TW200416129A - Resin covered metal plate, design sheet for resin covered metal plate and production method for resin covered metal plate - Google Patents

Abstract

A resin covered metal plate comprising a metal plate laminated by a non-stretched layer (A sheet and B sheet) mainly comprising at least two sheet of polyester type resin using the B sheet side as a adhesive surface, wherein the layered sheet has a total thickness of from 65 μm~300 μm, pigment is mainly added to the A layer for coloring and hiding, the A layer has a thickness of 50μm~250μm, the B layer has a thickness of 15μm~80μm, and an amount of pigment component added to the B layer is less than 10wt in 100wt of resin component, is obtained to be a resin covered metal plate having good durability (heat and moisture resistance). And by using an emboss creating machine used previously to create an emboss on a soft PVC sheet, a resin covered metal plate having a good emboss appearance is provided.

Description

200416129 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to the exterior of household appliances such as AV equipment, air conditioner covers, plywood furniture, steel furniture, elevator interiors, door materials, and bathroom walls Material, design materials for resin-coated metal plates, and methods for manufacturing resin-coated metal plates with excellent durability, such as ceiling materials for bathrooms, ceiling materials for bathrooms, and compartments. In more detail, it is excellent in scratch resistance and workability, and has excellent durability in wet and hot environments. It is suitable for bathrooms and other applications. It is not used for resin-coated metal plates containing resins or pattern-designed sheets for resin-coated metal plates. And a method for manufacturing a resin-coated metal plate. [Prior art] It is known that the resin-coated metal plates used in the above-mentioned applications are those in which a soft vinyl chloride sheet (hereinafter referred to as "soft PVC sheet") laminated with color is laminated, and an embossed pattern design is provided. The soft PVC sheet is coated on a synthetic resin molded article, a plywood, a wood fiber board, or a metal plate. The characteristics of soft PVC sheet can be exemplified as follows: ① Because it has excellent adaptability to embossing and forming, it can obtain a coating material with rich pattern design; ② In thermoplastic resin, generally, it is a processing of contradictory elements The balance between surface properties and surface scratchability is relatively good; ③ Because it has excellent compatibility with various additives, and has been carrying out discussions on improving physical properties due to additives for many years, it can easily improve weather resistance (particularly light stability) ). In addition, because filming can be easily performed by calender (6 200416129), even when the pattern is unfolded, compared with the time-consuming extrusion that requires color change purge for film formation, In this case, there are far greater advantages. The method of continuously embossing the soft PVC long sheet is generally a method in which the sheet after film formation is reheated and softened, and a engraved embossed pattern roll (hereinafter referred to as "embossed plate roll") is used. A method of pressing and continuously transferring a pattern. The method of heating the sheet can be considered such as: a contact type that makes contact with heated metal Xingkun and heating; a non-contact type that uses infrared heaters, hot air heaters, etc. to heat without contact with a roller, etc. . In the actual manufacturing line, although only one of these methods is taken separately, it is often used in combination. The equipment with such a series of steps is called "embossing forming machine". In this embossing forming machine, the design that can exchange and load the embossing plate rollers is very popular. By preparing multiple embossing plate rollers, the embossing pattern can be changed easily and economically, which is suitable. For coping with small batches of embossing. The soft PVC sheet still has excellent applicability in providing an embossing pattern design using this embossing forming machine. Although soft PVC-based sheet has these characteristics, in recent years, it has been caused by some stabilizers in gas-based vinyl resins due to heavy metal compounds, VOC (Volatile organic compound) problems caused by some plasticizers or stabilizers, or endocrine. Problems such as misregistration and the problem of hydrogen chloride gas and other gas-containing gases during combustion cause the use of vinyl chloride resins to be limited. In the case of using vinyl chloride resins or without using materials, from the viewpoint of the overall environmental load, 7 200416129, although the advantages and disadvantages are not yet clear, users of these products have strongly demanded that the unused gas be used. Trend of vinyl resin. Here, we replaced the soft gas resin with the colored resin layer structure, and used soft components such as styrene and copolyolefin based on polyolefin trees such as polypropylene to obtain soft chlorine. Vinyl resin. This structure is still suitable for applications such as polyolefin resin because of its excellent chemical resistance and good fishing heat resistance. In addition, polypropylene-based sheets can still be calendered. They are not inferior to PVC in terms of low-volume production or color matching. In addition, polypropylene sheet has a narrow temperature range for embossing. The sheet needs to be controlled more accurately. However, the embossing machine used to continuously emboss the sheet is generally directly applicable. advantage. However, when a large soft component is used to impart desired processability, the surface scratch resistance is inferior to that when a soft vinyl chloride resin is used. However, in contrast, when the damage is set to the case where the metal sheet is coated with a soft gas vinyl resin, the problem is that the workability is potentially unsatisfactory, and therefore it cannot be widely used. In addition, since polyolefin is an adhesive material in nature, it is necessary to work harder or more in the process of imparting a printed pattern or the product with a metal plate than in the case of soft PVC. In addition, from the standpoint of durability, the interfacial interface still has instability in peeling off after a long period of time (problems to be solved by the invention) (1) the necessity of imparting heat to the property, The vinyl-based grease is mainly close to the bathroom film, and the softer than the PVC. The PVC is thinner and has the energy distribution. When it is scratch-resistant, it will become a state with a more extensive adhesive layer and an additional metal plate. 8 200416129 From the viewpoint of considering both workability and surface scratchability, in recent years, it has been solved by commercially available metal plates coated with polyester resin. However, generally speaking, polyester resins are materials that are subject to water decomposition in a hot and humid environment and immediately become brittle. Therefore, when used in a hot and humid environment such as a bathroom, it may occur after a long period of time. Phenomenon of appearance change or peeling from metal plate.

Even among polyester resins, it is known that the sheet subjected to the extension crystallization treatment will greatly improve the fishing heat resistance. In addition, it has also been developed that the crystalline alignment on the non-adhesive surface side is not lost during the lamination with the base metal plate, and the solid adhesive force is also taken into account by melting only the vicinity of the side surface of the lamination surface. Technology with good thermal history. However, for applications such as bathrooms, it is required to provide an uneven pattern on the surface by using an embossing machine for providing pattern design. However, it is difficult for the sheet with the stretched alignment, and when the polyester resin is heated to a temperature higher than the melting point of the polyester resin capable of imparting an embossing pattern, the stretched alignment disappears.

