WO2004058495A1 - Feuille metallique recouverte de resine, feuille structuree pour feuille metallique, et procede de production de la feuille metallique recouverte de resine - Google Patents

Feuille metallique recouverte de resine, feuille structuree pour feuille metallique, et procede de production de la feuille metallique recouverte de resine Download PDF

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Publication number
WO2004058495A1
WO2004058495A1 PCT/JP2003/016387 JP0316387W WO2004058495A1 WO 2004058495 A1 WO2004058495 A1 WO 2004058495A1 JP 0316387 W JP0316387 W JP 0316387W WO 2004058495 A1 WO2004058495 A1 WO 2004058495A1
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Prior art keywords
layer
resin
metal plate
sheet
coated metal
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PCT/JP2003/016387
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English (en)
Japanese (ja)
Inventor
Toshiaki Ebitani
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Mitsubishi Plastics, Inc.
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Priority to JP2004562882A priority Critical patent/JP4209847B2/ja
Publication of WO2004058495A1 publication Critical patent/WO2004058495A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/06—Embossing

Definitions

  • the present invention relates to the exterior of home appliances such as AV equipment and air conditioner covers, plywood furniture, steel furniture, elevator interiors, and door interiors, unit pass wall materials, unit bath ceiling materials, and building interiors such as partitions.
  • the present invention relates to a highly durable resin-coated metal plate used for material applications, a design sheet for a resin-coated metal plate, and a method for producing a resin-coated metal plate. More specifically, it can be suitably used for applications such as unit pass which has excellent scratch resistance and workability, and has excellent durability in a wet heat environment, and is suitably used for coating applications having an embossed design such as a partition.
  • the present invention relates to a resin-coated metal plate that does not use a halogen-containing resin, a design sheet for the resin-coated metal plate, and a method for producing the resin-coated metal plate. Background art
  • a resin-coated metal plate used for the above-mentioned applications a laminate obtained by laminating a soft chloride-based sheet (hereinafter referred to as a “soft PVC sheet”) colored with a pigment, and a soft PVC provided with an embossed design Sheets coated with synthetic resin molded articles, plywood, wood fiber boards, metal sheets, etc., have been used.
  • a soft PVC sheet a laminate obtained by laminating a soft chloride-based sheet (hereinafter referred to as a “soft PVC sheet”) colored with a pigment
  • a coating material with excellent design properties can be obtained because of its excellent embossing suitability.
  • thermoplastic resins In thermoplastic resins, the balance between workability and scratch resistance on the surface, which are generally the trade-off factors, is relatively good.
  • a method of continuously embossing the long sheet of the soft PVC A method is generally used in which the sheet is softly heated by reheating, and the pattern is continuously transferred while being suppressed by a roll engraved with an embossed pattern (hereinafter referred to as “enbossed plate roll”).
  • Examples of the method of heating the sheet include a contact type in which the sheet is heated by being brought into contact with a heated metal roll, and a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater or a hot air heater. In an actual production line, only one of them may be used, but in general it is often used in combination, and equipment with these series of steps is called an embossing machine.
  • the embossing machine incorporates a design in which the embossing plate roll can be easily replaced and detached very easily.
  • the embossing pattern can be easily changed. It can be done economically and can be said to be an embossing method suitable for small lots.
  • the soft PVC sheet also had excellent suitability for giving an embossed design with the embossing machine.
  • a soft component such as a styrene-based or copolymerized olefin-based polymer mainly composed of a polyolefin-based resin such as polypropylene is blended.
  • the use of a resin with properties close to that of a soft vinyl chloride resin was carried out.
  • the polyolefin resin was basically excellent in chemical resistance and relatively good in wet heat resistance, so that it could be suitably used for applications such as a unit bath.
  • calendering of polypropylene-based sheets is also possible, which is comparable to flexible PVC in terms of small-lot production and color compatibility.
  • Polypropylene-based sheets have a narrower temperature range in which embossing can be performed than PVC sheets, and require more precise temperature control.However, embossing, which has been conventionally used to continuously emboss PVC sheets, has been used.
  • the advantage is that the application machine can be basically applied as it is. There is a However, when a large amount of the soft component was added to impart the required workability, the surface was inferior to the scratch resistance as compared with the case where the soft salted butyl resin was used. On the other hand, when the scratch resistance was made equal to that of a soft vinyl chloride resin-coated metal plate, there was a problem that satisfactory workability could not be obtained, so that it could not be widely used.
  • polyester resins are generally hydrolyzed in a moist heat environment and gradually become embrittled, so when used in a moist heat environment such as a unit bath, the appearance of the resin over time There is a risk of causing changes and peeling from the metal plate.
  • pigments are added to the sheet coated with the resin-coated metal plate for the purpose of imparting designability and concealing the groundwork.
  • a titanium oxide pigment is often used as a base as a white-based highly opaque pigment. It is necessary to use chromatic inorganic pigments and organic pigments in order to adjust the tint accordingly.
  • Inorganic pigments such as titanium oxide pigments themselves serve as catalysts for polyester resin degradation. In some cases, the deterioration of the polyester is also promoted by impurities in the pigment.
  • the void force formed between the pigment particles and the resin matrices has a water content in the thickness direction of the sheet. Will be increased. This is also a factor that promotes deterioration of the polyester resin itself, and at the same time, in the configuration of the resin-coated metal plate, there is a danger that the permeated moisture will corrode the metal plate surface and peel off between the sheet layer and the metal plate. Is increasing. For these reasons, when a sheet with no pigment and a titanium oxide pigment is prepared using a polyester resin of the same composition and formed into a resin-coated metal plate, the latter has a significantly higher wet heat resistance than the former. At present it is inferior.
  • the pigment-free kasumeng has no commercial value as a coated metal plate for interior building materials. Therefore, various attempts have been made to improve the durability of the white pigment-added system. Examples of such methods include sealing of catalyst activity by surface treatment of pigment particles and addition of various catalyst deactivators. However, the effect is not sufficient, and special surface treatment of pigment particles generally raises the cost significantly, and it is also difficult to balance dispersion with dispersibility. It has become a challenge.
  • the flexible PVC sheet is replaced with a sheet made of a polyester-based resin that is unstretched and is colored with a white pigment, the permeation of water is not affected because the biaxially stretched PET film exists on the surface layer. It is suppressed by the layer, and it is possible to obtain relatively good wet heat resistance. Further, it is suitably used for a unit bath because it has excellent specular reflectivity. However, with this configuration, it is not possible to obtain an embossed pattern.
  • Some non-crystalline polyester resins typified by so-called PETG can be made to have the ability to form a force render film by devising a lubricant or the like.
  • conventional soft PVC-based or polyolefin-based sheets are When embossing is applied (calender film forming method) using an embossing machine in the same manner as described above, a problem occurs in the emboss heat resistance.
  • the heat resistance of the emboss indicates whether the embossed design sheet or the embossed design sheet-covered metal plate is exposed to high heat in use, and the return of the emboss is large or small. In this case, it is assumed that the emboss heat resistance is good.
  • embossing can be regarded as the work of applying strain to a heated viscoelastic body and then cooling it to cool the strain.However, the frozen strain is heated to the temperature at which the strain is applied again. Then, a phenomenon of distortion recovery occurs. Therefore, in order to increase the emboss heat resistance, it is necessary to increase the temperature at which strain is applied.
  • the temperature at which distortion is applied (determined by the temperature of the sheet and the temperature of the embossing plate roll) to increase the emboss heat resistance
  • the melt tension of the sheet itself was remarkably reduced, and the width of the sheet was shrunk, wrinkled, and furthermore, the sheet was broken, and sufficient emboss heat resistance could not be imparted.
  • embossed patterns are often limited in terms of mold releasability and air embrace, for example, deep embossing / complex embossing cannot be applied.
  • casting rolls generally have a larger diameter than embossing rolls of embossing machines, and it is problematic in terms of equipment costs and replacement man-hours to arrange a number of casting rolls corresponding to the pattern.
  • Other methods include manufacturing a resin-coated metal sheet by extruding a molten resin onto a steel sheet and transferring the pattern by pressing it with an embossed pattern roll before the resin is cooled, or reusing a metal sheet coated with a resin sheet. There is a method of transferring by using an embossed pattern roll by heating.
  • the non-stretched polyester resin layer contains a large amount of pigment and mainly provides a colored design and a visual hiding effect of the base ( Hereinafter, it is referred to as a “layer A”) and a layer containing less than 10 parts by weight of a pigment and containing no pigment (hereinafter referred to as a “layer B”).
  • the layer (layer A) for which the moisture and heat resistance of the layer itself has to be reduced due to the necessity of adding a sufficient amount of pigment, is regarded as a layer (layer B) with a small amount of pigment added and having relatively good moisture and heat resistance.
  • a resin-coated metal plate having a configuration in which an unstretched polyester sheet capable of embossing can be laminated is provided with a sufficient coloring design, and also has excellent durability, particularly, moisture and heat resistance. can do.
  • the durability can be further improved by substantially not including a facial component in the layer B.
