JP6821466B2 - Laminated sheet and laminated board - Google Patents

Description

The present invention relates to a laminated sheet used for protecting various members and a laminated board with the laminated sheet.

In order to give design to various products such as refrigerators, washing machines and other electric appliances, buildings and vehicles, decorative steel sheets are used as interior materials, exterior materials or surface materials thereof. In addition, since decorative steel sheets have excellent durability in indoor and outdoor environments, they are also used as building materials such as wall materials for unit baths and outer walls of houses. As such a decorative steel sheet, one obtained by laminating a laminated sheet having a brilliant feeling on a metal plate or the like is used.

For example, in Patent Document 1, as a laminated sheet, a metal vapor deposition layer or a high-brightness ink layer for obtaining metallic luster is formed on a thermoplastic resin film layer, and then a support base resin layer is further formed on the metal vapor deposition layer or a high-brightness ink layer. The laminated sheet made of the above is disclosed.

Japanese Unexamined Patent Publication No. 2006-341388

However, in the laminated sheet described in Patent Document 1, there is a problem that when a metal vapor deposition layer is formed in order to obtain metallic luster, the corrosion resistance becomes inferior, while high brightness is obtained. When the ink layer is formed, there is a problem that the adhesion between the high-brightness ink layer and another layer is inferior. Further, since the laminated sheet used for the decorative steel sheet may be processed into a desired shape together with the metal plate as the base material, processability such as bendability is required. The laminated sheet described in Document 1 also has a problem of being inferior in processability.

An object of the present invention is to provide a laminated sheet having excellent designability and excellent processability and corrosion resistance.

The present inventors can achieve the above object by forming the laminated sheet by using a specific transparent resin layer (A), a specific bright layer (B), and a specific colored layer (C). The present invention has been completed.

That is, according to the present invention, the transparent resin layer (A) containing a crystalline polyester resin and a coloring pigment of 20% by weight or less and having a haze value of 20% or less measured in accordance with JIS K7136. The transparent resin layer (A) is formed as a lower layer, contains a crystalline polyester resin and 3 to 30 % by weight of a bright pigment, has a thickness of 10 to 100 μm, and has a haze value of 50% or more. A colored layer formed as a lower layer of a certain bright layer (B) and the bright layer (B), containing a crystalline polyester resin and 10 to 50% by weight of a coloring pigment, and having a haze value of 80% or more. (C) and a laminated sheet comprising the above are provided.

In the laminated sheet of the present embodiment, it is preferable that the bright pigment contained in the bright layer (B) is an aluminum pigment containing aluminum particles having an average particle size of 5 to 30 μm.
In the laminated sheet of the present embodiment, the direction perpendicular to the surface of the transparent resin layer (A) is set as a reference direction, and visible light is directed toward the transparent resin layer (A) from a direction at an angle of 75 ° from the reference direction. The brightness when irradiated with is preferably 0.1% or more.
In the laminated sheet of the present embodiment, the printed layer (D) formed on the transparent resin layer (A) and the protective layer (E) containing the transparent polyester resin formed on the printed layer (D). ), And more preferably.
In the laminated sheet of the present embodiment, it is preferable to further include a print protection layer (F) formed on the transparent resin layer (A) and printed on the polyester resin film.

Further, according to the present invention, there is provided a laminated board in which the above-mentioned laminated sheet is formed on a base material.

Further, according to the present invention, in the above method for producing a laminated sheet, the three layers of the transparent resin layer (A), the bright layer (B) and the colored layer (C) are once melt-coextruded. Provided is a method for producing a laminated sheet including a step of forming the laminated sheet.

According to the present invention, it is possible to provide a laminated sheet having excellent designability and excellent processability and corrosion resistance.

It is an embodiment of a laminated board using the laminated sheet of the present invention. It is sectional drawing which shows the other example of the laminated board using the laminated sheet of this invention. It is sectional drawing which shows still another example of the laminated board using the laminated sheet of this invention. It is sectional drawing which shows still another example of the laminated board using the laminated sheet of this invention.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The laminated sheet according to the present invention is used to impart design to various products such as refrigerators, washing machines and other electric appliances, buildings, vehicles, wall materials for unit baths, and building materials such as outer walls of houses. It is used as a member constituting the decorative steel sheet to be used. In the following, as an embodiment of the present invention, an example of a laminated board in which such a laminated sheet is used will be described with reference to the drawings.

As shown in FIG. 1, the laminated board 1 of the present embodiment includes a base material 12 and a laminated sheet 11. The laminated sheet 11 may be directly laminated on the base material 12, but is preferably laminated via the adhesive layer 17 as shown in FIG. First, the laminated sheet 11 constituting the laminated plate 1 will be described. As shown in FIG. 1, the laminated sheet 11 of the present embodiment has a transparent resin layer (A) represented by reference numeral 111, a bright layer (B) represented by reference numeral 112, and a colored layer represented by reference numeral 113. (C) is laminated in this order. In the present embodiment, the laminated sheet 11 is laminated on the base material 12 so that the colored layer (C) faces the base material 12.