In addition, for the sheet covered with a resin-coated metal plate, for the purpose of providing pattern design and concealment of the bottom layer, although pigments are added, bright colors are preferred due to the use of bathrooms, and the workability of the metal plate coated with resin. Due to the restrictions and other restrictions, the thickness of the laminated flakes will be limited. In most cases, white pigments with high concealment use titanium oxide pigments as a primer. In order to adjust the hue incorporated therein, it is necessary to use colored inorganic pigments or organic pigments. In the case of inorganic pigments such as titanium oxide pigments, they may act as degradation catalysts for polyester resins. Impurities used in the pigments will also promote the degradation of polyesters. In addition, in special cases where the pigment particles are formed into a flat shape, etc., generally, the voids formed between the pigment particles and the resin matrix generally increase the moisture permeability in the thickness direction of the sheet. This phenomenon will also be one of the factors that promote the degradation of the polyester resin itself. At the same time, the structure of the resin-coated metal plate has been penetrated. Moisture will corrode the surface of the metal plate, causing a risk of peeling between the sheet layer and the resin-coated metal plate. Sex increased. For this reason, the current situation is that when a polyester resin with the same composition is used to make a sheet without added pigments and titanium oxide pigments to form a resin-coated metal plate, the latter is significantly inferior in moisture and heat resistance. However, how to easily ensure durability is meaningless without adding pigments and has no commercial value for resin-coated metal plates used as interior building materials. Therefore, various attempts have been made to improve the durability of the white pigment-based additives. One such example is the use of surface treatment of pigment particles to perform catalytic active sealing, or the addition of various catalyst non-activators. However, this effect is hardly sufficient. Generally, the special surface treatment of pigment particles will obviously increase the cost, and it is potentially difficult to balance the balance between dispersibility. In addition, since the use of soft PVC foils to coat metal plates, the so-called "high mirror surface" has appeared. This structure is printed on the surface of soft PV C sheets, and a double layer with good smoothness is laminated on the surface. Axial extension PET (polyethyl terephthalate) film. In this case, even if the flexible PVC sheet is replaced with a sheet made of a polyester resin that is non-stretchable and colored with a white pigment, a biaxially-stretched PET film will be present on the surface layer. Permeability will be suppressed by this layer, and better humidity and heat resistance can be obtained. In addition, because of its superior specular reflectance, 2004 2004129 is suitable for bathrooms, this structure will still not be able to obtain embossed patterns. (2) Necessity of imparting thermal properties to embossing There are also concentrated efforts on lubricants such as non-crystalline polyester resins typified by PETG to make it suitable for calendaring. However, when the sheet made of this resin is embossed by a embossing shaper (ca 1 endev film-forming method) like a conventional soft PVC-based or polyolefin-based sheet, As a result, there will be problems in the embossed financial heat. The so-called "embossed heat resistance" means that when the embossed pattern design sheet or the embossed pattern design-covered metal sheet is' formed in a state of scorching heat during use, it shows that the embossing reset is larger or smaller, A smaller reset is called better financial heat. In other words, after embossing is applied to the heated viscoelastic body, the freezing stress can be captured by cooling, but if the frozen stress is heated to a temperature where the stress is re-applied, This will cause a stress reset phenomenon. Therefore, in order to improve the heat resistance of embossing, it is necessary to increase the temperature at which stress is applied. In addition, it can be said that the non-crystalline polyester resin which is provided with the calendering film property by the work of the lubricant, if the stress application temperature is to be increased (determined by the sheet temperature and the embossing plate temperature) in order to improve the heat resistance of embossing The melting tension of the sheet itself will be significantly reduced, the width of the sheet will shrink, wrinkle, and even result in the occurrence of sheet cracking, which cannot provide satisfactory embossed heat resistance. This result is that the embossing heat resistance will be insufficient in the actual use environment, such as the use of surface materials such as tables and when hot coffee is turned over, or the use of appliances with large internal heat dissipation 11 200416129. , It is easy to divide the embossing to become shallow, or disappear, and other appearance defects. In addition, when polyester resin is introduced by extrusion molding, the casting roller is not an ordinary mirror roller, but a pressure roller, which is used to impart embossing to the resin in a molten state flowing out of the τ film. Film method). This method can easily obtain high embossing heat resistance, and the crystallinity of the polyester resin can transfer the embossing pattern. However, compared with the film method, thin sheets of various shades can be efficiently produced in small batches. However, in terms of the film-making method, the time and raw materials required for color replacement are larger than those in small batch production. In addition, the related embossing patterns are also limited in terms of mold releasability and air infiltration, and can not give deeper embossing or complicated pattern embossing. In addition, the washing roller "(castingr 〇11)-generally has a large diameter under the embossing roller compared to the press, and integrates the corresponding pattern of the casting roller, which will be costly in terms of equipment costs and replacement steps. Other methods are, for example, a method in which resin is coated on a steel plate, and the resin is spread on a steel plate. Before the resin is cooled, it is convenient to use embossing to press and transfer the pattern, or the resin-coated sheet is applied again. The method of heating and then using the embossed pattern roller to transfer the embossed pattern can be given to the resin in the molten state regardless of polyester or amorphous polyester. When using a traction roller to transfer a pattern when filming, the restrictions in accordance with the case, and the warpage of the embossing plate roller in contact with the end of the metal plate may cause damage to the plate, so it is necessary to inventory a plurality of preparation triggering lines for film formation. Flower pattern t (extrusion and irrelevant calendering in the extrusion does not tend to the point of view and make a considerable amount of flower shape problem. Melting tree case roll-in metal method. Flowers, but, subject to the figure In the case of rollers, there are still problems from the viewpoint of equipment cost. [Summary of the Invention] In order to solve the above problems, the first invention in the scope of patent is applied, which is not a polyester resin layer system. Two layers containing more pigments (mainly referred to as "Layer A") that are mainly responsible for giving the design of the coloring pattern and the underlying visual concealment effect, and two layers of pigments containing only 10 parts by weight or less ("Layer B") That is, because of the need to add a sufficient amount of pigment, the layer (layer A), which has to reduce the humidity and heat resistance of the layer itself, is a layer that has a small amount of pigment added and has good fishing heat resistance. (Layer B) Integrated lamination can ensure the moisture and heat resistance of the entire laminated sheet, and even the fishing and heat resistance of the resin-coated metal plate. In addition, the presence of a layer with a small amount of pigment can suppress the influence of moisture on The permeation amount on the surface of the metal plate can also suppress the long-term peeling of the sheet and the metal plate caused by the corruption of the surface of the metal plate, and can also improve the safety. With the structure of the present invention, The resin-coated metal sheet that gives the embossed non-stretched polyester sheet structure can also be given a sufficiently colored design pattern and can form good durability (especially moisture and heat resistance). According to the second invention in the scope of the patent application In the third layer of the patent application, the resin component after the film formation of the B layer is set to a specific range, so that it can be made longer. During the period of deterioration, the physical properties can be maintained. In the fourth invention in the scope of the patent application, by adding 100 parts by weight of the resin component in the B layer, the ratio of 0.1 to 5 parts by weight is added. The carbodiimide compound, when extruded into a film or when a resin sheet is formed to cover a metal plate, will reduce the molecular weight reduction caused by the moisture in use, and thus can form a good durability (especially Department of heat and humidity resistance). In the fifth invention in the scope of patent application, because layer B contains