  • the physical properties can be maintained even after the deterioration with time.
  • the carbodiimide compound is added to the B layer at a ratio of 0.1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the resin, thereby extruding. Since a decrease in molecular weight due to the influence of moisture during use can be suppressed during film formation or as a resin-coated metal plate, durability, particularly wet heat resistance, can be improved.
  • the layer B contains a polybutylene terephthalate (hereinafter referred to as “PBT”) resin in an amount of 20% by weight or more of the resin component, the crystallinity during extrusion film formation of the layer B is improved. Regardless of the above, it is possible to impart boiling water immersion resistance.
  • the B layer contains 55% by weight or more of the PBT resin, and a highly crystalline B layer can be obtained depending on the casting conditions at the time of extrusion film formation. In this case, it is possible to obtain such a property that it does not stick to the heated metal part of the embossing machine without performing a crystallization treatment or the like in a later step.
  • the layer A is mainly composed of a non-crystalline or low-crystalline polyester resin
  • the sheet is heated to a temperature equal to or higher than the glass transition temperature (T ga) of the resin, so that an emboss pattern is formed by an embossing machine. Grants are possible.
  • the resin yarn of the layer A is made of a commercially available material, which is advantageous in cost, and the crystallization may progress with time. The problem is less likely to occur when embossing the sheet after long-term storage of the sheet.
  • a printed design can be provided simultaneously with the embossed design.
  • good embossing can be achieved by setting the sheet heating temperature of an embossing machine, which has been generally used for embossing a flexible PVC sheet, within the above range. Aptitude is obtained.
  • a printing design can be provided simultaneously with the embossed design, and a polyester resin layer (hereinafter, referred to as “E layer”) having a specific thickness and no pigment added on the printing layer.
  • E layer a polyester resin layer
  • the durability of the printing layer can be improved.
  • the E layer is mainly composed of a non-crystalline or low-crystalline polyester resin, the sheet is heated to a temperature equal to or higher than the glass transition temperature (T ga) of the resin, thereby giving an embossed pattern by an embossing machine. Is possible.
  • the resin composition of the E layer is made of a commercially available material, which has a merit of cost, and there is little possibility of crystallization progressing with time. Even when embossing is given after long-term storage, the problem hardly occurs.
  • the sheet heating temperature of an embossing machine which has been generally used for embossing a flexible PVC sheet, is set in the above range. Good embossing suitability can be obtained.
  • the layer A and the layer B are formed by co-extrusion, the risk of interfacial peeling over time is reduced, and the productivity is improved.
  • a fifteenth aspect of the present invention is a design sheet for a resin-coated metal plate in which at least two polyester-based resin layers of an embossing layer having different physical properties and a base resin layer are laminated, wherein the embossing layer is Since it is mainly made of non-crystalline resin and can be formed by the force rendering method, sheets of various colors can be efficiently obtained in small lots. Furthermore, since embossed pattern transfer can be performed by an embossing machine, not only color but also various patterns can be transferred with an embossed pattern.
  • the layer B having a predetermined thickness functions as a base resin layer and has crystallinity, even if the embossing machine is heated to a sheet temperature that would cause melt fracture in the embossing layer alone, If the melting point of the base resin layer is lower than T mb, the laminated sheet does not cause problems such as melt fracture and wrinkling. Therefore, it is possible to provide an embossed pattern having higher embossing heat resistance as compared to the case of using only the embossed layer alone, and there is little risk of appearance failure in an actual use environment.
  • the melting point T mb of the base resin layer is a crystal melting peak temperature at the time of primary temperature rise of the base resin layer by a differential scanning calorimeter (DSC).
  • the base resin layer is formed by extrusion film formation, but since various colors are imparted by the embossing layer, the base resin layer does not contain a pigment or is formed in a single color.
  • the color change loss which is a drawback of extrusion film formation, can be suppressed.
  • the base sheet resin layer contains a specific amount of a polybutylene terephthalate (PBT) -based resin having a high crystallization rate or more, and is extruded.
  • PBT polybutylene terephthalate
  • Preferred crystallinity can be imparted at the time of film formation. Therefore, crystallization treatment or the like in the subsequent step is not required, and since the melting point is not more than 25 ° C, the surface temperature of the metal sheet when laminating the conventional soft vinyl chloride-based sheet to the metal sheet is used. At about 230 ° C., a sufficient adhesive strength can be obtained.
  • a design sheet for a resin-coated metal plate that is effective in the sixteenth invention of the claims.
  • the design sheet for a resin-coated metal sheet according to the seventeenth aspect of the present invention is characterized in that the crystallinity of the base resin layer before passing through an embossing machine is measured by a differential scanning calorimeter (DSC) measurement value.
  • DSC differential scanning calorimeter
  • the design sheet for a resin-coated metal sheet according to the eighteenth invention of the claims has a track record of calender film formation as a resin component of an embossed layer, and is a commercially available amorphous polyester-based material. By using resin, stable production can be secured, which is also advantageous in terms of raw material prices.
  • the design sheet for a resin-coated metal sheet according to the ninth aspect of the present invention is obtained by coextruding a substantially non-crystalline resin layer on the surface of the base resin layer on the side to be laminated with the embossing layer. By providing them, it is possible to further ensure the interfacial adhesion strength by the heat fusion lamination.
  • the design sheet for a resin-coated metal sheet according to the twenty-first aspect of the present invention can further improve surface physical properties such as weather resistance, scratch resistance, and stain resistance.
  • an adhesive layer or the like is separately provided by laminating and integrating the embossing layer and the base resin layer by heat fusion. Man-hours can be reduced compared to the case of laminating and integrating, and it is also possible to supply each single sheet of the embossing layer and the base resin layer to the embossing machine and perform laminating and embossing simultaneously.
  • a resin-coated metal plate having various colors and embossed patterns and having high embossing heat resistance can be efficiently obtained with a small opening. it can.
  • the resin-coated metal plate after laminating is rapidly cooled to suppress the return of emboss during lamination.
  • an embossed design resin-coated metal plate having a deep design can be obtained.
  • FIG. 1 is a schematic diagram showing a resin-coated metal plate having a basic configuration of the first present invention.
  • FIG. 2 is a schematic view showing a laminated resin sheet having a basic configuration of the second invention.
  • FIG. 3 is a schematic view showing a general embossing apparatus for a flexible PVC sheet.
  • FIG. 1A is a schematic cross-sectional view showing the basic configuration of the resin-coated metal plate of the first invention.
  • a metal plate is formed via layer A, layer B, and adhesive layer.
  • FIG. 1 (b) in addition to the configuration of FIG. 1 (a), a printing ink layer (C layer) and a transparent coating layer (D layer) are provided.
  • FIG. 1 (c) a printing ink layer (C layer) and a transparent polyester resin layer (E layer) are provided in addition to the configuration of FIG. 1 (a).
  • the printing layer is composed of two layers (c-1 layer) and (c-12 layers), and the pattern printing layer and the solid printing layer are It corresponds to cases where it is granted. .
  • the laminated sheet of the present invention has a thickness of 65! Although it is more correct to write “film and sheet” because it has a range of up to 300 ⁇ , the term “sheet” is also used here for convenience in terms of the thickness range generally called film.
  • the non-stretched layer ( ⁇ layer) mainly composed of a polyester resin to which a pigment for coloring and hiding is mainly added may be simply referred to as ⁇ layer.
  • the resin component constituting the layer A may be referred to as a resin A.
  • the A layer is a non-stretched polyester resin layer, but the non-stretching means that the stretching operation is not applied intentionally, and there is even the orientation and the like generated by the drawing by the casting roll during extrusion film formation. That doesn't mean there isn't. These are the same for the layer B.
  • the pigment is added to the layer A for the purpose of giving a design by coloring and giving a visual hiding effect of the base.
  • the pigments used may be those generally used for coloring resins, but white pigments are needed to obtain a sufficient base hiding effect with the thickness of the sheet generally used for resin-coated metal plates. It is necessary to use a pigment mainly composed of a titanium oxide pigment as the pigment. Titanium oxide pigments are commonly used for resin kneading. This refers to the rutile crystal type that has been treated, and does not refer to titanium oxide without surface treatment—anatase type titanium with poor surface treatment effect. Of course, titanium oxide pigments and the like that have been subjected to special surface treatment may be used from the standpoint of improving durability, but at the present time, the corresponding effects have not been obtained despite the increase in cost.
  • Tones a desired white color tone using the titanium oxide pigment as a main component and inorganic and organic chromatic pigments in combination.
  • the preferred thickness of the A layer is in the range of 50; um to 250 / im. If the thickness is smaller than this, a titanium oxide pigment is used to secure the effect of concealing the base! It is necessary to add to the temperature, which may cause deterioration of the film forming property or the workability of the resin-coated metal plate. Further, the thickness is preferably 70 / m or more from the viewpoint that embossing patterns of various patterns can be transferred by an embossing machine described later. Further, even if the thickness exceeds 250 im, the effect of hiding the base is saturated, and only the cost is increased, which is not preferable.