<Transparent resin layer (A)>
The transparent resin layer (A) constituting the laminated sheet 11 of the present embodiment contains a crystalline polyester resin and a coloring pigment of 20% by weight or less, and the haze value is controlled to 20% or less. The transparent resin layer (A) of the present embodiment has an effect of protecting the brilliant layer (B) described later, and has transparency when the haze value is 20% or less. The bright layer (B) can be satisfactorily protected without impairing the bright feeling of the layer (B).

The crystalline polyester resin constituting the transparent resin layer (A) is not particularly limited, but a polyester composed of a dicarboxylic acid component and a glycol component is preferable, and the dicarboxylic acid component includes isophthalic acid (IA), orthophthalic acid, and P. Examples thereof include -β-oxyethoxybenzoic acid, naphthalene 2,6-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, adipic acid, and sebacic acid. Examples of the glycol component include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexylene glycol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, and the like, and one or more of each. May include. Further, a small amount of trivalent or higher valent components such as trimellitic acid and pyromellitic acid may be contained. More specifically, examples of the crystalline polyester resin constituting the transparent resin layer (A) include polyethylene terephthalate (PET), modified polyethylene terephthalate (modified PET), polybutylene terephthalate (PBT), and modified polybutylene terephthalate (PBT). Examples thereof include crystalline polyester resins such as modified PBT), and among these, polybutylene terephthalate (PBT) is particularly preferable. These crystalline polyester resins can be used alone or in a blend of two or more.

The coloring pigment that may be contained in the transparent resin layer (A) is not particularly limited, and known coloring pigments such as white pigment, black pigment, red pigment, blue pigment, and yellow pigment can be used. Examples of white pigments include rutile-type or anatase-type titanium dioxide, zinc white, gloss white, pearlite, precipitated pearlite sulfate, calcium carbonate, gypsum, precipitated silica, aerodyl, talc, calcined or unburned clay, and carbonic acid. Examples thereof include barium, alumina white, synthetic or natural mica, synthetic calcium silicate, magnesium carbonate and the like, and among these, rutile-type or anatase-type titanium dioxide is preferable. Examples of the black pigment include carbon black and magnetite. Examples of the red pigment include red iron oxide and lead tan. Examples of the blue pigment include ultramarine blue and cobalt blue. Examples of the yellow pigment include chrome yellow and zinc chromate.

The particle size of these coloring pigments is preferably 0.05 to 2 μm, more preferably 0.1 to 0.5 μm. By setting the particle size of the coloring pigment to 0.05 μm or more, the surface area per unit volume can be made appropriate, and it is possible to more effectively suppress the coloring pigment from adsorbing too much water. The viscosity of the mixture obtained when the coloring pigment is mixed with the crystalline polyester resin becomes appropriate, and the occurrence of aggregation of the coloring pigment particles in the mixture can be more effectively suppressed. Further, by setting the particle size of the coloring pigment to 2 μm or less, it is possible to more effectively prevent the laminated sheet 11 from being torn when the laminated sheet 11 is laminated on the base material 12. , When the laminated plate 1 formed by laminating the laminated sheet 11 on the base material 12 is molded into a desired shape, it is possible to effectively prevent the laminated sheet 11 from peeling off, and the bending property is as good as possible. Workability such as is further improved.

The method for forming the transparent resin layer (A) is not particularly limited, but for example, by extrusion-molding a mixture containing a crystalline polyester resin and a coloring pigment of 20% by weight or less by an extrusion film forming machine. Can be formed. The transparent resin layer (A) is preferably unstretched, but may be stretched in the uniaxial direction or the biaxial direction. Further, the transparent resin layer (A) may be a single layer, or may be formed by laminating two or more layers of the same or different resins. Further, the transparent resin layer (A) may be extruded alone, or may be molded by coextrusion together with the bright layer (B) and / or the colored layer (C), and the bright layer (B) and It is preferable to mold by co-extrusion of three layers together with the colored layer (C).

The content ratio of the coloring pigment in the transparent resin layer (A) may be 20% by weight or less, preferably 12% by weight or less, and more preferably 5% by weight or less. Further, the transparent resin layer (A) does not substantially contain a coloring pigment and may be uncolored. If the content ratio of the coloring pigment is too large, the transparent resin layer (A) becomes opaque, and as a result, the brilliant feeling of the brilliant layer (B) of the obtained laminated sheet 11 is impaired, and the design It will be inferior in sex. Further, if the content ratio of the coloring pigment is too large, the laminated sheet 11 is formed into a desired shape when the laminated sheet 1 obtained by laminating the obtained laminated sheet 11 is laminated on the base material 12, and the bending property of the laminated sheet 11 is increased. Workability is reduced.