polybutylene terephthalate resin (hereinafter referred to as "PBT") resin with a resin content of more than 20% by weight, it is not relevant when the layer B is extruded into a film. Regardless of crystallinity, it can be imparted with boiling water impregnation. In the sixth invention in the scope of patent application, the B layer contains 55% by weight or more of PBT resin, and the washing and casting conditions at the time of extrusion film formation can obtain the B layer with high crystallinity, even if not implemented The crystallization treatment and the like in the subsequent steps can still obtain the characteristics of not sticking to the heated metal part of the embossing shaper. Furthermore, because layer A is mainly composed of non-crystalline or low-crystalline polyester resin, by heating the sheet to a temperature above the glass transition temperature (Tga) of the resin, an embossing machine can be used to impart embossing. Pattern. According to the seventh invention in the scope of patent application, by setting the resin composition of layer A to a commercially available material, there is a cost advantage. In addition, there are fewer concerns about crystallization over time. When the sheet is stored and then embossed, it is still difficult to cause problems. According to the eighth invention in the scope of patent application, printing pattern design can be performed at the same time as embossing pattern design. According to the 9th invention in the scope of the patent application, an embossing machine generally used to impart embossing on soft PVC sheets. By setting the sheet heating temperature to this range, a good embossing applicability can be obtained. Sex. In the 10th invention in the scope of the patent application, embossing pattern design and printing pattern design can be given at the same time, and a polyester resin layer (hereinafter referred to as "" E "layer), and those with good durability of the printed layer can be obtained. In addition, because the E layer is mainly composed of an amorphous or low-crystalline polyester resin, by heating the sheet to a temperature above the glass transition temperature (Tga) of the resin, an embossing machine can be used to impart pressure. • A /-Ah ϋ 化 样 ° In the Π invention of the scope of patent application, by setting the resin composition of the E layer to a commercially easily available material, it has a cost advantage, and it changes with time. There is less concern about crystallization, and it is still difficult to cause problems when embossing is given after the sheet is stored for a long time. In the 12th invention in the scope of patent application, an embossing machine generally used to impart embossing to soft PV C sheets, and by setting the sheet heating temperature within this range, good embossing can be obtained Give adaptability. According to the 13th invention in the scope of patent application, if the A layer and the B layer are co-extruded, the film can be formed without interfacial peeling for a long period of time, and the productivity will be improved. In the 14th invention in the scope of the patent application, because at least two layers of embossing forming layers having different physical properties and a polyester resin of the base resin layer are laminated, the pattern design sheet for the resin-coated metal plate is laminated, and the embossing The shape layer is mainly composed of an amorphous resin, and can be formed into a film by a calendering method. Therefore, thin sheets of various colors can be obtained efficiently in small batches. Even by embossing pattern transfer using an embossing shaper, not only the color tone, but also the related embossing pattern can transfer a variety of patterns in small batches. The layer B with a predetermined thickness functions as a substrate resin layer, because it has 15 200416129 crystallinity, so in the embossing forming machine _ even if the embossing forming layer monomer is heated to the temperature of the sheet that does not cause melt fracture If the melting point T o] b of the base resin layer is below, the laminated structure will not cause problems such as melt cracking and wrinkling. Therefore, an embossed pattern having higher heat resistance for embossing can be provided compared to the case where the embossing forming layer is alone. There are fewer concerns about appearance defects in the actual use environment. Here, the melting point T m b of the base resin layer refers to a peak temperature of crystal melting when the base resin layer is subjected to a differential scanning calorimeter (D S C) for one temperature increase. In addition, although the base resin layer is produced by extrusion filming, since the embossing forming layer is responsible for providing various shades, the base resin layer only needs to be made without added pigments or made with a single tone. A film is sufficient, and it is possible to suppress the color replacement loss which is a difficult point of extrusion film formation. The patent design sheet for the resin-coated metal plate of the 15th invention in the scope of the related application includes a polybutylene terephthalate (PBT) -based resin with a rapid crystallization rate in the base resin layer. If it is more than the above amount, better crystallinity can be imparted when the film is extruded. Therefore, because the subsequent crystallization treatment is not required, and the melting point is below 25 ° C, when the conventional soft gas vinyl sheet is based on a metal plate, it can be determined based on the surface temperature of the metal plate. Full adhesive strength is obtained at a temperature of 2 3 0 ° C. The same applies to the pattern design sheet for a resin-coated metal plate according to the 16th invention of the related patent application. In the 17th invention of the related patent application, the pattern design sheet for the resin-coated metal plate, because the crystallinity of the resin layer of the base material is required before the embossing forming machine is introduced, and a DSC (D ifferentia) is conveniently used. 1 S ca η ning C a 1 orimetry)) The measurement values are standardized to take advantage of the embossing and shaping 16 200416129. Even if the machine comes into contact with a conventional contact heating device (ie, heating metal rollers, etc.), there is still no sticking phenomenon. And even if the sheet is heated, no melt fracture occurs. In the 18th invention of the related application patent, the pattern design sheet for the resin-coated metal plate, the resin component of the embossing shaper is the actual performance of calendaring, and by using a commercially available non-crystalline polyester resin, This ensures stable production and has advantages in terms of raw material prices.

The patent design sheet for the resin-coated metal plate of the 19th invention of the related application, the surface of the base resin layer on which the embossing forming layer is laminated, and the amorphous resin layer is substantially designed together by the extrusion method. , You can more surely use the thermal fusion lamination to ensure the interface adhesion strength. The pattern-designed sheet for resin-coated metal plates of the 20th invention in the scope of the related application patents can form surface properties to be superior in weather resistance, scratch resistance, pollution resistance, and the like.

In the 21st invention of the related patent application, the pattern design sheet for a resin-coated metal plate is formed by integrating the embossing forming layer and the base resin layer by thermal fusion lamination, which is more effective than providing an adhesive layer. In the case of lamination and integration, the number of steps can be reduced, and even embossing forming layers and substrate resin layers can be supplied to the embossing forming machine, and lamination integration and pressing can be performed at the same time. Flowers confer. The resin-coated metal plate according to the 22nd invention of the patent application range is provided with various color tones and embossed patterns, and a resin-coated metal plate with high heat resistance during embossing can be obtained in small batches and efficiently. According to the manufacturing method of the resin-coated metal plate 17 200416129 described in the invention in the 23rd item of the patent application range, by rapidly cooling the laminated resin-coated metal plate, the embossing reset phenomenon during lamination can be suppressed. An embossed pattern design resin-coated metal plate with a deep pattern design can be obtained. [Embodiment] (First invention) Hereinafter, a specific embodiment of the first invention will be described. Fig. 1 (a) is a schematic sectional view showing the basic structure of a resin-coated metal plate of the first invention. From the surface side, a layer A, a layer B, and a metal plate structure with an adhesive layer formed thereon are sequentially formed. In FIG. 1 (b), in addition to the structure of FIG. 1 (a), a printing ink layer (C layer) and a transparent coating layer (D layer) are provided. In FIG. 1 (c), in addition to the structure of FIG. 1 (a), a printing ink layer (C layer) and a transparent polystyrene resin layer (E layer) are provided. In Fig. 1 (d), in the structure of Fig. 1 (c), the printing layer is composed of 2 layers (c-1 layer) and (c-2 layer), etc., which should deal with the printing layer and In the case of a solid printing layer, etc. Furthermore, because the laminated sheet of the present invention adopts a thickness ranging from 65 μm to 300 μηι, although it is more accurately described as "film