  • the embossing machine conventionally used for embossing a soft PVC sheet offline is easy to replace the embossing plate roll, and is suitable for small-lot production. It is preferable that the embossing machine can be used also when giving an embossed pattern to the laminated sheet used for the coated metal plate.
  • the layer A is mainly composed of a substantially non-crystalline or low-crystalline polyester resin
  • the elastic modulus of the layer is increased by heating the resin to a temperature equal to or higher than the glass transition temperature (T ga) of the resin. Can be reduced to the extent that emboss transfer is possible.
  • the layer A is not used as a single layer but is used in a laminated structure with the layer B, by specifying the composition of the layer B, the layer A can be converted into a glass transition temperature ( T ga) In this case as well, functions such as prevention of breakage due to a decrease in sheet tension can be assigned to the layer B, and it is easy to provide suitability to an embossing machine.
  • non-crystalline polyester resin that forms the main component of the A layer terephthalic acid or dimethyl terephthalic acid is the main component of the acid component, and about 20 to about 80 mo 1.% Of the alcohol component is converted to 1,4-cyclohexane.
  • Xanthimethanol is preferably a copolymerized polyester resin in which the remaining about 80 to 20 mol% of ethylene glycol is ethylene glycol.
  • a resin composition in which approximately 30% of the alcohol component is 1,4-cyclohexanedimethanol and the remaining approximately 70mo1.% Is ethylene glycol is widely used and has a stable supply. This is preferable from the viewpoint of cost and the advantage of mass production.
  • "Easter PET G6763" manufactured by Yeastman Chemical Co., Ltd. can be mentioned as an example.
  • the non-crystalline or low-crystalline polyester resin referred to in the present invention means that the temperature of the A layer is at least the glass transition temperature (T ga) at least in the heating step using an embossing machine. Even if heated, the crystallization proceeds so that embossing becomes difficult.
  • alcohol components such as ethylene glycol, propanediol, butanediol, hexahexane dimethanol, 1,4-cyclohexane dimethanol, neopentyl glycol, etc., and terephthalic acid, isophthalic acid and adipine as acid components Resin arbitrarily selected from the polymer or copolymer of each single component such as acid, 1,4-cyclohexanedicarboxylic acid, etc. A substance having a low absolute value, a substance having a low crystallization rate, or the like can be appropriately selected and used.
  • additives may be added to the layer A in appropriate amounts to the extent that the properties are not impaired.
  • Additives include phosphorus-based phenolic and other antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, metal deactivators, residual polymerization catalyst deactivators, antibacterial and antifungal agents, Examples include those generally used in a wide variety of resin materials such as antistatic agents, lubricants, flame retardants, and fillers.
  • the film formation method of the A layer may be based on a force-rendering single film forming method.However, from the viewpoint of securing the durability of the laminated sheet as a whole, It is better to laminate firmly with layer B in a die by extrusion film forming method.
  • the layer B is a layer provided for ensuring the durability of the resin-coated metal plate, and the mechanism of expressing the durability is as described in “Means for Solving the Problems”.
  • the B layer first has a low pigment addition concentration, and it is particularly preferable that the pigment is not added. If the effect of concealing the base is not sufficient only by adding the pigment to the layer A, the pigment may be added to the layer B in an amount of 10 parts by weight or less based on 100 parts by weight of the resin component. From the viewpoint of ensuring the durability of the laminated sheet structure, which is the original meaning of the layer, and the durability of the resin-coated metal plate that covers it, it is particularly preferable that no pigment is contained. It is.
  • the layer B has a weight average molecular weight in terms of styrene by GPC (gel permeation chromatography) in the state after extrusion film formation in the range of 750 to 4,000. .
  • Hydrolysis is considered to be the main deterioration factor in the use of polyester resin in a moist heat environment, but this leads to brittleness as a deterioration in mechanical properties and breaks when folded in films etc. State. Even in the state of a resin-coated metal plate, cracks due to embrittlement of the film layer, and partial peeling of the film layer, etc. occur in conjunction with a decrease in adhesion strength to the metal plate, which significantly impairs the design in appearance. At the same time, the effect of coating the metal plate with the resin layer, ie, the effect of preventing corrosion of the metal surface and the effect of imparting design properties, cannot be obtained.
  • the degradation due to hydrolysis occurs at the ester bond portion in the polyester chain, resulting in a decrease in molecular weight.
  • the mechanical properties as described above will deteriorate in a short period of use in the wet heat environment, and a relatively high molecular weight will be obtained during film formation.
  • the durability of the material for a relatively long period of time before deteriorating the mechanical properties of the humid environment is similar to that in the humid environment, although the molecular weight is similarly reduced.
  • the layer B of the present invention contains only a small amount of pigment or contains no pigment at all, a decrease in the molecular weight during molding is suppressed as compared with the case where a large amount of pigment is added.
  • the fact that it is easy to obtain a polymer having a high molecular weight after film formation also has an advantageous effect on durability.
  • the weight-average molecular weight of the layer B according to the present invention at the time of the film-forming sheet is 7500 or more, it is relatively early when the resin-coated metal plate is used in a moist heat environment as described above. Hydrolysis to a molecular weight that causes embrittlement can be prevented, and sufficient durability can be achieved. In addition, when the molecular weight is 140,000 or less, the cost can be sufficiently reduced. This is because it is necessary to use a higher molecular weight for the raw material of the polyester resin itself, which is not generally and continuously obtained, resulting in high costs.
  • the resin composition of the layer B of the present invention it is preferable to select a composition that can easily obtain the above-mentioned molecular weight range.
  • PET resin or PBT which can be obtained as a raw material having a high molecular weight such as a solid phase polymerized product, is preferred.
  • a resin can be preferably used, and a single composition of the resin or a blend with another polyester resin can be used.
  • 3Crystalline ⁇ Although it is a resin, its elastic modulus in the crystalline region is lower than that of polyethylene terephthalate-based resin and its flexibility in the crystal part is high, so even if it is coated on a metal plate with relatively high crystallinity, it can be processed well. Showing sex,
  • Tm melting point
  • Etc. PBT resin whose melting point is lowered by isophthalic acid copolymerization is preferable from the viewpoint that the laminating temperature can be further lowered.However, this PBT resin tends to be less resistant to moist heat than homo PBT having the same molecular weight, and conventional equipment has If lamination at a temperature equal to or higher than the melting point of homo PBT is possible, it is preferable to use homo PBT resin from the viewpoint of wet heat resistance.
  • the crystallization rate of PBT resin is higher than that of PET resin, if the amount of PBT resin exceeding 20% by weight is used as the resin composition of the B layer, the resin-coated metal plate will have poor water transfer resistance. It is possible that the PBT resin crystallizes immediately when immersed in boiling water, even if the layer B of the resin-coated metal plate is in an amorphous or low crystalline state. As a result, an elastic modulus that does not cause deformation of the sheet or detachment from the metal plate even in boiling water can be obtained.
  • the layer A is made into the above-mentioned substantially amorphous or low-crystalline polyester layer, and does not break even when the laminated sheet is heated to a temperature higher than the glass transition temperature of the layer A.
  • the layered sheet can secure the tension of the layer B and does not stick to the metal drum for preheating of the embossing machine, and can be a laminated sheet suitable for giving an embossed pattern by the embossing machine.
  • the same resin component as that preferable for the layer A can be used, but it is difficult to obtain a resin component other than PBT having a high raw material molecular weight. From that point, it is easy to obtain a sheet having a PBT rich composition, a sheet having a weight average molecular weight within the range of the present invention, and
  • the wet heat resistance of the non-crystalline or low-crystalline polyester blended with PBT resin depends not only on its molecular weight but also on its molecular structure, of course, the number of ester bonds in the same weight, acid component, The structure of the alcohol component and the presence or absence of steric hindrance to water molecules are different, and there are parts that cannot be discussed solely based on the initial molecular weight alone.However, in a system where these industrially available raw materials are blended with PBT resin, It is possible to correlate the molecular weight of near-initial sheet with wet heat resistance.
  • additives may be added to the layer B in appropriate amounts to the extent that the properties are not impaired.
  • Additives include phosphorus-based and phenol-based antioxidants, heat stabilizers, light stabilizers (room temperature-acting radical scavengers), nucleating agents, metal deactivators, residual polymerization catalyst deactivators, Examples include those commonly used in a wide variety of resin materials such as nucleating agents, antibacterial and antifungal agents, antistatic agents, lubricants, flame retardants, and fillers. However, it is preferable not to add an additive that increases the amount of permeated moisture in the thickness direction of the layer B.
  • the additive is used as a method for suppressing the molecular weight reduction during extrusion film formation of the layer B to obtain a colored sheet having a molecular weight within the range of the present invention, or as a method for forming a resin-coated metal plate under a wet heat environment.
  • a carbodiimide compound may be added as a method for suppressing the decomposition and degradation.
  • the carbopimide compound suppresses hydrolysis in the molding machine during extrusion film formation, and as a result, has the effect of making it easier to obtain a colored sheet having a molecular weight within the scope of the present invention.