The haze value of the transparent resin layer (A) may be 20% or less, but is preferably 15% or less, more preferably 10% or less. By setting the haze value in the above range, the transparent resin layer (A) can be made excellent in transparency, so that the resulting laminated sheet 11 does not impair the brilliant feeling of the brilliant layer (B). It becomes possible to make it more excellent in design. The haze value of the transparent resin layer (A) can be obtained based on the results of measurement of a single transparent resin layer (A) in accordance with JIS K7136. The haze value of the transparent resin layer (A) may be obtained by directly measuring the transparent resin layer (A) to be used, but the haze value of the transparent resin layer (A) whose thickness has been changed in advance is used. The haze value of the transparent resin layer (A) to be used may be calculated based on the measurement results.

The thickness of the transparent resin layer (A) is not particularly limited, but is preferably 1 to 75 μm, more preferably 5 to 50 μm, and even more preferably 10 to 30 μm. By setting the thickness of the transparent resin layer (A) in the above range, the transparent resin layer (A) has an appropriate transparency, and the transparent resin layer (A) has a sufficient thickness to protect the bright layer (B). This makes it possible to better protect the bright layer (B) of the obtained laminated sheet 11 without impairing the bright feeling of the bright layer (B).

<Glow layer (B)>
The bright layer (B) constituting the laminated sheet 11 of the present embodiment contains a crystalline polyester resin and 1 to 50% by weight of a bright pigment, and the haze value is controlled to 50% or more. The brilliant layer (B) of the present embodiment has an action of imparting a brilliant feeling to the laminated sheet 11.

The crystalline polyester resin constituting the bright layer (B) is not particularly limited, and examples thereof include the same as the crystalline polyester resin constituting the transparent resin layer (A) described above. When the laminated sheet 11 is produced, the crystalline polyester resin constituting the bright layer (B), the crystalline polyester resin constituting the transparent resin layer (A), and the crystals constituting the colored layer (C) described later are used. It is preferable to use the same sex polyester resin.

The bright pigment constituting the bright layer (B) may be any one capable of imparting a bright feeling to the bright layer (B), and is not particularly limited, but is limited to aluminum pigments containing aluminum particles, aluminum flakes and titanium. Metal flakes such as flakes, finely cut metal foils such as aluminum foil, various pearl pigments with surface modifications such as titanium coat (for example, "Iriodin" manufactured by Merck), silver, nickel and other various metals. Electrolytic plating-treated glass flakes (for example, "Metashine" manufactured by Nippon Plate Glass Co., Ltd.), metal foil such as aluminum foil surface-treated with a heat-curable resin such as epoxy resin, cut into small pieces (for example, diamond) Industrial company's "Diamond Piece", "Aluminum", etc.), finely cut resin sheets made by electroless plating various metals, finely cut hologram foil laminated on resin sheets, etc. Among them, the aluminum pigment is particularly preferable from the viewpoint that the laminated sheet 11 can give a good brilliant feeling.

When an aluminum pigment is used as the bright pigment, the average particle size of the aluminum particles in the aluminum pigment can be selected from the range of preferably 5 to 30 μm according to the desired brightness. By setting the average particle size of the aluminum particles in the above range, the formed brilliant layer (B) can be made more excellent in brilliant sensation, and the obtained laminated sheet 11 has more excellent design. Become.

The method for forming the bright layer (B) is not particularly limited, but for example, by extrusion-molding a mixture containing a crystalline polyester resin and 1 to 50% by weight of a bright pigment by an extrusion film forming machine. Can be formed. The bright layer (B) is preferably unstretched, which is excellent in workability, but may be stretched in the uniaxial direction or the biaxial direction. Further, the bright layer (B) may be a single layer, or may be formed by laminating two or more layers of the same or different resins. The bright layer (B) may be extruded alone, or may be co-extruded together with the transparent resin layer (A) and / or the colored layer (C), and the transparent resin layer (A) may be formed. And it is preferable to mold by coextrusion of three layers together with the colored layer (C).

The method of mixing the crystalline polyester resin and 1 to 50% by weight of the bright pigment is not particularly limited, and for example, a method of kneading the bright pigment into the crystalline polyester resin can be used.

The content ratio of the bright pigment in the bright layer (B) may be 1 to 50% by weight, preferably 3 to 30% by weight, and more preferably 5 to 20% by weight. If the content ratio of the bright pigment is too small, the bright feeling of the bright layer (B) becomes insufficient, and the obtained laminated sheet 11 is inferior in design. On the other hand, if the content ratio of the bright pigment is too large, when the laminated plate 1 formed by laminating the obtained laminated sheet 11 on the base material 12 is molded into a desired shape, the bending property of the laminated sheet 11 or the like is formed. Workability is reduced.

The haze value of the bright layer (B) may be 50% or more, but is preferably 55% or more, more preferably 60% or more. The haze value of the bright layer (B) usually tends to increase as the content ratio of the bright pigment in the bright layer (B) increases. By setting the haze value in the above range, that is, by incorporating the bright pigment in the bright layer (B) so that the haze value is in the above range, the bright layer (B) is made more excellent in the bright feeling. This makes it possible to improve the design of the obtained laminated sheet 11. The haze value of the bright layer (B) can be obtained based on the results of measurement of a single bright layer (B) in accordance with JIS K7136. The haze value of the bright layer (B) may be obtained by directly measuring the bright layer (B) to be used, but the haze value of the bright layer (B) whose thickness has been changed in advance is measured. Then, the haze value of the bright layer (B) to be used may be calculated based on the measurement result.