and sheet", in this connection, generally referred to as the thickness range of "film", For convenience, we will use the term "sheet". &lt; 1> Add layer (A layer) mainly containing pigments for coloring and concealing. Below, add an unstretched layer (layer A) containing polyester resin as main component mainly for pigments for coloring and hiding. , Referred to as "Layer A". The resin component constituting the A layer is referred to as resin A. 18 200416129 Although layer A is a non-stretching polyester resin layer, the so-called "non-stretching" means that the stretching operation is not intentionally given, and it does not mean that the alignment caused by pulling with the casting roller during film extrusion Nor does it exist. The relevant layer B is the same as those definitions. In layer A, pigments are added for the purpose of giving a pattern design by coloring and giving a visual concealment effect to the bottom layer. Although the pigments used only need to be those commonly used in resin coloring, but for resin-coated metal plates to obtain a sufficient underlying concealing effect by the thickness of the generally used flakes, titanium oxide must be used. The pigment is mainly a white pigment. The so-called titanium oxide pigment refers to the rutile 1 etype that has been treated with a general type and the amount of surface treated for resin kneading. It does not refer to titanium oxide without a surface treatment or a sharp surface treatment with poor surface treatment effect. Anatase type titanium (anatase). Of course, from the standpoint of improving durability, although a titanium oxide pigment that has been subjected to a special surface treatment may be used, the cost will increase on the contrary, and the current situation cannot achieve a balanced effect. The above-mentioned titanium oxide pigment is mainly used, and various inorganic and organic colored pigments are used in combination, and the color tone is a desired white-based hue. The thickness of layer A is preferably in the range of 50 μm to 250 μμ. If it is thinner than this range, in order to ensure the hidden effect of the bottom layer, even if a titanium oxide pigment is used, it is still necessary to add a very high concentration of pigment. This may cause deterioration of the film forming property or decrease of the workability of the resin-coated metal plate, so it is not preferable. From the viewpoint that various patterns can be transferred using an embossing forming machine described later, it is preferable to have a thickness of 70 μm or more. In addition, even if the thickness exceeds 250 μm, the concealment effect of the bottom layer will be saturated, which only increases the cost, so it is best not to use it. 19 200416129 Poly-S resin, which is the main component of layer A, can be used instead of a mirror roll when extruding and forming a film, even when a non-oriented, crystalline polyester resin is used. After the method of engraving the embossing plate roll, or after laminating on the metal plate, it is heated to a temperature above the melting point of layer A and melted by reheating or additional heating, and then the embossing plate roll is used to press and The method of transferring embossed patterns, etc., imparts embossed patterns, but both methods have limitations on the embossed patterns that can be imparted, and the equipment cost will increase. Related to these methods, because it is known that the embossing shaper used when embossing soft PVC sheets with embossing (0ff 1 in) is easy to replace the embossing plate roller, and is suitable for small batches. Production, therefore, in the present invention, when an embossing pattern is imparted to a laminated sheet used for a resin-coated metal plate, the embossing shaper can be preferably used. In this case, if the layer A is composed mainly of an amorphous or low-crystalline polyester resin, the elasticity of the layer can be reduced to a value that can be achieved by heating to a temperature above the glass transition temperature (Tga) of the resin. The degree of embossing. In addition, in the present invention, because the A layer is not a single layer, but a layered structure with the B layer, the specific composition of the B layer, even if the A layer is heated to a temperature above the glass transition temperature (T ga) In this case, the function of preventing the occurrence of cracks and the like due to a decrease in the tension of the sheet can be shared by the B layer, and the adaptability to the embossing forming machine can be easily provided. The non-crystalline polyester resin constituting the main body of the layer A is preferably composed of terephthalic acid or di-terephthalate as the main acid component, about 20 to about 80 mo 1. 1% of the alcohol component , 4-cyclohexanedimethanol, about 20.200416129 8 0 ~ 2 0 mo 1. The copolymer polyester resin based on ethylene glycol. Among them, about 30% of 1,4-cyclohexanedimethanol in the alcohol component is widely used, and about 70% in the remaining alcohol component 1.% is a resin composition of ethylene glycol. From the viewpoint of cost advantages derived from mass production effects, it is a better composition. An example of the non-crystalline polyester resin having this composition is, for example, "Ystar-PETG 6 7 6 3" (trade name) manufactured by Eastman Chemical Company. In order not to be limited to this, the so-called "amorphous or low-crystalline polyester resin" in the present invention covers at least the heating step of the embossing forming machine, even if the temperature of the layer A is heated to the glass transition temperature (Tga ) Above, the resin composition which does not make embossing provision difficult as the crystallization progresses. From this point of view, the alcohol component can be appropriately selected from the group consisting of ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol, 1,4-cyclohexanedimethanol, neopentyl glycol, and the like. The acid component is Resin selected arbitrarily from polymers or copolymers of individual components such as terephthalic acid, isophthalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, etc., and the resin is monomer or The polymer has such characteristics that the absolute degree of crystallization is low and the crystallization rate is relatively slow. In addition to the pigment component in the layer A, various additives may be added in an appropriate amount without impairing its properties. Additives such as: filling system, benzene S system and other various antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, metal non-activators, residual polymerization catalyst non-activators, antibacterial / fungicides, Antistatic agents, lubricants, flame retardants, fillers and other general resin materials commonly used additives. Although the method for forming the layer A film can be produced by a calendar film method when the resin composition of the layer A is a non-crystalline polyester, from the viewpoint of ensuring the overall durability of 21 200416129 laminated sheets, It is best to use the co-extrusion film-forming method to solidly laminate the B layer in the die, and there are fewer concerns about interfacial peeling over a long period of time. <2> Layer for ensuring durability (layer B) Layer B is a layer provided to ensure the durability of the resin-coated metal plate, and the durability display mechanism is as described in "Means for Solving Problems". Therefore, firstly, the B layer must belong to a less pigment concentration, and preferably no pigment is added. When pigment is added to the A layer but the hiding effect on the bottom layer is insufficient, although the pigment in the B layer is also added to the resin component in an amount of 10 parts by weight or less, the meaning of the B layer originally exists. From the viewpoint of ensuring the durability of the laminated sheet structure and ensuring the durability of the resin-coated metal sheet covered therewith, it is particularly preferred that it is completely free of pigment. In addition, in the state after the layer B is extruded, it is best to use a GPC (Ge 1 Permeati ο n C hromatogvaphy gel permeation chromatography) to measure the weight-average molecular weight in terms of styrene. 