  • the remaining carbodiimide compound has an effect of suppressing hydrolysis during use in a moist heat environment.
  • Examples of the carbodiimide compound include those having a basic structure represented by the following general formula.
  • n represents an integer of 1 or more.
  • R represents another organic bonding unit.
  • the R moiety is any of aliphatic, alicyclic, and aromatic. Good. Specifically, for example, poly (4,4'-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (tolylcarbodiimide), poly (Disopropylphenylenecarbodiimide), poly (methyldiisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like, and their monomers.
  • the imide compounds may be used alone or in combination of two or more.
  • the preferable addition amount of the carbodiimide compound is 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 as the resin content.
  • the content is 0.1 part by weight or more, more preferably 0.5 part by weight or more, the effect of improving hydrolysis resistance can be sufficiently obtained.
  • the amount is 5 parts by weight or less, the effect of suppressing the reduction of the molecular weight is saturated, and various problems occur in the extrusion film forming property. Doing so may cause poor appearance and reduced mechanical properties: Also, it is possible to avoid a situation in which the compounding cost of the layer B becomes expensive.
  • Additives having a hydrolysis preventing function include block copolymers and graft copolymers having polyfunctional epoxy groups. ) Can be added in an appropriate amount within a range that does not deteriorate the properties. It is known that these additives improve the hydrolyzability of the polyester resin.
  • an additive having a similar hydrolysis preventing effect may be added to the layer A, but these reactive additives also react with hydroxyl groups on the surface of the titanium oxide added as a pigment. Therefore, it is difficult to obtain the effect just by adding the pigment, and it is also easy to cause the aggregation of the pigment particles.
  • the thickness of layer B is 15 / in! It is preferably in the range of up to 80 m.
  • the thickness of layer B is 15 / in! It is preferably in the range of up to 80 m.
  • the total thickness of the sheet where the layer A and the layer B are laminated is 65 / in! , Preferably in the range of ⁇ 300 ⁇ . 6 5] If it is 1 or more, it is easy to achieve both the function of the above-mentioned layer and the function of the layer. If the value is less than 300 ⁇ , the processing die used for secondary forming such as punching, bending, and drawing of a conventional soft PVC coated metal plate is used as it is.
  • a layer C may be provided on the surface of the layer A to give a print design.
  • the printing layer is applied by gravure, offset, screen or other known methods. The purpose is to give print designability such as stone tones, wood tones or geometric patterns, and abstract patterns.
  • the printing may be partial printing or solid printing, and both the partial printing layer and the solid printing layer may be applied. From the viewpoint of ensuring the durability of the printing layer (dropout, discoloration, and fading of the printing layer), it is preferable to provide a transparent coating layer or a transparent resin layer on the printing layer.
  • the application of the coating layer may be performed before or after the laminated sheet is passed through the embossing machine.However, the handleability of the coating line in the smooth state of the sheet before embossing is better. Yes, it is preferable to print and coat layer A in advance.
  • the coating layer can be applied by various ordinary methods.
  • the resin composition of the coating layer D include silanol-condensation types such as silicone-based and acrylic-silicone-based resins, and ethylene-butyl ether having a mouth opening.
  • Cyanate cross-linkable types such as copolymers, ataryl polyols, urethane polyols, polyester polyols, etc. can be cited, but are not limited thereto, and adhesion to the A layer can be obtained. Any material can be used without particular limitation as long as it has non-adhesion to the heated metal in the embossing step.
  • the coating layer D is composed of two or more layers, and the outermost layer is a layer having non-adhesiveness to the metal, and a layer having the function of an adhesive layer between the layer and the printing layer C or the A layer is interposed.
  • An ultraviolet absorber, silica particles, an antistatic agent, a translucent pigment, a dye, and the like are added to the coating layer according to the purpose.
  • the preferred thickness of the D layer is in the range of 1 to 10 inches. If the thickness is smaller than this, problems such as difficulty in uniform coating may occur, which is not preferred. On the other hand, if the thickness is larger than this, the suitability for giving an enboss and the secondary workability of the resin-coated metal plate are likely to deteriorate, which is not preferable.
  • An E layer mainly composed of a substantially non-crystalline or low-crystalline polyester resin having a thickness in the range of 25 ⁇ to 100 ⁇ may be further provided on the C layer.
  • the layer is capable of expressing a deep design, and is preferred for the layer A except that it does not contain a pigment.By forming an unstretched layer having the same composition as the resin composition, the It is also possible to provide a pattern.
  • the A layer and the E layer do not necessarily need to be made of the same resin yarn.
  • the E layer must be laminated after printing on the A layer, so if the thickness is too thin, the handling of the single layer sheet before lamination is very It becomes worse and is not preferred. Conversely, if the thickness is greater than this, yellowing due to light irradiation during use becomes remarkable, and the workability of the resin-coated metal plate is unfavorably deteriorated.
  • Various additives may be added to the E layer as well as the A layer and the B layer, and it is particularly preferable to add an ultraviolet absorber for the purpose of preventing discoloration and fading of the printed layer due to light deterioration. Further, mica powder, hologram foil and the like may be added to the extent that it is not difficult to see through the printed layer, so as to impart design properties.
  • the method of laminating the layer E on the printed layer C may depend on various adhesives.
  • the adhesive is mainly composed of a polyester-based resin or a polyether-based resin, and isocyanate-based cross-linking.
  • An adhesive that cures with an agent or the like and is generally called an adhesive for dry lamination can be used.
  • the sheet is heated by an embossing machine by forming the C layer with a printing ink having a heat-fusing property, or by applying a coating layer having a heat-fusing property to the outermost layer in a printing process. Heat fusion lamination may be performed using a process.
  • the total thickness of the laminated sheet is preferably not more than 300 ⁇ .
  • Various types of steel sheets such as hot-rolled steel sheets, cold-rolled steel sheets, hot-dip galvanized steel sheets, electro-galvanized steel sheets, tin-plated steel sheets, and stainless steel sheets, and aluminum sheets can be used as the metal sheets covered by the present invention. You may use it after giving.
  • the thickness of the base metal plate varies depending on the application of the resin-coated metal plate, etc., but it is 0. ⁇ ! It can be selected within the range of ⁇ 10 mm.
  • the resin-coated metal plate of the present invention can be obtained by laminating a laminated sheet composed of at least two layers of the A layer and the B layer on the base metal plate.
  • the thermosetting adhesive layer (hereinafter referred to as “F layer”) used for lamination is made of epoxy adhesive, urethane adhesive, etc.
  • the adhesive film thickness after drying on the metal surface where the laminated and integrated sheets are bonded is about 2 to 10 ⁇ m. Apply the adhesive as described above.
  • the coated surface is dried and heated using an infrared heater or a hot-air heating furnace, and the laminated sheet is immediately coated and cooled using a roll laminator while maintaining the surface temperature of the metal plate at an arbitrary temperature.
  • a resin-coated metal plate is obtained.
  • FIG. 2 (la) is a schematic view of a design sheet for a resin-coated metal plate having the basic structure of the second invention.
  • a design sheet for a resin-coated metal plate is basically composed of an embossing layer A and a base resin layer B.
  • a layer C made of a substantially non-crystalline polyester resin is provided between the embossing layer A and the base resin layer B. I have.
  • a coating layer D having a non-adhesive property to the heating metal is provided on the surface of the embossing layer A.
  • Fig. 2 (Id) shows an example of a resin-coated metal plate.
  • a design sheet for a resin-coated metal plate having the configuration shown in Fig. 2 (la) is placed on a metal plate F via a thermosetting adhesive E. Are stacked. Further, the design sheet for the resin-coated metal plate having the configuration shown in FIGS. 2 (lb) and 2 (1c) may be similarly laminated on the metal plate F.
  • FIG. 3 shows an example of an embossing machine generally used to give an embossed pattern to a flexible PVC sheet.
  • the embossing layer A and the base resin layer B are formed of polyester resins having different physical properties.
  • the polyester resin forming the embossing layer is referred to as “polyester resin A” (or simply “resin A”)
  • the polyester resin forming the base resin layer is referred to as “polyester resin B” (or It may simply be called “resin B”).
  • any substantially non-crystalline polyester resin capable of forming a force render film can be used without particular limitation.
  • Non here A crystalline polyester resin is a polyester resin that does not show a clear crystallization behavior as measured by a differential scanning calorimeter (DSC). Specifically, it includes those that can be handled as an amorphous polyester resin.
  • DSC differential scanning calorimeter
  • Easter PETG 66763 J by Yeastman Chemical Co., Ltd. which has many achievements in force-rendering film formation, has little concern about the stable supply of raw materials, and is advantageous in terms of raw material prices, is given as a preferred example.
  • the present invention is not limited to this example, for example, the “TSU NAM I” series, which is a PETG grade for calendars of Eastman Chemical Company,
  • the acid component is mainly terephthalic acid or dimethyl terephthalic acid, including ⁇ PCTG ⁇ 5445 '' from Yeastman Chemical Co., Ltd.
