash, and the like. In addition, the high-design metal substrate laminate of the present invention can be used for metal hardware such as hinges, hinges, and tablets. Where a metal plate is conventionally used, the high-design metal substrate laminate of the present invention is used. While a metal plate as it is has an inorganic cold touch, a soft warm texture can be obtained. Similarly, the look ("look") can be calming. 2. Excellent design. It can be used as a new material with a sense of quality that does not seem to be metal. 3. On the contrary, the corrosion resistance is improved by the anticorrosion effect of the protective layer and the paper without impairing the workability and strength of the metal plate. 4. Even if a cigarette or the like is pressed, the metal plate absorbs heat, so that it is superior in fire resistance and flame spread to paper itself. Also, even if it burns, no toxic gas is generated as in the case of a PVC steel sheet. 5. The strength is remarkably improved as compared with the paper itself. 6. Due to the presence of the protective layer, the paper is not damaged or contaminated, and its design is maintained semipermanently. The effect is obtained.

Further, when used in place of a wood-based decorative board such as decorative plywood, in addition to the above items 4 to 6, it is possible to obtain an effect that processing is easy, termite resistance can be imparted, and recycling is possible. Furthermore, by manufacturing a metal object using the laminated plate of the present invention, it is possible to make the same pattern and texture as the article to which the metal object is attached, and to enhance the design of the article and the metal object without discomfort. .

(2) Use of Furniture The highly decorative metal base laminate of the present invention can be applied to all furniture manufactured as steel furniture.
Desks, chairs, lockers, cabinets, stands, bookshelves,
A library, partition, bed, etc. In addition, furniture that was previously only made of wood or resin,
It can be manufactured using the laminate of the present invention. The effects are 1 to 6 described above. In addition, by using the high-design metal substrate laminate of the present invention as hardware for furniture,
The design can be improved by eliminating the discomfort of furniture and hardware.

(3) Exterior members of home appliances For home appliances such as televisions, refrigerators, washing machines, coolers, lighting fixtures, etc., where the metal plate is used as the exterior member, the high design metal base of the present invention is used. A material laminate can be used, and the design is enhanced. The effects are 1 to 6 described above.

The use of the highly designable metal substrate laminate of the present invention is not limited to the above-mentioned fields (1) to (3), but can be applied to various fields such as containers, interior materials of automobiles and vehicles. is there.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention.

Examples and Comparative Examples Chromate treatments (Cr:
After applying 30 mg / m ² ), an acrylic pressure-sensitive adhesive is applied by a roll coating method so as to be 10 g / m ² after drying, and various laminating materials (printing paper, paper, embossed paper, creped paper, Corrugated paper, calendered paper,
(Colored polyvinyl chloride film), and dried at 80 ° C. (plate temperature) for 1 minute. Then, Tables 1-4
Using a resin of the type shown in
After drying, a protective layer was formed. The thickness (μm) in the table is the thickness of the protective layer after drying.

The obtained laminates were evaluated for the following characteristics, and the results are shown in Tables 1 to 4. Comparative Example No. 55
Then, plywood was used in place of the metal plate. All the substrates other than the Al foil of Example No. 36 had a thickness of 0.3 mm. The No. 36 Al foil used had a thickness of 15 μm.

A contact angle of water A liquid for forming a water droplet on the protective layer and measuring the contact angle at a temperature of 23 ° C. using a contact angle meter CD-DT · A manufactured by Kyowa Interface Chemical Co., Ltd. The measured value by the drop method was adopted.

180-degree peel strength 180-degree peel strength between paper and metal plate (kgf / 10 mm
The width) is measured according to JIS Z 0237, and is a resistance force when the laminated paper (10 mm width) and the metal plate are sandwiched between upper and lower chucks and peeled off at a speed of 200 mm / min. Atmospheric temperature 23 ° C, humidity 80%
Was measured.

Breaking strength and elongation of paper The breaking strength (kgf / 10 mm width) and the maximum elongation (%) of the paper itself are the maximum values of the breaking strength and elongation when the sample is pulled at a speed of 1 mm / min. Atmospheric temperature 23 ° C,
It was measured at a humidity of 80%.

Processability-1 A 90-degree bending test was performed at R: 1 mm, and the occurrence of breaks (cracks) and peeling of the paper near the bent portion were visually observed. ◎ indicates that no cracks occurred, ○ indicates that cracks occurred slightly, △ indicates that cracks occurred significantly,
Those that could not be bent were evaluated as x.

Workability-2 A 180 ° OT bending test was performed. The state of occurrence of a break (crack) and the state of peeling of the paper near the bent portion were evaluated in the same manner as in the 90-degree bending test.

Adhesion 180 degree peel strength between paper and metal plate (kgf / 10mm width)
Is more than 0.01 when the value is 0.01 or more.
Is less than 0, Δ is more than 0.005 to 0.008 or less, and X is 0.005 or less.