0 0 to 1 4 0 0 0 0 range. The main degradation factor of polyester resins used in hot and humid environments can be considered to be hydrolytic decomposition, followed by embrittlement, resulting in deterioration of mechanical properties, resulting in films, etc. in the state of help, flex and crack. Because in the state of the resin-coated metal plate, cracks will also occur due to the embrittlement of the thin film layer, and the adhesion strength with the metal plate will be reduced, resulting in partial peeling of the thin film layer, etc., so the appearance will be significantly damaged. Pattern design, and at the same time, for the purpose of covering the metal plate with the resin layer, it is not possible to obtain the anti-corrosion effect of the metal surface and the effect of imparting pattern design. In addition, degradation due to hydrolysis occurs in the ester-bonded portion of the polyester chain, which results in a decrease in molecular weight. In the state of the film-forming sheet that was previously placed in 22 200416129 in a hot and humid environment, the molecular weight is already low, and it will be used in a hot and humid environment for a short period of time. As described above, the mechanical properties will be deteriorated, and those with higher molecular weight can be obtained during film formation. It shows that even if used in a hot and humid environment, the mechanical and physical properties are lower than the current one, which has a longer durability. This phenomenon shows that the use in a hot and humid environment will cause the same molecular weight reduction regardless of the same, but the higher the initial molecular weight If the molecular weight is still high after the same period, and physical degradation such as film cracking occurs, it will obviously start to occur when the absolute value of the molecular weight drops to a certain value. Therefore, in order to make the layer B a layer with better fishing and heat resistance properties, the following measures must be implemented: ① In terms of using resin raw materials, choose a molecular weight that is high to a certain degree; ② In terms of film-forming equipment, to suppress molecular weight reduction Therefore, the spiral design is optimized; ③ by installing the exhaust device in an appropriate position, 俾 reduce water decomposition during molding; ④ keep the residence time longer than necessary; ⑤ work on the drying step of the raw materials, 俾 reduce moisture absorption The effect of moisture and so on. In addition, because the layer B of the present invention contains only a small amount of pigment or does not contain any pigment at all, compared with the case of adding a large amount of raw materials, the molecular weight decrease during the forming process is also suppressed, and it is easier to obtain a molecular weight after film formation. From the higher point of view, it also has a beneficial effect on durability. If the layer B of the present invention has a weight average molecular weight of 7500 or more at the time of film formation, the above-mentioned resin-coated metal plate can be prevented from being decomposed to be brittle when it is used in a hot and humid environment. The amount of chemical molecules 23 200416129 is sufficient to form those with sufficient durability. In addition, if the molecular weight is below 14,000, the cost can be sufficiently reduced. The reason is that the molecular weight of the polyester resin raw material used needs to be higher, but this is not generally sustainable and will result in higher costs. In addition, even if such a resin raw material is obtained, the effect of mechanically cutting the molecular chains in the molding machine during film formation will be significant. Therefore, when a thin film is formed, it is often impossible to obtain a desired high molecular weight. , Not only the durability improvement effect reaches saturation, but also causes the situation that the energy required during film formation is too large. In the composition of the B layer resin of the present invention, it is preferable to select a composition that can easily obtain the above molecular weight range. From this point of view, it is preferable to use materials with higher molecular weight such as available solid phase polymers, such as PET resin and PB resin. This resin can be used alone or in combination with other polyester resins. Among them, it is particularly preferable to use a homogeneous PBT resin, which is based on the following viewpoints: ① Extrusion grades will have higher initial molecular weight grades; ② Hydrolysis reaction speed is slower than that of polyethylene terephthalate Ester-based resins (refer to "Thermal and Hydrolytic Decomposition of Poly (1,4 _ Butylene Terephthalate)", Journal of the Fiber Society, vol. 43, No. 7 (1 98 7), Donglei Co., Ltd. By the Institute of Textile Research, Mitsuhiko Tanaka); ③ Although it has a crystalline resin, because the elasticity of the crystal region is lower than that of poly (ethylene terephthalate) resin, the flexibility of the crystal portion (f 1 e X ibi 1 ity) is high, so even if it is coated on a metal plate in a state of high crystallinity, it will still show good processability; 24 200416129 ④ From the melting point (T m) to the metal when laminated with the conventional soft PVC sheet From the viewpoint of the same degree of plate temperature or slightly lower temperature, the equipment and the like used in the production of high-quality PVC sheet-coated metal plates can be directly applied. From the viewpoint of lower temperature, although it is best to use a PBT resin whose isophthalic acid co-results in its melting point, the moisture and heat resistance of this PBT tree is worse than homogeneous molecular weight PBT. If it is known that the device is laminated at a temperature higher than the melting point of the homogeneous PBT, it is preferable to use a homogeneous PBT resin from the viewpoint of moist heat resistance. Furthermore, because PBT resin has a faster conversion speed than PET resin, when the PBT resin composition is used in the case where the amount of PBT exceeds wt%, it is possible to impart boiling-resistant ice to the resin-coated metal plate. Because even when the layer B of the resin-coated metal plate is in a non-crystalline and low-crystalline state, the PBT resin crystallizes immediately when it is immersed in boiling water. The degree of elasticity at which the metal plate is detached. When PBT resin is used in layer B in excess of 55% by weight, the layer B can be obtained in a highly crystalline state in accordance with the casting conditions during film formation. The crystallization treatment in the subsequent steps of extrusion film formation, etc., can still be performed. When A becomes the above-mentioned amorphous or low-crystalline polyester layer, when the laminate is heated above the glass transition temperature of layer A, the tension of layer B can still be used to ensure the fracture tension, and it will not cause adhesion to the pressure. The flower forming machine can heat the metal roller and other phenomena to form a better laminated sheet that is imparted to the pattern by the embossing forming machine. Although the resin component blended with PBT resin in layer B can be used as the surface of the soft layer accumulating grease, it can be extruded from the crystallinity of 20, or below, even if the layered surface is not pre-embossed. For example, 25 200416129 is the same as the better resin component used in the above-mentioned A layer, but resin components other than PBT are less likely to be obtained with raw material molecules located south. From this point of view, it is set to a PBRT-rich composition. It is easier to obtain a sheet having a weight average molecular weight in the range of the present invention, and it is a better situation for the adaptability of the embossing shaper. The non-crystalline or low-crystalline polyester blended with PBT resin is not only dependent on its molecular weight but also its molecular structure. The number of S bonds, acid component, and alcohol component structure in the same weight, and There are differences in the presence or absence of steric effects on water molecules. Although there are also parts that cannot be generalized only by the initial molecular weight, in a system where these materials can be obtained industrially and blended with PBT resin, the initial sheet can be almost The relationship between molecular weight and humidity and heat resistance. Various additives may be added to the B layer to such an extent that its properties are not impaired. Additives can be used such as: phosphorous / phenol-based and other various antioxidants, thermal stabilizers, light stabilizers (normal-temperature-acting radical scavengers), nuclear agents, metal non-activators, residual polymerization catalyst non-activators, General-purpose resin materials such as nucleating agents, antibacterial / anti-mold agents, antistatic agents, lubricants, flame retardants, and fillers. Among them, it is preferable not to add an additive that increases the amount of water penetrating in the thickness direction of the B layer. In addition, the method of suppressing the decrease in molecular weight during extrusion of the B-layer film by the additive, a method of obtaining a colored sheet having a molecular weight within the scope of the present invention, or a method of suppressing the degradation of water in a hot and humid environment after forming a resin-coated metal plate It is also possible to add carbodiimide compounds. This carbodiimide compound inhibits water decomposition in the molding machine during extrusion film formation. The results show that 26 200416129 shows the effect of easily obtaining colored flakes with a molecular weight in the range of the present patent application, and it is not affected in the molding machine. The carbodiimide compound remaining in the flakes after being consumed will have the effect of suppressing hydrolysis during use in a hot and humid environment. Examples of the carbodiimide compound include those having a basic structure represented by the general formula shown below. -(N = C = NR) n- (In the above formula, η is an integer of 1 or more. R is another organic bonding unit.) The R portion of these carbodiimide compounds may be aliphatic or aliphatic. Either ring or aromatic. Specifically, for example: poly (4,4′-diphenylphosphonium carbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide) Amine), poly (tricarbodiimide), poly (diisopropylphenylene diimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropyl Propylendiene carbodiimide), and the like. This carbodiimide compound can be used alone or in combination of two or more kinds. The added amount of the carbodiimide compound is less than 100 parts by weight and less than 0.1 parts by weight and less than 5 parts by weight relative to the resin content, especially 0.5 parts by weight or more and 5 parts by weight or less. Better. If it is 0.1 part by weight or more (especially 0.5 part by weight