The thickness of the bright layer (B) is not particularly limited, but is preferably 10 to 100 μm, more preferably 20 to 80 μm, and even more preferably 25 to 60 μm. By setting the thickness of the bright layer (B) to the above range, the laminated sheet 11 is excellent in design, and the laminated plate 1 formed by forming the laminated sheet 11 on the base material 12 is processed into a desired shape. Workability such as bendability at the time of molding can be further improved.

<Colored layer (C)>
The colored layer (C) constituting the laminated sheet 11 of the present embodiment contains a crystalline polyester resin and 10 to 50% by weight of a colored pigment, and the haze value is controlled to 80% or more. In the colored layer (C) of the present embodiment, the laminated sheet 11 is laminated on the base material 12 so that the laminated plate 1 shown in FIG. 1 (the colored layer (C) of the laminated sheet 11 faces the base material 12). In the laminated board 1), it acts as a concealing layer for concealing the base material 12. As a result, in the laminated board 1, the base material 12 is concealed by the colored layer (C), and the brilliant feeling of the brilliant layer (B) formed on the colored layer (C) is appropriately exhibited, and the laminated plate 1 is laminated. The design of the plate 1 can be improved.

The crystalline polyester resin constituting the colored layer (C) is not particularly limited, and examples thereof include the same crystalline polyester resin constituting the transparent resin layer (A) described above. When the laminated sheet 11 is produced, the crystalline polyester resin forming the colored layer (C), the crystalline polyester resin forming the bright layer (B), and the crystalline polyester forming the transparent resin layer (A) are formed. It is preferable to use the same resin.

The coloring pigments constituting the coloring layer (C) are not particularly limited, and like the coloring pigments that can be contained in the transparent resin layer (A) described above, white pigments, black pigments, red pigments, blue pigments, etc. Known coloring pigments such as yellow pigments can be used.

The method for forming the colored layer (C) is not particularly limited, but for example, by extrusion-molding a mixture containing a crystalline polyester resin and 10 to 50% by weight of a colored pigment by an extrusion film forming machine. Can be formed. The colored layer (C) is preferably unstretched, but may be stretched in the uniaxial direction or the biaxial direction. Further, the colored layer (C) may be a single layer, or may be formed by laminating two or more layers of the same or different resins. Further, the colored layer (C) may be extruded alone, or may be molded by coextrusion together with the transparent resin layer (A) and / or the bright layer (B), and the transparent resin layer (A) may be formed. And it is preferable to mold by coextrusion of three layers together with the bright layer (B).

The content ratio of the coloring pigment in the colored layer (C) may be 10 to 50% by weight, preferably 13 to 35% by weight, and more preferably 15 to 25% by weight. If the content ratio of the coloring pigment is too small, the base material 12 is not sufficiently concealed by the coloring layer (C), and the obtained laminated sheet 11 is inferior in design. On the other hand, if the content ratio of the coloring pigment is too large, the laminated sheet 11 is formed into a desired shape when the laminated sheet 11 obtained by laminating the obtained laminated sheet 11 is laminated on the base material 12, or the like. Workability is reduced.

The haze value of the colored layer (C) may be 80% or more, but is preferably 90% or more, more preferably 95% or more. By setting the haze value in the above range, the colored layer (C) can satisfactorily conceal the base material 12, which is formed on the colored layer (C) in the laminated board 1. The brilliant feeling of the brilliant layer (B) is appropriately exhibited, and the design of the laminated plate 1 can be improved. The haze value of the colored layer (C) can be obtained based on the results of measurement of a single colored layer (C) in accordance with JIS K7136. The haze value of the colored layer (C) may be obtained by directly measuring the colored layer (C) to be used, but the haze value of the colored layer (C) whose thickness has been changed in advance is measured. Then, the haze value of the colored layer (C) to be used may be calculated based on the measurement result.

The thickness of the colored layer (C) is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 80 μm, and even more preferably 20 to 60 μm. By setting the thickness of the colored layer (C) within the above range, the colored layer (C) can satisfactorily conceal the base material 12, whereby the colored layer (C) in the laminated board 1 can be covered. The brilliant feeling of the brilliant layer (B) formed above is appropriately exhibited, and the design of the laminated plate 1 can be improved.

As described above, the laminated sheet 11 of the present embodiment is configured.

According to the laminated sheet 11 of the present embodiment, the transparent resin layer (A), the bright layer (B) and the colored layer (C) described above are laminated in this order, so that the colored layer (C) is the base material 12 Can be well concealed, the brilliant feeling of the brilliant layer (B) can be appropriately exhibited, the design of the laminated plate 1 can be improved, and the transparent resin layer (A) and the brilliant layer (B) can be improved. Since the content ratio of the colored pigment or the bright pigment in the colored layer (C) is controlled within the above range, the processability is also excellent.