  • neopentyl glycol copolymer PET which is substantially non-crystalline and has a composition can also be used.
  • a pigment is added to the embossing layer for the purpose of imparting a design property, imparting a visual concealing effect of a base, and the like.
  • the pigment to be used may be a pigment generally used for coloring a resin, and the amount of the pigment may be the amount generally added for the above purpose.
  • white tint can be adjusted in a chromatic inorganic or organic facial department based on a titanium oxide pigment having a high hiding effect.
  • the base resin layer is colored by adding a pigment to the base resin layer, the pigment concentration of the embossing layer is reduced, and a colorant having a low organic concealing effect such as a translucent pigment or dye is added.
  • a color design may be formed in combination with the color of the base resin layer.
  • a design property may be imparted by adding a hologram foil, a coloring strength, or the like to the emboss-provided layer.
  • additives necessary for improving the force render film forming properties may be appropriately added.
  • these additives include, for example, various lubricants for improving the releasability from a calender roll, or reducing the load at the time of film formation, and a linear ultra-high dispersion for improving the melt tension.
  • Acrylic resin or polytetraflu treated with easy dispersion to develop into fibrils examples thereof include processing aids such as polyethylene, Görich accelerators, and additives added for the purpose of improving bank shape and improving flow marks.
  • an additive other than the above may be appropriately added to the embossed layer to the extent that its properties are not impaired.
  • additives include various antioxidants such as phosphorus and phenol, heat stabilizers, ultraviolet absorbers, light stabilizers, impact modifiers, metal deactivators, residual polymerization catalyst deactivators, Antibacterial and antifungal agents, antistatic agents, flame retardants, fillers, and other materials commonly used in resin materials, carboxyimide-based epoxy-type terminal carboxylic acid sealants, or hydrolysis inhibitors Those particularly preferably used for the above polyester resin can be mentioned.
  • the preferred thickness of the embossing layer is in the range of 50 / im to 300 ⁇ m.
  • the length is 50 m or more, it is easy to obtain a uniform sheet by improving the force-rendering film-forming property.
  • it is not necessary to add a pigment at a high concentration in order to obtain the effect of hiding the base, and it is easy to avoid a decrease in workability and the like due to the addition of a facial treatment at a high concentration.
  • it is not more than 300 ⁇ it is possible to avoid unfavorable situations in terms of cost and efficiency, such as unnecessary energy for heating to a sufficient temperature in heating at the time of embossing. Further, it is possible to prevent the effects in various performances required for the design sheet from being saturated.
  • the necessary thickness of the embossed layer is determined in consideration of the depth of the embossed plate to be provided within the above thickness range.
  • the embossing layer of the present invention has a thickness range of 50 Azm to 300 ⁇ , it is more correctly described as “film and sheet”.
  • a sheet having a so-called thickness is also called a sheet. The same applies to the base resin layer.
  • embossing layer is formed into a sheet by a force render film forming method, various colors can be efficiently produced in a small lot.
  • the embossed layer When the sheet is heated to give an embossed pattern by an embossing machine, the embossed layer alone causes melt fracture, wrinkling, width shrinkage, etc., whereas the presence of the base resin layer reduces this. It functions as a support layer to prevent it. Therefore, the performance required for the base resin layer is that no sticking occurs when it comes into contact with a heated metal roll, etc. And melt fracture, No wrinkling or ⁇ ⁇ ⁇ shrinkage. Furthermore, if the heat-sealing lamination with the embossing layer is possible, the lamination and integration can be performed in a simultaneous step when the sheet is heated by the embossing machine.
  • the polyester resin when used as a resin-coated metal plate, it is preferable that a strong adhesive force can be obtained under the temperature conditions for laminating a conventional soft PVC-based resin-coated metal plate.
  • the polyester resin In order to function as a support layer, the polyester resin must be a crystallized polyester resin to a certain degree or more, and more specifically, the value measured by a differential scanning calorimeter (DSC) at the time of primary temperature rise is “0”. It must be a sheet that satisfies the relationship of (AHm-AHc) / AHm. This is because, even if the resin has a crystalline composition, if the crystallinity is low, sticking to the heated metal nozzle of the embossing machine occurs.
  • DSC differential scanning calorimeter
  • the melting point (T mb) of the base resin layer is in the range of 180 ° C to 240 ° C, and the base resin layer is not stretched.
  • the sheet is preferred. This is due to the fact that the same laminating temperature conditions as in the past can be directly applied to the laminating equipment that has been used for laminating conventional soft PVC sheets to metal plates. Since the base resin layer has the above melting point range, the surface temperature of the metal plate during lamination can be set higher than the melting point of the base resin layer, and the vicinity of the bonding interface of the base resin layer is melted to obtain a strong adhesive force. be able to. By setting the melting point of the base resin layer to 240 ° C.
  • the temperature is set to 180 ° C or more, when laminating to a metal plate, the advantage that the adhesive force can be secured at a lower laminating temperature is eliminated, but the laminating layer is used as a support layer in an enbossing machine. The function becomes excellent, and the sheet temperature at the time of embossing can be increased as compared with the case where the embossing layer is passed through an embossing machine alone. It is not preferable to use a stretched film for the base resin layer, since remarkable shrinkage may occur before the melting point of the base resin layer is reached during lamination, and wrinkles may occur in the resin layer of the resin-coated metal plate.
  • polyester resin forming the resin B various crystalline polyester resins can be used.
  • Polyethylene terephthalate (hereinafter referred to as “PET”)-based resins and the like have a low crystallization rate, and in order to obtain the preferred crystallinity of the present invention, it is necessary to separately perform crystallization treatment after extrusion film formation. The number of processes increases. Furthermore, in the case of PET resin, when crystallized, its melting point is high. Nate is not preferable because sufficient adhesive strength cannot be obtained.
  • PET Polyethylene terephthalate
  • polybutylene terephthalate (hereinafter referred to as “PBT”)-based resins and polytrimethylene terephthalate (hereinafter referred to as “PTT”)-based resins have a high crystallization rate. Therefore, by appropriately setting the casting roll temperature at the time of extrusion film formation, it can be used particularly preferably because necessary crystallinity can be imparted to the base resin layer at the time of extrusion film formation.
  • the melting point of these resins is about 225 ° C for so-called homo- and homo-, each of which has a single composition of an acid component and an alcohol component. It is also preferable in that a strong adhesive force can be obtained. From the viewpoint of the adhesive strength to a steel sheet, it is possible to obtain a PET resin having a melting point in the above-mentioned preferred temperature range depending on the copolymer composition, such as isophthalic acid copolymerized PET. However, in this case, the crystallization speed is further slower than that of homo-PET, and the time required for the crystallization process is undesirably long.
  • the base resin layer may be a homo- ⁇ ⁇ resin or a homo- 'resin as a main component, and may be used by blending an amorphous resin.
  • the adhesive Shinare in order to obtain a beta resin extent crystallization is in progress, as blanking trend composition of the resin beta, homo ⁇ Robetatau resin, or homo ⁇ Rotautau resin 60 weight 0/0 or more free Preferably, it is rare.
  • the ratio of the crystalline resin By setting the ratio of the crystalline resin to 60% by weight or more, it becomes easy to impart preferable crystallinity in the extrusion film forming process.
  • its composition indicated by the heat of crystal fusion ( ⁇ ) of the differential scanning calorimeter (DSC), reduces the crystallinity when maximal crystallization occurs. It is possible. This makes it possible to reduce the amount of heat consumed for crystal melting when laminating to a metal plate, and to increase the volume of the amorphous part, thereby making it easier to obtain a strong adhesive force.
  • Various necessary additives may be appropriately added to the base resin layer similarly to the resin A.
  • the base resin layer is made by extrusion film formation, and it is possible to prevent loss of raw materials and time due to color change by using a transparent sheet containing no pigment or coloring a specific single color. It is possible.
  • the preferred thickness of the base resin layer is 20! 3300 / im.
  • the length is 20 m or more, the effect as a support layer when the laminated sheet is heated by the embossing machine can be sufficiently ensured.
  • the content is not more than 300 ⁇ , it is possible to prevent the effect as a support layer at the time of embossing from being saturated and to increase only the cost.
  • Film formation of the base resin layer is performed by a method known as extrusion film formation, for example, an inflation method or a T-die method.
  • extrusion film formation for example, an inflation method or a T-die method.
  • a configuration in which a layer made of a substantially non-crystalline polyester-based resin is co-extruded for the purpose of ensuring the heat-fusibility with the embossing layer is also possible.
  • the same resins and compositions as the non-crystalline polyester resin that can be used for the resin composition of the embossing layer can be used. This may be the same yarn or different composition as the embossed layer.
  • the embossing layer and the base resin layer are heat-sealed and laminated in the sheet heating step of the embossing machine, the embossing layer is in a state of being heated and softened.
  • the base resin layer needs to maintain a high elastic modulus in its role. Depending on the equipment, the adhesion between the embossing layer and the base resin layer may be insufficient.