or more), a sufficient effect of improving water-decomposability can be obtained. In addition, if it is less than 5 parts by weight, the effect of suppressing the reduction of molecular weight will be saturated, which can avoid various problems in extrusion film formation, and related films can also be avoided due to carbonization. Exudation of amine compounds (b 1 eed 〇ut) caused poor appearance or reduced mechanical properties 27 200416129. In addition, it can avoid the situation that the B-level deployment cost becomes a high unit price. Additives having the function of preventing hydrolysis include, for example, block copolymers or graft copolymers having polyfunctional epoxy groups, and the related properties can still be properties other than the heat and humidity resistance required for layer B (bending resistance, etc.) ) Deteriorated range, add appropriate amount. It is known that these additives can improve the hydrolyzability of polyester resins. Of course, although the same additives can be added to layer A to prevent hydrolysis, the reactive additives will react with the hydroxyl groups on the surface of titanium oxide added as pigments. It is more difficult to obtain the effect of addition, and because it is easier to cause the pigment particles to aggregate, the effect is worse than when it is added to the B layer. The thickness of layer B is preferably within a range of 15 μm to 80 μl. By setting it to 15 μm or more, the entire laminated sheet can be formed to have a sufficient durability maintenance effect, and it is possible to sufficiently suppress moisture from penetrating the surface of the metal plate. In addition, by setting it below 80 μηι, it is possible to avoid such durability maintenance effects from reaching saturation, and to avoid the need for the relative thickness of the A layer due to the limitation of the total thickness of the laminated sheet used on the resin-coated metal plate. The necessity of thinning can prevent the phenomenon that makes it difficult to obtain sufficient concealing effect with pigments. The total thickness of the layers laminated with the A layer and the B layer is preferably in the range of 65 μ ni to 300 μ m. If it is set to 65 μm or more, the functions of the above-mentioned layer A and the functions of the layer B can be easily taken into consideration. In addition, if it is set to less than 300 μη, it is possible to directly use a processing mold used in a conventional soft PVC-coated metal plate for secondary forming such as penetration, bending, and extrusion, so it is 28% from a cost perspective. 200416129 There is &lt; a layer whose regulating surface is falling &lt; a pressure is applied by a tree-type poly-A layer is a layer 0 3 &gt; a printing layer (layer c) Setting c ^ 'on the surface of layer A can also give a printing pattern design. Printing can be done by gravure, off-set printing, screen printing or other known methods. The purpose is to give stone pattern hue, eye pattern color, or geometric patterns, sampling patterns and other printing design. It can be used for partial printing, full-face printing, or both partial and whole printing layers. From the viewpoint of ensuring the durability of the printed layer (printing layer discoloration, discoloration, and fading), it is preferable to provide a transparent coating or a transparent resin layer on the printed layer. 4 &gt; Transparent coating layer (D layer) The function of the coating layer can be implemented before the lamination sheet is passed into the embossing forming machine, or it can be implemented later, but the disposal of the coating line is best to be given before the flower. For smooth sheet, it is best to print and cover layer A beforehand. The coating layer can be applied by various common methods. The coating layer d

For example, the composition of J may be silane polycondensation such as polysiloxane, silicon acrylate, etc., fluorinated ethylene-vinyl ether copolymer, acrylic polyalcohol, aminomethyl polyalcohol, ester polyalcohol, etc. But the type and the like are not limited to this, and the "adhesion to the layer" is only required if it has non-adhesiveness with the heating gold in the embossing step, and there is no particular limitation. In addition, the covering layer D may be composed of two or more layers. 'Set the outermost layer as a non-stick metal layer, and interpose the layer with an adhesive function between this layer and the printing layer C (or A layer). . In this coating layer, it is also possible to match the purpose. Adding UV absorber 29, oxygen D layer. It is difficult to live evenly, embossing is easy to deteriorate, &lt; 5 &gt;through-day; It is not necessary to make the non-stretching layer without pigment because of the thickness of E. If the thickness is more manageable, the E-layer of the metal-clad plate is also difficult to prevent the addition of purple and so on. , Antistatic agents, translucent pigments, dyes, etc. Gui Huihou: / Ί It is also in the range of 1 to 10 μm. If it is thinner, I am afraid that problems such as sentence coating will be best avoided. & If it is thicker than this, it will be better not to give the adaptability or the secondary workability of the resin-coated metal sheet. 5 The coating layer (E layer) may further provide a layer with a thickness of 25 μm to 100 μm as a main layer, which is mainly a polyester resin. This can highlight the deep pattern design of the printed layer, and at the same time, by forming the same composition layer as the preferred resin composition of the A layer in the outer region, the embossing machine can be used to give the embossing pattern. Layer A and E must belong to the same resin composition. The layer must be laminated after applying it to the layer A. Therefore, in this case, the single-layer sheet before lamination is very poor, and it is best avoided. On the other hand, if the thickness is thicker than the yellowing due to light irradiation during use, and the workability of the resin will be deteriorated, it is not preferable in this regard. Various additives are added like door A or b, especially for the purpose of discoloring and fading of the printing layer due to light deterioration. In addition, mica powder or laser hot stamping (h010 gram) can be added to the extent that the printed layer cannot be seen through. The method of laminating on the c layer of the printing layer can be based on various adhesives and the & agent can be based on polyester resins, polyether resins, etc. 30 200416129 and cross-linking using isocyanate 6 Such curing is generally referred to as an adhesive for dry lamination. In addition, 'also' can be used to form the c-layer with a heat-fusible printing ink 'or in the printing step 10, the first member is given a heat-fusible coating layer to the outermost surface layer, etc. The sheet heating step is performed by a method such as thermal fusion lamination. When the E layer is given, 'the total thickness of the laminated plate is preferably not more than 300 μm. &Lt; 6 &gt; The metal plate constituting the object of the present invention can be used as hot rolled steel plate, cold Various types of steel plates, such as rolled steel plates, dazzling fusion zinc steel plates, electro-zinc steel steels, Qianxi steel steels, non-recorded steel plates, or aluminum plates, are also used after being processed by ordinary chemical conversion. The thickness of the base metal plate varies depending on the application of the coated metal plate, and it can be selected within the range of 0.1 mm to 100 mm. The resin-coated metal plate of the present invention can be obtained by laminating a laminated sheet composed of at least * A layer and B layer on a base metal plate. Examples of the thermosetting adhesive layer (hereinafter referred to as "E layer") used in the lamination include various well-known ones such as epoxy-based adhesives and amine ester-based adhesives. Apply coating equipment such as reverse coater and kiss coa ter to metal plates, and apply adhesive on the metal surface where the laminated integrated sheet is laminated. The thickness of the adhesive film after drying was about 2 to 10 μηι. Secondly, the infrared heater and / or hot air heating furnace is used to dry and heat the coated surface. The surface temperature of the metal plate is maintained at an arbitrary temperature, and the laminated sheet is immediately covered with a roll laminator, and the resin is obtained after cooling. Covered by 31 200416129 metal sheet. (Second invention) Hereinafter, the second invention will be described based on the illustrated embodiment. Fig. 2 (1a) is a schematic diagram of a pattern design sheet for a resin-coated metal plate having a basic structure of the second invention. The pattern design sheet for a resin-coated metal plate is basically composed of an embossing forming layer A and a base resin layer B. In FIG. 2 (1 b), in addition to the structure of FIG. 2 (1 a), the design is substantially made of an amorphous polyester resin between the embossing forming layer A and the substrate resin layer B. Composition of layer C. In FIG. 2 (1 c), in addition to the structure of FIG. 2 (1 a), a non-adhesive coating layer D is provided on the surface of the embossing forming layer A and the heating metal. An example of the resin-coated metal plate shown in FIG. 2 (1 d), and the pattern design sheet for the resin-coated metal plate having the structure shown in FIG. 2 (1 a) is laminated on the metal plate F through the thermosetting adhesive E . In addition, the pattern design sheet for a resin-coated metal plate having the structure shown in Figs. 2 (1b) and 2 (1c) may be laminated on the metal plate F in the same