Further, the laminated sheet 11 of the present embodiment is also excellent in corrosion resistance. That is, the laminated sheet 11 of the present embodiment has a transparent resin layer (A), a bright layer (B), and a colored layer (C) as a thermosetting adhesive (for example, a polyester adhesive, a urethane adhesive, or the like). It can be obtained by laminating without using an adhesive for dry laminating such as, and a defect due to the use of such an adhesive for dry laminating, that is, the appearance of the obtained laminated sheet deteriorates, and the design A problem that the laminated sheet peels off between layers when the property is deteriorated or when it is used for a long period of time (especially when it is used in a high temperature and high humidity environment such as a wall material of a unit bath). It becomes possible to prevent the occurrence of the above, and as a result, the corrosion resistance is also excellent.

Further, conventionally, as a laminated sheet, a metal vapor deposition layer or a high-brightness ink layer for obtaining metal luster is formed on a thermoplastic resin film layer, and then a support base material resin layer is further formed on the metal vapor deposition layer or a high-brightness ink layer. However, when a metal-deposited layer is formed, the corrosion resistance becomes inferior (particularly, the metal-deposited layer elutes when it comes into contact with a corrosive solution such as a household detergent. ), On the other hand, when a high-brightness ink layer is formed, there is a problem that the adhesion between the high-brightness ink layer and another layer becomes inferior.

On the other hand, the laminated sheet 11 of the present embodiment does not use such a metal vapor deposition layer or a high-brightness ink layer, and has a transparent resin layer (A) and a bright layer (B) having the above-mentioned unique structure. Since it is formed by using the colored layer (C) and the colored layer (C), it has excellent corrosion resistance when it comes into contact with a corrosive solution, and also has excellent adhesion of each layer constituting the laminated sheet 11. ..

The laminated sheet 11 of the present embodiment has a reference direction in the direction perpendicular to the surface of the transparent resin layer (A), and visible light toward the transparent resin layer (A) from a direction at an angle of 75 ° from the reference direction. The brightness when irradiated with is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1.0% or more. The brightness of the laminated sheet 11 is measured in the direction perpendicular to the surface of the transparent resin layer (A) of the laminated sheet by using, for example, a multi-angle colorimeter (model number "YK-mac", manufactured by BYK-Gardner). Can be obtained by irradiating visible light toward the transparent resin layer (A) from a direction at an angle of 75 ° from the reference direction and measuring.

Next, the base material 12 constituting the laminated board 1 of the present embodiment will be described.

The base material 12 is not particularly limited, but a steel plate or another metal plate (for example, an aluminum plate) can be used. As steel sheets, cold-rolled steel sheets, plated steel sheets obtained by plating cold-rolled steel sheets with zinc, zinc alloys, aluminum alloys, etc., and cold-rolled steel sheets are subjected to chemical conversion treatments such as electrolytic chromium acid treatment, phosphoric acid chromate treatment, and various non-chromium treatments. It is preferable to use a surface-treated steel sheet, or a surface-treated plated steel sheet obtained by subjecting these plated steel sheets to these chemical conversion treatments. Further, depending on the use of the laminated board 1, a wood board such as a wooden board or plywood, or a non-metal board such as a gypsum board or a plastic board can be used as the base material 12.

As described above, the laminated board 1 of the present embodiment is configured.

Since the laminated board 1 of the present embodiment is formed by using the above-mentioned laminated sheet 11, it is excellent in designability, and also excellent in processability and corrosion resistance. Therefore, the laminated board 1 of the present embodiment can be used as an interior material, an exterior material or a surface layer material, a wall material of a unit bath, an outer wall of a house, etc. of various products such as refrigerators, washing machines and other electric appliances, buildings, and vehicles. It can be suitably used as a building material.

In the example of FIG. 1 described above, the laminated plate 1 is composed of the laminated sheet 11 and the base material 12, but another layer such as a printing layer is further formed on the laminated sheet 11. You may.

For example, as in the laminated board 1a shown in FIG. 2, in the laminated board 1a, a print layer (D) represented by reference numeral 14 is formed on the laminated sheet 11, and the printed layer (D) represented by reference numeral 14 is formed on the laminated plate 1a with reference numeral 15. The represented protective layer (E) may be formed in this order.

The adhesive layer 13 is not particularly limited as long as it can satisfactorily bond the printed layer (D) and the protective layer (E), but examples of the adhesive constituting the adhesive layer 13 include. , Emulsion-type adhesives such as vinyl acetate resin, ethylene-vinyl acetate resin, urea resin, urethane resin, acrylic resin, polyester resin, polyester urethane resin, and adhesives such as epoxy-phenol resin. Among these, it is preferable to use an adhesive containing a polyester resin as a main component.