Designability It was determined whether or not there was designability. That is, ◎ indicates that a paper having a design property is adhered, △ indicates a mere colored polyvinyl chloride film-laminated steel sheet, and × indicates a metal surface as it is.

Safety The materials (adhesive, paper, colored polyvinyl chloride film, protective layer) other than the metal plate are heated to about 700 ° C. in a tubular furnace and burned, and the generated gas is trapped by a cooling trap tube. After that, the sample was collected in a Tedlar bag and analyzed by gas chromatography. X: Those that generate toxic gas (chlorine-containing gas) (level 3,000,000 μg per sample);
And

Chemical resistance A 5% acetic acid aqueous solution and a 1% sodium hydroxide aqueous solution are respectively dropped on the protective layer of the laminate, and the watch glass is covered with the solution.
After standing for a while, the surface state of the protective layer after wiping the chemical was visually observed. No abnormality was evaluated as 、, slight discoloration was evaluated as △, slight discoloration was evaluated as Δ, and marked discoloration was evaluated as x.

Stain resistance Oil-based magic ink and soy sauce are respectively dropped on the protective layer of the laminated board, covered with a watch glass and left for 24 hours, and then the surface state of the protective layer after wiping off the chemical is visually observed. Observed. ◎ indicates no abnormality, ○ indicates slight contamination, ○ indicates slight contamination, and × indicates marked contamination.

Flame spread resistance Evaluated by a self-extinguishing test specified in JIS K 6744.
場合: Immediately after quenching, ◎: Flame extinction within 5 seconds, △: Flame extinction within 10 seconds, X: Flame extinction: 10 seconds or more.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

The abbreviations in the table are as follows. PU: Polyurethane resin EPO: Epoxy resin UPE: Polyester resin AL: Alkyd resin SB: Styrene-butadiene copolymer VA: Vinyl acetate resin PVC: Polyvinyl chloride Also, the unit of 180 ° peel strength and paper breaking strength is kg.
f / 10 mm width.

[0051]

According to the present invention, the design of the paper is imparted to the metal plate with a simple structure in which a protective layer is formed by bonding paper to at least one side of the metal plate. The metal base laminate of the present invention can eliminate the inorganic texture and the cold touch unique to metal while maintaining the strength and durability of the metal base, and provide a warm texture unique to paper. . Further, the presence of the protective layer can prevent breakage of the paper during processing or during use as a product.
The use of printed paper can further enhance the design. For example, when wood-grained printing paper is used, it can be applied to various fields as a high-quality new material. Therefore, the present invention can be applied not only to a field in which a conventional metal plate or a painted metal plate is used, but also to a field in which wood or a resin material such as plywood is used.

──────────────────────────────────────────────────続 き Continued on the front page (73) Patent holder 000209636 Danya Sangyo Co., Ltd. 2-5-12 Higashiko, Kokurakita-ku, Kitakyushu-shi, Fukuoka (73) Patent holder 597105555 Tokyo Color Gravure Industrial Co., Ltd. Sarushima-gun, Ibaraki 8 Okari, Sowa-cho (72) Inventor Tadashige Nakamoto 1 Kanazawacho, Kakogawa-shi, Hyogo Prefecture Kobe Steel Works Kakogawa Works (72) Inventor Hideki Nakamura 1 Kanazawacho, Kakogawa-shi, Hyogo Kobe Steel, Ltd. Location Kakogawa Works (72) Inventor Takeshi Joshi 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Mitsui & Co., Steel Construction Materials Co., Ltd. (72) Inventor Noboru Kishida 1-2-1 Otemachi, Chiyoda-ku, Tokyo Mitsui & Co., Ltd. Inside (72) Inventor Koji Ishimoto 2-5-12 Higashiko, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Inside Danya Sangyo Co., Ltd. (72) Inventor Mitsuo Ikeda 8 Kazura, Sawa-machi, Sarushima-gun, Ibaraki Prefecture Inside Tokyo Color Gravure Industry Co., Ltd. (56) References JP-A-7-256822 (JP, A) JP-A-52-50384 (JP, A) JP-A-1-108727 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 15/12

Claims (5)

(57) [Claims] On at least one surface according to claim 1 the metal plate, at least a piece of paper through an adhesive layer or an adhesive layer is laminated
A laminate are, trees on the outermost surface layer of the paper stacking surface of the water repellent
A protective layer made of a grease film is formed, and the paper
The breaking elongation is 2% or more, and the laminated paper and the metal plate
180 degree peel strength is 0.01 to 5.0 kgf / 10 mm
Within the range of the width, and this peel strength
A highly designable metal base laminate having a strength lower than that of the laminate. 2. The high-design metal substrate laminate according to claim 1, wherein the protective layer is formed of a resin film having a contact angle of water of at least 60 ° measured at 23 ° C. by a droplet method. . 3. is to use as a building material according to claim 1 or 2 high design metal substrate laminate according to. 4. A high-design metal substrate laminate according to claim 1 or 2 is to use as a furniture material. 5. A is to use as an exterior member of appliances according to claim 1 or 2 high design metal substrate laminate according to.