  • the surface of the base resin layer side (from the substantially non-crystalline polyester resin) also softens when heated. In this case, it is easy to obtain a strong adhesion to the strong embossing layer.
  • the layer made of a substantially non-crystalline polyester resin is a layer having an adhesive layer function
  • the preferable thickness is in the range of about 3 m to 30 m.
  • the total thickness of the laminated sheet (A + B or A + C + B) is preferably 500 ⁇ or less, more preferably 300 ⁇ or less. 5 0 0 111 or less, further to preferably by less 3 0 0 ⁇ ⁇ , secondary processability such as punching as a resin-coated metal sheet becomes sufficiently good.
  • secondary processability such as punching as a resin-coated metal sheet becomes sufficiently good.
  • FIG. 3 shows an example of an embossing machine 10 that has been generally used for conventionally giving an embossed pattern to a soft PVC sheet.
  • the sheet 2 is preheated by the heated metal roll 1, the sheet temperature is further raised by the non-contact heater 3, and then the embossed pattern is transferred to the sheet by passing it between the embossing plate roll 4 and the pressing roll 5. It is structured to be used.
  • an embossing layer formed by a calendar method and a base resin layer formed by an extrusion method or a base resin layer formed by co-extruding a layer made of a substantially non-crystalline polyester resin.
  • the embossed pattern can be applied in the same manner as in the case of conventional soft PVC.
  • the sheet heating temperature in the embossing machine is set to 160 ° C or higher and (Tmb_20) ° C or lower, adhesion to the heated metal roll or There is no occurrence of sheet melting fracture. Therefore, high embossing heat resistance, which cannot be obtained by the embossing layer alone, can be obtained.
  • the surface of the laminated sheet (A + B or A + C + B) has improved weather resistance by imparting UV absorption, improved scratch resistance, improved stain resistance, improved solvent resistance, and deepness.
  • the coating layer D may be provided for various purposes such as providing a design.
  • the application of the coating layer D may be performed before or after the laminated sheet is passed through the embossing machine.
  • the handling property in the coating line is better for a sheet in a smooth state before embossing, and it is preferable to coat the embossing layer in advance. In this case, it is necessary for the coating layer to have non-adhesiveness to the heated metal in addition to the above purpose.
  • the application of the coating layer can be performed by a known method.
  • the resin composition of the coating layer D include a silanol condensation type such as a silicone type and an acrylic silicone type, a fluoroethylene vinyl ether copolymer, and an ataryl polyol. Cyanate cross-linking type and the like can be mentioned.
  • the present invention is not limited to these, and can be used without any particular limitation as long as the adhesiveness to the embossing layer is obtained and the adhesiveness to the heated metal is non-adhesive.
  • the coating layer D may be composed of two or more layers, the outermost layer may be a layer having non-adhesiveness to the metal, and a layer having the function of an adhesive layer between the layer and the resin A may be interposed.
  • the coating layer may contain an ultraviolet absorber, a silica particle, an antistatic agent, a translucent pigment, a dye, or the like, depending on the purpose.
  • the preferred thickness of the coating layer D is in the range from 1 to 10 m. When the thickness is 1 ⁇ m or more, uniform application becomes easy. When the length is 10 m or less, the aptitude for applying the enboss becomes sufficiently good.
  • Various types of steel sheets such as a hot-rolled steel sheet, a cold-rolled steel sheet, a molten dumbbell steel sheet, an electro-zinc coated steel sheet, a tin plated steel sheet, a stainless steel sheet, an aluminum sheet, and an aluminum alloy sheet are used as the metal sheet to be subjected to the present invention. It may be used after normal chemical conversion treatment.
  • the thickness of the base metal plate varies depending on the application of the resin-coated metal plate and the like, but can be selected in the range of 0.1 mm to: L O mm.
  • Adhesives used for laminating a laminated sheet (A + B or A + B + C) provided with an embossed pattern by an embossing device on a base metal plate include epoxy adhesives, urethane adhesives, and polyesters. Examples thereof include generally used thermosetting adhesives such as a system adhesive.
  • a commonly used coating equipment such as a reverse coater or kiss coater is used for the metal plate, and a laminated adhesive sheet is bonded to the metal surface.
  • the epoxy, urethane, polyester, etc. thermosetting adhesive is applied so that the film thickness becomes 2 to 10 ⁇ m.
  • the coated surface is dried and heated by an infrared heater or a hot air heating furnace, and immediately while using a roll laminator while maintaining the surface temperature of the metal plate at an arbitrary temperature, the base resin layer of the laminated sheet is used.
  • a resin-coated metal plate is obtained by coating and cooling so that the side becomes an adhesive surface.
  • the melting point (Tm) of the base resin layer located on the side of the bonding surface to the metal plate is in the range of 180 to 240 ° C. In that case, the surface of the metal plate By setting the temperature to be equal to that of the conventional flexible PVC sheet laminate-coated metal sheet, it is possible to obtain a strong adhesive force.
  • a resin-coated metal plate having relatively good embossing heat resistance can be obtained.
  • rapid cooling such as water cooling is preferably performed to reduce emboss return due to heating of the sheet during lamination.
  • a resin-coated metal plate was subjected to an impact adhesion bending test, and the surface state of the decorative sheet in the bent portion was visually judged. If there was almost no change ( ⁇ ), if there was slight cracking ( ⁇ ), it was cracked. The occurrence of is indicated as (X).
  • the impact bending test was performed as follows. Prepare 5 Omm X 15 Omm samples from the length direction and width direction of the coated metal plate, keep them at 23 ° C for 1 hour or more, and then use a bending tester to make them 180 ° (internal bending radius 2 mm). The sample was bent, and a cylindrical weight having a diameter of 75 mm and a mass of 5 kg was dropped on the sample from a height of 50 cm.
  • Table 1 shows the “B layer” compositions of Examples al to a7 and Comparative examples a:! To a6.
  • Examples a1 to a7 and Comparative examples a1 to a6 shown in Table 1 two ⁇ 65 mm twin-screw kneading extruders were used to perform the coextrusion of the feed block method.
  • a two-layer laminated sheet having the B layer of the resin composition shown in 1 was obtained.
  • the total thickness of the laminated sheet was 120 / m, and the thickness of the layer B is shown in Table 1.
  • Table 1 also shows the weight average molecular weight of layer B after film formation.
  • the composition of layer A is a blend composition of PBT resin (Novaduran 5002S: 20 parts by weight) and PETG resin (Easter 6763: 80 parts by weight), and 24 parts by weight of titanium oxide pigment (resin component).
  • the quantity is 100). This is the same except for Comparative Examples a7 to a13, which are single-layer sheets.
  • Table 2 shows the compositions of the single-layer sheets of Comparative Examples a7 to a13.
  • Comparative Examples a7 to a13 shown in Table 2 are single-layer films consisting of only the layer with a large amount of pigment added, and were formed using only one twin-screw extruder with a diameter of 65 mm. ing. All thicknesses are 120 zm. In all cases, the cast film forming method using a T die is used. You.
  • Table 3 shows the compositions of Example a8a9 and Comparative example a14a19.
  • Table 4 shows the compositions of Example a10a15 and Comparative Example a20a21.
  • Example a8a9, Comparative example a14a19, and Example a13a15 shown in Table 4 the printed layer ⁇ Coating layer is provided.
  • the printing method is the usual gravure coating method, in which the surface of layer A is solid-printed with white ink, and then the abstract pattern is partially printed. Further, a transparent tinting layer of a cine-crosslinkable acrylic polyol is applied thereon with a thickness shown in Table 4.
  • composition of layer B of these coated layer-provided products is as shown in Tables 3 and 4, and those in Table 3 do not satisfy claim 6 of the present invention, so there is no suitability for embossing with an embossing machine. .
  • the thickness of each of the B layers is 30 ⁇ .
  • the composition of each layer is
  • Examples a8 and a9 and Comparative examples a14 to a19 shown in Table 3 a printed layer and a transparent film layer were provided on the layer A side surface of the laminated sheet.
  • the printing method is a normal black coating method.
  • the surface of the layer A is solid printed with white ink, and then the abstract pattern is partially printed.
  • a polyester-based adhesive resin layer is provided thereon by a printing line, and a transparent film layer is provided by heat fusion lamination.
  • the composition of the transparent film layer is a blend composition of PBT resin (Novaduran 5020 S: 20 parts by weight) and PETG resin (Easter 6763: 80 parts by weight), and contains substantially no inorganic pigments such as titanium oxide pigment.
  • the thickness is 50 m.
  • the ones shown in Table 4 have the composition suitable for the embossing machine since the layer B has the composition satisfying the claim 6.
  • PET RT-580 (manufactured by Nippon Corporation)
  • Raw material MW 134000
  • Calposilite H CM—8 V (Nisshinbo) Carbodimid-based hydrolysis inhibitor
  • An embossing pattern was applied by a continuous embossing machine 10, which is also commonly used for the flexible PVC sheet shown in FIG.