The printing layer (D) is a layer formed on the laminated sheet 11 by printing ink, and is a layer formed by printing a desired pattern, pattern, or the like within a range that does not impair the brilliance of the laminated sheet 11. .. As the printing ink for forming the printing layer (D), for example, a cellulose derivative such as nitrocellulose or cellulose acetate, or a printing ink containing a polyester resin, a urethane-modified polyester resin, or the like as a vehicle can be used. Among these, polyester resin-based inks are preferable from the viewpoints of both adhesion and thermal adhesion. The print layer (D) is preferably translucent or has a pattern having a region in which printing ink is not partially formed.

The protective layer (E) is preferably formed from the viewpoint of protecting the printed layer (D) and contains a transparent polyester resin. The transparent polyester resin constituting the protective layer (E) is not particularly limited, but is limited to polyethylene terephthalate (PET), modified polyethylene terephthalate (modified PET), polybutylene terephthalate (PBT), modified polybutylene terephthalate (modified PBT), and the like. Examples thereof include transparent polyester resin, and among these, polybutylene terephthalate (PBT) is particularly preferable. These transparent polyester resins can be used alone or in a blend of two or more.

The adhesive layer 13, the printing layer (D) represented by reference numeral 14, and the protective layer (E) represented by reference numeral 15 are on the laminated sheet 11 as in the laminated board 1b shown in FIG. The adhesive layer 13, the printed layer (D), and the protective layer (E) may be formed in this order.

Further, in the present embodiment, as in the laminated plate 1c shown in FIG. 4, a print protection layer (F) represented by reference numeral 16 is formed on the laminated sheet 11 via the adhesive layer 13. May be good. The print protection layer (F) is formed by forming the above-mentioned print layer (D) in advance on the above-mentioned protection layer (E). Stretched polyester is preferable as the base material constituting the print protection layer (F), and the print layer (D) is usually formed on the adhesive surface side.

Further, in the present embodiment, the above-mentioned laminated sheet 11 may be laminated on the base material 12 as it is, but is laminated on the base material 12 via an adhesive layer. Is preferable. For example, as in the example shown in FIGS. 1 to 4, the laminated sheet 11 is preferably laminated on the base material 12 via an adhesive layer 17 or the like. As the adhesive layer 17, the same adhesive layer 13 as the adhesive layer 13 can be used.

The laminated board of this embodiment is not limited to the above-mentioned examples of FIGS. 2 to 4, and for example, in the laminated boards 1a to 1c of each of the embodiments shown in FIGS. 2 to 4, the printed layers (D) ( The stacking order of the other layers on the laminated sheet 11, such as reference numeral 14), protective layer (E) (reference numeral 15), and printed protective layer (F) (reference numeral 16), is not particularly limited, and the other layers may be used. The formed laminated sheet 11 can be laminated on the base material 12, or the laminated sheet 11 can be laminated on the base material 12 and then another layer can be laminated.

Further, in the laminated plates 1, 1a to 1c and the like of the respective embodiments shown in FIGS. 1 to 4, in order to further enhance the design, the laminated sheet 11 in which the uneven pattern is formed by embossing can be used. As a method for manufacturing such a laminated plate 1, a method in which the laminated sheet 11 is embossed when the laminated sheet 11 is extruded to form a laminated sheet 11 having an uneven pattern, and the laminated sheet 11 is laminated on the base material 12. Alternatively, there is a method of embossing when laminating the laminated sheet 11 on the base material 12. Further, the laminated sheet 11 on the laminated plate 1 may be embossed by post-processing.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The evaluation method of each characteristic is as follows.

<Brightness>
Using a multi-angle colorimeter (model number "YK-mac", manufactured by BYK-Gardner), the direction perpendicular to the surface of the transparent resin layer (A) of the laminated sheet of the laminated board is set as the reference direction, and from the reference direction. The brightness when visible light was irradiated toward the transparent resin layer (A) from the direction of an angle of 75 ° was measured.

<Haze value>
Each single-layer film of the transparent resin layer (A), the bright layer (B), and the colored layer (C) was formed, and the haze value was evaluated by a method according to JIS K7136.

<Concealment>
The surface of the laminated board was visually confirmed, and whether or not the base material, which is the base of the laminated sheet, was sufficiently concealed by the laminated sheet was evaluated according to the following criteria.
A: The base material that is the base of the laminated sheet was sufficiently concealed by the laminated sheet.
B: The base material, which is the base of the laminated sheet, was seen through.

<Workability>
The laminated board was evaluated according to JIS Z2248 bent at 180 °. The bendability during processing was evaluated according to the following criteria.
A: No visual cracks B: Visual cracks

<Corrosion resistance>
After allowing the laminated board to stand in a high-temperature and high-humidity tank at a temperature of 60 ° C., a humidity of 95% RH, and 1000 hours, the laminated board is taken out from the high-temperature and high-humidity tank, and whether or not the laminated sheet is peeled off from the substrate Was visually confirmed. Then, based on the confirmed results, the corrosion resistance of the laminated board was evaluated according to the following criteria.
A: The laminated sheet did not peel off, and the metal contained in the laminated sheet was not exposed.
B: The laminated sheet was partially peeled off.
C: The laminated sheet has peeled off.