manner. FIG. 3 shows an example of an embossing machine conventionally used for imparting an embossing pattern to a soft P V C sheet. The embossing forming layer A and the base resin layer B are each formed of a polyester resin having different physical properties. Hereinafter, the polyester resin that forms the embossing forming layer is referred to as "polyester resin A" (or simply "resin A"), and the polyester resin that forms the base resin layer is referred to as "polyester resin B" "(Or" Resin B "for short). &lt; 1 &gt; The resin component of the resin embossing forming layer forming the embossing forming layer A, as long as it is generally a non-crystalline polyester resin 32 that can be embossed and formed into a film, 2004 2004129 is not particularly required limit. The term "amorphous polyester resin" as used herein refers to polyester resins that show no crystallinity, as measured by a differential scanning calorimeter (DSC). However, because the crystallization rate is extremely slow, it is considered to be a substantially non-crystalline polyester resin handler. Among these, there are more cases of calendering film. From the viewpoint of stable supply of raw materials, less and unstable, and raw material prices, one of the better examples is "Estar" manufactured by Eastman Chemical Company. -PETG 6 7 6 3 "(trade name). However, the present invention is not limited to this. For example, it is possible to use the "TSUNAMI" series of PETG grades made by Eastman Chemical Co., Ltd., or if it shows crystallinity under specific conditions, but can be treated as a non-crystalline resin under ordinary conditions. Including "PCTG · 544 5" produced by MAN Chemical Co., Ltd., the acid component is mainly composed of terephthalic acid or dimethyl terephthalate, which accounts for about 20% to 80%. 1,4-cyclohexanedimethanol as an alcohol component, and about 80 to 20 m ο 1.% Of the remaining alcohol component are polyester resins within a composition range of ethylene glycol. If the composition ratio of the alcohol component exceeds this range, the crystallinity will be noticeable, so it is best avoided. Furthermore, neopentyl glycol copolymerized PET may be used, which is essentially a non-crystalline composition. In the embossing forming layer, pigments are added for the purpose of giving the design of the pattern and giving the underlying visual concealment effect. The pigments used can be those generally used in the conventional resin coloring, and the added amounts are also for the above-mentioned purposes, so only the ordinary added amounts are required. For example, in white coloring, you can use titanium oxide with a high concealing effect as a primer, and use colored 33 200416129 colored inorganic and organic pigments to adjust the hue. Alternatively, when pigment is added to the base resin layer by adding pigments, a method such as adding a translucent pigment or a dye with a low organic concealing effect such as reducing the pigment concentration of the embossing forming layer, etc. A color pattern design that matches the hue of the resin layer of the substrate can be formed. In addition, in this case, it is possible to add a laser hot stamping foil, colored mica, or the like to the embossing forming layer to provide pattern designability. In addition, the required amount of addition may be appropriately added in order to improve the rolling film forming property. Examples of such additives include various lubricants for improving the mold release from the calender roll or reducing the load during film formation, linear ultra-high molecular weight acrylic resins for increasing the melt tension, or unfolding after the application. Fibre-like processing aids such as polytetrafluoroethylene, gelation promoters, or additives added for the purpose of improving bank shape and improving flow pattern (f 1 0wwark). In addition, additives other than the above may be appropriately added to the embossing forming layer within the range of not being damaged. Such additives include: various antioxidants such as barriers, benzene S, and other stabilizers, heat stabilizers, ultraviolet absorbers, light stabilizers, impact modifiers, metal non-activators, residual polymerization catalyst non-activators, antibacterial / anti-mold Additives commonly used in general resin materials such as agents, antistatic agents, flame retardants, and fillers, or terminal carboxylic acid blocking agents such as carbodiimide-based or epoxy-based, or anti-hydrolytic agents are particularly suitable Among the polyester resins. The preferred thickness of the embossing forming layer is in the range of 50 μm to 300 μn. If it is set to 50 μm or more, the film-forming property is good, and homogeneous flakes can be easily obtained. In addition, it is not necessary to add pigments at a high concentration of 34 200416129 degrees in order to highlight the concealing effect of the bottom layer, which can easily avoid the reduction of processability caused by the addition of high concentration pigments. In addition, if it is set to less than 300 μπί, heating during embossing will cause unnecessary cost and efficiency due to heating to a sufficient temperature, which is disadvantageous to cost and efficiency, so it is best avoided. In addition, the effects of various properties required for the pattern design sheet can be prevented from reaching a saturated state. Within the above thickness range, the thickness of the embossing forming layer is determined after investigating the depth of the plate to be embossed. As described above, because the embossing forming layer of the present invention adopts a thickness range of 50 μm to 300 μm, it is more accurate to describe it as “film and sheet”. In this connection, the thickness of the film is generally referred to as the thickness of the film. Also called "flakes". The same is true of the related substrate resin layer. The embossing-imparting layer is thinned by a calendering method, so that various shades can be efficiently produced in small batches. &lt; 2 &gt; When the resin forming the base resin layer B is used to heat a sheet to give an embossing pattern by an embossing forming machine, melt cracking, wrinkling, and shrinking occur only on the embossing forming layer. The presence of a substrate resin layer has the function of a support layer that prevents this phenomenon. Therefore, the required properties of the substrate resin layer are such that adhesion does not occur even when it comes into contact with heated-metal rolls, etc., and the above problems do not occur on the embossing forming layer monomer, and it can better impart embossing. At higher temperatures, melt cracking, wrinkling and shrinkage will not occur. In addition, if heat-bonding lamination can be formed with the embossing forming layer, the lamination integration can be performed in the same step at the same time when the sheet is heated by the embossing forming machine. In addition, when using a resin-coated metal plate, it is best to use a conventional temperature condition when laminating a soft PVC-based resin-coated metal plate to obtain a strong adhesive force. From the viewpoint of functioning as a support layer, a polyester-based resin having a crystallized state of a certain degree or more is required, and more specifically, it needs to be a measurement value that satisfies a single temperature increase using a differential scanning calorimeter (DSC) , Is a sheet with a relationship of "0.5 &lt; (△ Hm- △ He) / △ Ηιη". This is because even if the resin B is composed of a crystalline composition, when the crystallinity is low, the phenomenon that the embossing shaper adheres to the heated metal roll will occur. Furthermore, when the pattern design sheet is coated on a metal plate, the melting point (Tmb) of the base resin layer is in the range of 18 (TC ~ 24 0 ° C), and the base resin layer is preferably an unstretched sheet. This is because the conventional lamination equipment used for laminating soft PVC sheets on metal plates can be directly adapted to the same lamination temperature conditions as conventional. By using the above-mentioned melting point range for the substrate resin layer, The surface temperature of the metal plate during lamination can be set to a temperature 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 adhesion. By melting the base resin layer The point is set below 240 ° C, and strong adhesion can be obtained even under the conventional lamination conditions. In addition, it can easily avoid the deterioration of the surface coating treatment of the metal plate. In addition, by setting it at 1 Above 80 ° C, when the metal plates are laminated, although the advantage of ensuring the adhesive force at a lower laminating temperature has disappeared, the function as a support layer in the embossing forming machine will become superior. Compared with embossing forming layer in a single way In the case of an over-embossing forming machine, the sheet temperature at the time of embossing can be increased. The use of a stretch film on the substrate resin layer may occur before the melting point of the substrate resin layer is reached during lamination. Significant shrinkage, and sensitization on the resin layer of the resin-coated metal plate, 36 200416129, so it is best not to use. Polyester resins forming resin B can use various crystalline polyester resins. Polyparaphenylene terephthalate Crystallization rates of diethyl acid (hereinafter referred to as "PET") resins are relatively slow. In order to obtain the preferred crystallinity of the present invention, it is necessary to perform additional crystallization treatment after extrusion to form a film, leading