  • the outline of the apparatus is as follows. First, the sheet 2 is preheated by contact-type heating using a metal heating roll 1, and then the infrared heater is used. The sheet is heated to an arbitrary temperature by non-contact heating using the method (1), and the emboss pattern is transferred to the sheet by the embossing plate roll (4).
  • embossing was performed at a sheet heating temperature of 180 ° C and an embossing plate roll temperature of 60 ° C.
  • a polyester-based adhesive generally used for a polyvinyl chloride-coated metal plate is applied to the metal surface so that the thickness of the dried adhesive is about 2 to 4 / ⁇ .
  • the coated surface is dried and heated by a hot-air heating furnace and infrared heater, and the surface temperature of the zinc-plated steel sheet (0.45 mm thick) immediately before lamination is set to 235 ° C.
  • the laminated sheet was coated using a single laminator and cooled by natural air cooling to produce a resin-coated steel sheet, and the above-described items were evaluated.
  • the type of adhesive and the application conditions are the same in all Examples and Comparative Examples.
  • Table 5 shows the evaluation results of Examples a1 to a7 and Comparative examples a1 to a13.
  • Table 6 shows the evaluation results of Examples a8 and a9 and Comparative examples a14 to a19.
  • Comparative Example a19 X ⁇ ⁇ Table 2 shows the evaluation results of Examples a0 to a15 and Comparative examples a20 and a21.
  • Comparative Examples a7 to a13 a single-layer polyester film colored with a titanium oxide pigment was laminated on a metal plate, but all had poor durability results. Comparative Examples a7 to a9 had the weight-average molecular weight that should be included in the layer B of claim 3 of the present invention. However, a large number of blisters were observed in the sample after the moist heat test. It is presumed that the increase in the amount of permeated water in the sheet thickness direction due to the addition of the titanium oxide pigment promoted the corrosion of the metal plate surface and caused partial peeling between the sheet and the metal plate.
  • Comparative Examples a10 to a13 In Comparative Examples a10 to a13, many cracks were observed in the resin layer, and it seems that the adhesion to the metal plate was also reduced. In Comparative Examples a7 to a9, since the film layer maintained relatively strength, water bubbles were generated in a portion where the adhesive force was reduced, whereas in Comparative Examples a10 to a13, the resin layer itself was not. It is considered that the deterioration was remarkable and the difference was that cracks occurred. In Comparative Examples a7 to a9, the resin composition was within the composition range of the layer B in claim 6 of the present invention. The emboss transfer could not be performed due to the high property.
  • Comparative Examples al to a6 have a force in which the sheet is composed of two layers, A layer and B layer. Comparative Examples a3 to a6, the weight average molecular weight of the B layer is lower than the range of the present invention. Has not been obtained. In Comparative Example a1, the thickness was smaller than the thickness that should be provided for the layer B of the present invention. Means that the amount of pigment added to the B layer is large. These also have poor wet heat resistance and result.
  • Examples al to a7 of the present invention in which the addition of the pigment to the layer on the side of the bonding surface with the metal plate was restricted by using two resin layers, good durability (moist heat resistance) was obtained. .
  • Examples al to a4 in which the resin composition of the layer B conforms to claim 6 of the present invention, a resin-coated metal plate having a good embossed appearance can be obtained by embossing the sheet with an embossing machine. ing.
  • Example a7 the wet heat resistance was good, but the layer B was made of PET resin with a low crystallization speed, so it could not be crystallized during extrusion film formation, and it was given the suitability for an enbosser. I could't.
  • a composition of the layer B As a composition of the layer B, a composition having no suitability for an embossing machine was used, and a design by printing and coating was applied.
  • the resin composition was the same as in Example a6. Although the same as the layer B, the weight average molecular weight after extrusion film formation is lower than that of the example a6 due to the addition of the titanium oxide pigment. As a result, cracks occurred after the moisture heat resistance test due to deterioration of the resin layer itself. Also in Comparative Example a14 in which a karposimid-based hydrolysis inhibitor was added, the amount of the added syrup was too small to obtain an effect.
  • Comparative Examples a 17 and a 19 are those to which the carbodiimide-based hydrolysis inhibitor in the range shown in Claim 4 of the present invention was added, but were added to the same layer as the titanium oxide pigment. Seemed to reduce the effect of addition, and could not obtain a sufficient effect of suppressing a decrease in molecular weight during extrusion film formation.
  • the laminated sheet is provided with a printing layer and a coating layer, or a coating of a printing layer and a transparent resin layer.
  • the A layer and the B layer are within the scope of the present invention, the heat and humidity resistance There is no problem.
  • the metal plate laminated with the sheet embossed by the embossing machine 10 shown in Fig. 3 was allowed to stand in a hot air circulating oven at 105 ° C for 3 hours, visually observed, and before being placed in an oven.
  • ⁇ indicates that the shape of the emboss has hardly changed compared to “ ⁇ ”.
  • ⁇ indicates that the emboss has returned slightly, and “ ⁇ ⁇ ⁇ ” indicates that the emboss has returned significantly, or the emboss pattern has completely disappeared.
  • those with simply rough surfaces are indicated by "X”.
  • base resin layer base resin layer or C + base resin layer
  • a laminated sheet A + B or A + B + C having the resin composition and thickness shown in Table 8 was prepared. Extrusion-formed sheet by the casting method using a T-die, and when a layer composed of a substantially non-crystalline polyester resin is involved, co-extrusion by the feed block method is performed, and a substantially non-crystalline polyester resin is used. The thickness of the resin layer was 10 / im.
  • Example b9 the sheet of Example b9 was introduced into a heating furnace having an infrared heater after being taken up by a casting roll, and was subjected to a post-heating treatment at 160 ° C for 30 seconds by non-contact heating.
  • (AHm-AHc) / ⁇ of the base resin layer after the post-heating treatment was 0.6.
  • the raw materials used in Table 8 are as follows.
  • NOVADURAN 500 S Homo PBT resin manufactured by Mitsubishi Engineering-Plastics Corporation (glass transition point; 45 ° C crystal melting peak temperature; 23 ° C)
  • c o _PET BK—218 Isophthalic acid copolymerized PET resin manufactured by Mitsubishi Chemical Corporation (glass transition point; 76 ° C. crystal melting peak temperature: 246 ° C.)
  • Cortera C P 5 0 9 2 0 0 Homo resin Shell Co. (glass transition point: 49 ° C crystal melting peak mixture: 2 25 ° C),
  • P CTG 5 4 4 5 Amorphous polyester resin obtained by replacing 70% of the ethylene glycol in polyethylene terephthalate with 1,4-six-hexane dimethanol (manufactured by Yeastman Chemical Co., Ltd.) : 88 ° C crystal melting peak temperature; not observed)
  • the embossing pattern was applied by a continuous embossing machine 10 (see Fig. 3), which is also commonly used for soft vinyl chloride sheets.
  • the heating drum was set at 100 ° C, and in Examples bl to b9 and Comparative Examples bl to b8, the heater heated the sheet before contact with the embossed pattern roll to 165 ° C. You.
  • the heating drum (metal hole 1) was set at 10 ° C and the sheet temperature was changed by heating the heater. It is. Also in this case, the temperature of the embossing plate roll 4 and the pattern of the embossing plate are the same as in Examples b1 to b9 and Comparative Examples bl to b8. The type and thickness of the base resin layer when the base resin layer is present are the same.
  • a polyester-based thermosetting adhesive which is generally used for polychlorinated vinyl coated metal sheets, is applied to the metal surface so that the adhesive thickness after drying is about 2 to 4 ⁇ m (
  • the adhesive layer (E)) is then dried and heated with a hot-air heating furnace and an infrared heater to reduce the surface temperature of the zinc-plated steel sheet (metal plate (F): thickness 0, 45 thighs).
  • metal plate (F) thickness 0, 45 thighs
  • Comparative Examples b3, b4, and b5 are cases where “(A Hm—AH c) / ⁇ ” of the base resin layer is lower than the claims of the present invention, and are laminated on the heating drum of the embossing machine. The sheet became sticky. Therefore, an embossed pattern could not be provided on the sheet.
  • Comparative Example b3 having the comparatively large numerical value showed the smallest adhesion, and the peeling from the heating drum force was possible. As a result, the sheet elasticity decreased due to the heating of the heater, and the sticking to the drum caused a break in the sheet.
  • Comparative Example b6 is a case where only the calender-formed embossing layer was passed through the embossing machine without using the base resin layer, but because the lubricant was added in a relatively large amount, the mixture was transferred to the heating drum. Although the adhesion is slight, the decrease in the porosity when the sheet is heated by a heater is remarkable, which also causes a melt fracture. In Comparative Examples b1 and b2, only the base resin layer conforming to the scope of the present invention was passed through an embossing machine. However, embossing cannot be performed due to its high crystallinity.
  • Comparative Example b7 is a case where the force having the crystallinity suitable for the range of the base resin layer of the present invention is thinner than the preferable range, and the adhesion to the heating drum is prevented. Is insufficient in sheet strength and melt fracture occurs.