<< Example 1 >>
First, a hot-dip galvanized steel sheet having a thickness of 0.45 mm was prepared as a base material for laminating the laminated sheet 11, and an adhesive was applied to the surface of the prepared hot-dip galvanized steel sheet.

On the other hand, polybutylene terephthalate (PBT) was prepared as a raw material for forming the transparent resin layer (A). Further, as a raw material for forming the bright layer (B), a mixture of polybutylene terephthalate (PBT) and 5% by weight of an aluminum pigment (bright pigment) containing aluminum particles having a particle size of 30 μm was prepared. Further, as a raw material for forming the colored layer (C), a mixture of polybutylene terephthalate (PBT) and 20% by weight of an inorganic colored pigment was prepared.

Then, using the raw material of the transparent resin layer (A), the raw material of the bright layer (B), and the raw material of the colored layer (C) described above, the thickness of each layer is co-extruded by a three-layer coextrusion film forming machine. A laminated sheet having a total thickness of 100 μm was prepared so that the transparent resin layer (A): the bright layer (B): the colored layer (C) = 15 μm: 35 μm: 50 μm. The haze values of the transparent resin layer (A), the bright layer (B), and the colored layer (C) were the values shown in Table 1, respectively.

Next, the produced laminated sheet was laminated on the surface coated with the adhesive of the above-mentioned hot-dip galvanized steel sheet to obtain a laminated plate.

Then, using the obtained laminated board, the brightness, hiding property, processability, and corrosion resistance were evaluated according to the above method. The results are shown in Table 1.

<< Example 2 >>
A laminated board was prepared in the same manner as in Example 1 except that a mixture of polybutylene terephthalate (PBT) and 5% by weight of an inorganic coloring pigment was used as a raw material for the transparent resin layer (A), and evaluated in the same manner. .. The results are shown in Table 1.

<< Example 3 >>
The content ratio of the aluminum pigment in the raw material of the bright layer (B) was changed to 15% by weight, the content ratio of the inorganic coloring pigment in the coloring layer (C) was changed to 25% by weight, and the thickness of each layer was changed to the transparent resin layer (A). ): Bright layer (B): Colored layer (C) = 50 μm: 75 μm: 75 μm, except that the total thickness was changed to 200 μm, a laminated board was prepared in the same manner as in Example 2 and evaluated in the same manner. did. The results are shown in Table 1.

<< Example 4 >>
A laminated board was produced in the same manner as in Example 2 except that the content ratio of the inorganic coloring pigment in the raw material of the transparent resin layer (A) was changed to 15% by weight, and evaluated in the same manner. The results are shown in Table 1.

<< Example 5 >>
A laminated board was prepared in the same manner as in Example 2 except that a mixture of polybutylene terephthalate (PBT) and 5% by weight of an aluminum pigment containing aluminum particles having a particle size of 5 μm was used as a raw material for the bright layer (B). And evaluated in the same way. The results are shown in Table 1.

<< Example 6 >>
A laminated board was produced in the same manner as in Example 1 except that the content ratio of the aluminum pigment in the raw material of the bright layer (B) was changed to 20% by weight, and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
The content ratio of the inorganic coloring pigment in the raw material of the transparent resin layer (A) is 0.5% by weight, the content ratio of the aluminum pigment in the raw material of the bright layer (B) is 0.5% by weight, and the coloring layer (C). ), The laminated board was prepared in the same manner as in Example 1 except that the content ratio of the inorganic coloring pigment in the raw material was changed to 5% by weight, and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 2 >>
Except for changing the content ratio of the inorganic coloring pigment in the raw material of the transparent resin layer (A) to 0.5% by weight and the content ratio of the inorganic coloring pigment in the raw material of the coloring layer (C) to 50% by weight. , A laminated board was prepared in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 3 >>
A laminated board was produced in the same manner as in Example 1 except that the content ratio of the inorganic coloring pigment in the raw material of the transparent resin layer (A) was changed to 30% by weight, and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 4 >>
A metal vapor deposition layer was formed on the stretched PET layer by vacuum-depositing aluminum on the surface of a film (stretched PET layer) of stretched polyethylene terephthalate (PET) having a thickness of 12 μm. On the other hand, as a base resin, an unoriented PET film having a thickness of 100 μm was prepared. Then, an adhesive layer is formed by applying an adhesive on the base resin, and then the adhesive layer is formed on the base resin so that the adhesive layer and the metal vapor deposition layer face each other. , A laminated board was obtained by laminating a stretched PET layer on which a metal vapor deposition layer was formed. In Comparative Example 4, the stretched PET layer and the metal vapor deposition layer correspond to the laminated sheet, and the base resin corresponds to the base material, respectively. Then, the corrosion resistance of the obtained laminated board was evaluated according to the above method. The results are shown in Table 1.

<< Comparative Example 5 >>
A laminated board was produced in the same manner as in Comparative Example 4 and evaluated in the same manner, except that a glitter ink layer formed by applying a glitter ink was formed on the stretched PET layer instead of the metal vapor deposition layer. The results are shown in Table 1. In Comparative Example 5, the stretched PET layer and the brilliant ink layer correspond to the laminated sheet, and the base resin corresponds to the base material, respectively.
The following inks were used as the glitter inks. First, 10 parts by weight of aluminum thin film fragments (thickness 0.04 μm, size in the plane direction 5 to 25 μm), 37.25 parts by weight of ethyl acetate, 30 parts by weight of methyl ethyl ketone, 31.5 parts by weight of isopropyl alcohol, nitrocellulose. 1.25 parts by weight were mixed (110 parts by weight in total) to prepare an aluminum thin film fragment slurry. Next, 30 parts by weight of the obtained aluminum thin film fragment slurry, 3 parts by weight of a carboxylic acid-containing vinyl chloride-vinyl acetate resin (commercial surface "Vinilite VMCH", manufactured by UCC) as a binder resin, and a urethane resin (trade name). "Polyurethane 2593" non-volatile content 32%, manufactured by Arakawa Chemical Industries, Ltd.) is mixed by 8 parts by weight, ethyl acetate by 23 parts by weight, 4-methyl-2-pentanone by 26 parts by weight, and isopropyl alcohol by 10 parts by weight (total 100 parts by weight). ), And a high-brightness ink having a concentration of 35% by weight of aluminum thin film fragments in the non-volatile content was prepared and used.

As shown in Table 1, when the laminated sheet is formed of the transparent resin layer (A), the bright layer (B) and the colored layer (C) peculiar to the present invention, the obtained laminated plates have comparative brightness. It was highly targeted and had excellent concealing property, processability and corrosion resistance (Examples 1 to 6).

On the other hand, as shown in Table 1, when the content ratio of the bright pigment in the bright layer (B) was too small, the brightness of the obtained laminated board was lowered (Comparative Example 1).
Further, as shown in Table 1, when the content ratio of the coloring pigment in the colored layer (C) was too small, the obtained laminated board was inferior in the hiding property of the base material by the laminated sheet (comparison). Example 1). On the other hand, when the content ratio of the colored pigment in the colored layer (C) was too large, the obtained laminated board was inferior in processability (Comparative Example 2).
Further, as shown in Table 1, when the content ratio of the coloring pigment in the transparent resin layer (A) is too large, the bright layer (B) is concealed by the transparent resin layer (A), and the resulting laminate is obtained. The brightness of the board has decreased (Comparative Example 3).

Further, as shown in Table 1, the laminated board on which the metal vapor deposition film was formed was a result of the laminated sheet being partially peeled off from the base material, and was inferior in corrosion resistance (Comparative Example 4).
Further, as shown in Table 1, the laminated board on which the glitter ink layer was formed was inferior in corrosion resistance because the laminated sheet was peeled off from the base material (Comparative Example 5).

1 ... Laminated plate 11 ... Laminated sheet 111 ... Transparent resin layer (A)
112 ... Bright layer (B)
113 ... Colored layer (C)
12 ... Base material 13 ... Adhesive layer 14 ... Printing layer (D)
15 ... Protective layer (E)
16 ... Protective layer to be printed (F)
17 ... Adhesive layer

Claims (7)

A transparent resin layer (A) containing a crystalline polyester resin and a coloring pigment of 20% by weight or less and having a haze value of 20% or less measured in accordance with JIS K7136.
It is formed as a lower layer of the transparent resin layer (A), contains a crystalline polyester resin and 3 to 30 % by weight of a bright pigment, has a thickness of 10 to 100 μm, and has a haze value of 50% or more. Layer (B) and
A laminate including a colored layer (C) formed as a lower layer of the bright layer (B), containing a crystalline polyester resin and 10 to 50% by weight of a coloring pigment, and having a haze value of 80% or more. Sheet. The laminated sheet according to claim 1, wherein the bright pigment contained in the bright layer (B) is an aluminum pigment containing aluminum particles having an average particle size of 5 to 30 μm. The brightness when visible light is irradiated toward the transparent resin layer (A) from a direction at an angle of 75 ° from the reference direction with a direction perpendicular to the surface of the transparent resin layer (A) as a reference direction is determined. The laminated sheet according to claim 1 or 2, which is 0.1% or more. The printing layer (D) formed on the transparent resin layer (A) and
The laminated sheet according to any one of claims 1 to 3, further comprising a protective layer (E) containing a transparent polyester resin formed on the printed layer (D). The laminated sheet according to any one of claims 1 to 3, further comprising a print protection layer (F) formed on the transparent resin layer (A) and printed on a polyester resin film. A laminated board in which the laminated sheet according to any one of claims 1 to 5 is formed on a base material. The method for manufacturing a laminated sheet according to any one of claims 1 to 5.
A method for producing a laminated sheet, comprising a step of forming the three layers of the transparent resin layer (A), the bright layer (B), and the colored layer (C) at once by coextrusion.

Images