  • Comparative Example b 8 which is thicker than Comparative Example b 7 in terms of the thickness of the extruded sheet. It can be seen that the substrate resin layer having crystallinity of the present invention needs to have a specific thickness or more in order to prevent breakage due to heating by heating.
  • Example b9 the same composition as that of Comparative Example b4 was used as the composition of the base resin layer, and the heat treatment was performed after the extrusion film formation. Neither adhesion nor sheet breakage due to heating with a heater occurred, and good emboss transferability was obtained.
  • Example b 9 is a case where it does not conform to Claims 15 or 16 but conforms to Claims 14 and 17, and the base resin layer has a low crystallinity during extrusion film formation. In particular, if heat treatment is performed before embossing, suitability as the base resin layer of the present invention can be imparted.
  • Example b:! To b8 have the preferred crystallinity of the present invention at the time of extrusion film formation when the composition and thickness of the base resin layer are within the preferred ranges of the present invention, and Good embossability can be obtained without the need for crystallization treatment, and the heat resistance of emboss is also good.
  • Examples b10 to b13 and Comparative Examples b9 to b14 shown in Tables 11 and 12 above pass through the embossed pattern roll with and without the base resin layer.
  • the sheet temperature before embossing was the lowest due to the presence of the base resin layer and Comparative Example b9, the emboss heat resistance was insufficient.
  • Comparative Example b10 in which the sheet temperature was higher than L the emboss heat resistance was slightly improved, but it cannot be said that it is still sufficient.
  • Examples b10 to b13 in which the sheet temperature was further increased sufficient embossing heat resistance was obtained.
  • Example b13 in which the sheet temperature gradually approached the upper limit temperature (Tm b-20) ° C defined in claim 22, the width of the sheet was slightly reduced by heating the heater.
  • the resin-coated metal plate and the design sheet for the resin-coated metal plate of the present invention have two polyester resin layers, and the pigment addition amount of the resin layer on the side of the bonding surface with the metal plate is not more than a specific value.
  • the molecular weight by setting the molecular weight to a specific range, it is a resin-coated metal plate that has improved durability (moisture and heat resistance), and reduces the occurrence of melt fracture and wrinkling when applying an embossed design to a sheet. In addition, stable production can be realized at low cost.
  • a resin-coated metal plate having a good embossed appearance can be obtained using an embossing machine conventionally used for embossing a flexible PVC sheet. Can be.

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Abstract

L'invention concerne une feuille métallique recouverte de résine présentant une excellente durabilité (résistance à la chaleur humide), obtenue par lamination d'une feuille métallique avec une feuille stratifiée composée au moins de deux couches non étirables (couches A et B) constituées principalement d'une résine de polyester, au moyen d'un adhésif, une face de la couche B étant utilisée comme surface adhésive. La feuille stratifiée présente une épaisseur totale de 65 à 250 νm, et un pigment de coloration et d'occultation est incorporé dans la couche A. Les couches A et B présentent une épaisseur de 50 à 250 νm et de 15 à 80 νm, respectivement, la teneur de la composante pigment présente dans la couche B étant limitée à au maximum 10 parties en poids pour 100 parties en poids de la composante résine. L'invention concerne en outre des feuilles métalliques recouvertes de résine présentant un bel aspect estampé, qui peuvent être produites par une machine à graver en relief généralement utilisée pour le gaufrage de feuilles de PVC souples.
PCT/JP2003/016387 2002-12-26 2003-12-19 Feuille metallique recouverte de resine, feuille structuree pour feuille metallique, et procede de production de la feuille metallique recouverte de resine WO2004058495A1 (fr)

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JP2006297917A (ja) * 2005-03-23 2006-11-02 Riken Technos Corp 積層化粧シート
JP2006305809A (ja) * 2005-04-27 2006-11-09 Sekisui Home Techno Kk エンボス化粧シートおよびその製造方法
WO2006121070A1 (fr) * 2005-05-10 2006-11-16 Mitsubishi Plastics, Inc. Pellicule stratifiée pour revêtement de métal et pellicule stratifiée pour revêtement de métal utilisée dans les panneaux d’affichage
JP2007022047A (ja) * 2005-07-21 2007-02-01 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シート、および積層シート被覆金属板
JP2007203464A (ja) * 2006-01-30 2007-08-16 Riken Technos Corp 積層化粧シート
JP2008100383A (ja) * 2006-10-17 2008-05-01 Mitsubishi Plastics Ind Ltd 積層シ−ト、エンボス意匠シートおよびエンボス意匠シート被覆金属板
JP2008254348A (ja) * 2007-04-05 2008-10-23 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シートおよび積層シート被覆金属板
JP2010510102A (ja) * 2006-11-25 2010-04-02 レオンハード クルツ シュティフトゥング ウント コー． カーゲー 冷間成形可能な金属材料をコーティングするためのラミネートフィルム
JP2010094890A (ja) * 2008-10-16 2010-04-30 Mitsubishi Plastics Inc 樹脂被覆金属板用積層シ−ト、該積層シートの製造方法、および、意匠性積層シート被覆金属板、ユニットバス部材、建築内装材、および、鋼製家具部材
WO2020059836A1 (fr) * 2018-09-21 2020-03-26 三菱エンジニアリングプラスチックス株式会社 Composite résine-métal et sa méthode de production
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JP2022019535A (ja) * 2020-07-15 2022-01-27 南亞塑膠工業股▲分▼有限公司 レーザエンボス用ポリエステルフィルム及びその製造方法

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JP4898220B2 (ja) * 2003-05-09 2012-03-14 三菱樹脂株式会社 エンボス意匠シート及びエンボス意匠シート被覆金属板
JP2006095892A (ja) * 2004-09-29 2006-04-13 Mitsubishi Plastics Ind Ltd 積層シ−ト、エンボス意匠シートおよびエンボス意匠シート被覆金属板
JP2006110722A (ja) * 2004-10-12 2006-04-27 C I Kasei Co Ltd 表面に紫外線硬化樹脂塗膜を有する立体成型品の製造方法
JP4583867B2 (ja) * 2004-10-12 2010-11-17 シーアイ化成株式会社 表面に紫外線硬化樹脂塗膜を有する立体成型品の製造方法
JP2006297917A (ja) * 2005-03-23 2006-11-02 Riken Technos Corp 積層化粧シート
JP2006305809A (ja) * 2005-04-27 2006-11-09 Sekisui Home Techno Kk エンボス化粧シートおよびその製造方法
KR100966062B1 (ko) * 2005-05-10 2010-06-28 미쓰비시 쥬시 가부시끼가이샤 금속 피복용 적층 필름, 스크린 보드용 금속 피복용 적층필름
WO2006121070A1 (fr) * 2005-05-10 2006-11-16 Mitsubishi Plastics, Inc. Pellicule stratifiée pour revêtement de métal et pellicule stratifiée pour revêtement de métal utilisée dans les panneaux d’affichage
CN101175636B (zh) * 2005-05-10 2012-08-22 三菱树脂株式会社 金属被覆用叠层膜、用于屏幕板的金属被覆用叠层膜
JP4801668B2 (ja) * 2005-05-10 2011-10-26 三菱樹脂株式会社 金属被覆用積層フィルム、スクリーンボード用金属被覆用積層フィルム
JPWO2006121070A1 (ja) * 2005-05-10 2008-12-18 三菱樹脂株式会社 金属被覆用積層フィルム、スクリーンボード用金属被覆用積層フィルム
JP2007022047A (ja) * 2005-07-21 2007-02-01 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シート、および積層シート被覆金属板
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JP2007203464A (ja) * 2006-01-30 2007-08-16 Riken Technos Corp 積層化粧シート
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JP2010510102A (ja) * 2006-11-25 2010-04-02 レオンハード クルツ シュティフトゥング ウント コー． カーゲー 冷間成形可能な金属材料をコーティングするためのラミネートフィルム
JP2008254348A (ja) * 2007-04-05 2008-10-23 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シートおよび積層シート被覆金属板
JP2010094890A (ja) * 2008-10-16 2010-04-30 Mitsubishi Plastics Inc 樹脂被覆金属板用積層シ−ト、該積層シートの製造方法、および、意匠性積層シート被覆金属板、ユニットバス部材、建築内装材、および、鋼製家具部材
WO2020059836A1 (fr) * 2018-09-21 2020-03-26 三菱エンジニアリングプラスチックス株式会社 Composite résine-métal et sa méthode de production
JP2020199754A (ja) * 2018-09-21 2020-12-17 三菱ケミカル株式会社 樹脂金属複合体及びその製造方法
JP7476504B2 (ja) 2018-09-21 2024-05-01 三菱ケミカル株式会社 樹脂金属複合体及びその製造方法
JP2022019535A (ja) * 2020-07-15 2022-01-27 南亞塑膠工業股▲分▼有限公司 レーザエンボス用ポリエステルフィルム及びその製造方法
JP7244566B2 (ja) 2020-07-15 2023-03-22 南亞塑膠工業股▲分▼有限公司 レーザエンボス用ポリエステルフィルム及びその製造方法

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