to an increase in steps. In addition, In the case of PET-based resins, when crystallization is performed, the melting point is high, and it is not possible to obtain sufficient adhesion strength on the laminate with the metal plate using conventional conditions, so it is best not to use it. Therefore, polybutylene terephthalate (hereinafter referred to as "PBT") based resin or polytrimethylene terephthalate (hereinafter referred to as "PTT") based resin has a relatively rapid crystallization rate. Therefore, borrow by When setting the temperature of the casting roll during extrusion film formation, it is particularly suitable from the viewpoint that the crystallinity required for the substrate resin layer can be imparted at the time of extrusion film formation. The melting point is a so-called homogeneous · PBT or homogeneous · PTT composed of a single component of an acid component and an alcohol component, about 2 2 5 ° C, which can be laminated on a metal plate under the above-mentioned conventional conditions. From the viewpoint of obtaining strong adhesion, it is a better situation. From the viewpoint of the adhesion strength with steel plates, even in PET resins, it is composed of copolymerization of isophthalic acid copolymerized PET, etc. It is possible to obtain those having a melting point within the above-mentioned preferred temperature range. However, in this case, the crystallization rate is slower than that of the homogeneous PETT because the time required for the crystallization process step will be longer, so it is better not to. When using the conditions of lamination equipment, if you want to obtain a strong adhesion at the melting point of homogeneous · PBT resin or homogeneous · PTT resin at a slightly low temperature, you can also use isophthalic acid copolymerization to reduce the melting point. Department of resin and so on. In this case of 20042004129, it is preferable to set a copolymerization ratio in the range of (Δ Hm- Δ H c) / Δ H m value of 0.5 or more in the thin film forming step. In addition, the base resin layer may be composed of a homogeneous · PBT resin or a homogeneous · PTT resin and blended with a non-crystalline resin. However, in this case, it is still possible to obtain non-adhesion during extrusion film formation. The resin B which has been crystallized before the degree of heating the metal roller is preferably blended with a homogeneous · PBT resin or a homogeneous · PTT resin containing 60% by weight or more. By setting the ratio of the crystalline resin to 60% by weight or more, it is possible to easily provide better crystallinity in the extrusion film-forming step. By blending less than 40% by weight of an amorphous resin, the composition shown by the crystalline melting heat (ΔHm) of a differential scanning calorimeter (DSC) can be reduced, and the degree of crystallization at the maximum crystallization can be reduced. In this way, it is possible to reduce the amount of heat consumed by the crystallization during the lamination on the metal plate, and even to increase the volume of the amorphous portion, it is easy to obtain a strong adhesion. Various kinds of additives can be appropriately added to the base resin layer as well as the resin A. The base resin layer is produced when the film is drawn out. By forming transparent flakes without added pigments or coloring them into a specific single color, the loss of raw materials and time caused by color switching can be prevented. The thickness of the substrate resin layer is preferably in the range of 20 μm to 300 μm. By setting the thickness above 20 μηι, it can be fully ensured that when the laminated sheet is heated by an embossing shaper, it is treated as The effect of the support layer. In addition, by setting it below 300 μm, the effect of using it as a support layer when embossing is given can be prevented from saturating, resulting in only a cost increase. When the substrate resin layer is formed into a film, a well-known method at the time of broadcasting film formation can be used, for example, 38 200416129, for example, an inflation method (i n f 1 a t i ο n w e t h 〇 d), or a T-die method. For the purpose of ensuring thermal fusion with the embossed forming layer, a structure of coextrusion of a layer consisting essentially of an amorphous polyester resin may be used. The resin composed of a layer composed of an amorphous polyester resin may be substantially the same as the amorphous polyester resin that can be used in the resin composition of the embossing forming layer. This may be the same composition as the embossing forming layer or a different composition. When the sheet heating step of the embossing forming machine is used to thermally fuse the embossing forming layer and the substrate resin layer, the embossing forming layer will be heated and softened. The base resin layer needs to maintain a high elastic modulus for this function. Depending on the equipment, there is a possibility that the adhesion between the embossing forming layer and the base resin layer is insufficient. In the case of using a base resin layer provided by a co-extrusion and having a layer consisting essentially of an amorphous polyester resin, the base resin layer side surface (the layer consisting essentially of an amorphous polyester resin) ) Will also be heated and softened. In this way, a firm adhesion can be easily obtained between the embossed forming layer. Since the layer consisting essentially of an amorphous polyester resin is a layer having the function of an adhesive layer, the thickness is preferably within a range of about 3 μm to 30 μm. The total thickness of the laminated sheet (A + B, or A + C + B) is preferably set to less than 5 ◦ 0 μπί, and particularly preferably set to less than 300 μπι. By setting it to 500 μm or less (especially 300 μm or less), it is possible to fully obtain secondary processing adaptability such as penetration processing when used as a resin-coated metal plate. In addition, it is possible to use a molding die conventionally used for coating a metal plate with a soft gasified vinyl resin, which is preferable from the viewpoint that it is not necessary to newly manufacture the molding die. 39 200416129 &lt; 3 &gt; Lamination integration and embossing of thin sheets Fig. 3 shows a conventional example of applying embossing shaper 10 to a soft P V C sheet. After the sheet 2 is overheated by the heated metal roll 1, the sheet temperature is further increased by the non-contact heater 3, and then the embossing can be formed by passing between the embossing plate roll 4 and the pressing roll 5. A structure in which a pattern is transferred to a sheet. To this equipment, an embossing forming layer for film formation by the calendering method and a base resin layer for film formation by the extrusion method (or coextrusion with a layer consisting essentially of a non-crystalline polyester resin) were simultaneously supplied. As an example, there is a method in which these sheets are laminated by using a supply portion to a heated metal roller, and the two sheets are laminated and integrated by using the heat of the heated metal roller. The application of the related embossing pattern can be performed like the conventional soft PVC. In this case, unlike the case of the embossing-imparting layer monomer, even if the sheet heating temperature by the embossing forming machine is set to 160 ° C or higher (T mb-2 0) ° C, There will be no adhesion to the heated metal I or melting and cracking of the sheet. Therefore, a higher embossing heat resistance which cannot be obtained with the embossing forming layer monomer can be obtained. &lt; 4 &gt; The metallic non-adhesive coating layer D is provided on the surface of the laminated sheet (A + B, or A + C + B) to improve the weather resistance, the scratch resistance, and the ultraviolet absorbing property, For special purposes such as improving pollution resistance, improving solvent resistance, and imparting a deep pattern design, the coating layer D may also be provided. The coating layer D may be applied before the laminated sheet enters the embossing forming machine, or may be performed afterwards. Utilizing the disposition of the covered thread, it is best to apply the sheet in a smooth state before embossing, and it is better to apply a coating on the embossing layer in advance. In this case, in addition to the above-mentioned purpose, the coating layer needs to have non-adhesiveness with the heating metal.

The coating layer can be provided by a known method. The resin composition of the coating layer D may be, for example, polysilicon oxide (si 1 ic ο ne), sulphuric acid syrup, etc. polysilicon condensation, fluorinated ethylene-vinyl ether copolymer Materials, acrylic polyols, etc. The present invention is not limited to these, as long as it can obtain the adhesion between the embossed forming layer and non-adhesion to the heating metal, the rest is not particularly limited. In addition, the coating layer D may be composed of two or more layers, and the outermost layer may be a metal non-adhesive layer, and a layer having an adhesive layer function with the layer and the resin A may be interposed. To this coating layer, ultraviolet absorbers, silicon particles, antistatic agents, translucent pigments, dyes, and the like can be added according to the purpose. The preferable thickness of the coating layer D is in the range of 1 to 10 μm. By setting above 1 μm, uniform coating can be easily formed. In addition, by setting it to 10 μm or less, good embossing property can be formed.

&lt; 5 &gt; Metal plate F The metal plate constituting the object of the present invention may be various steel plates such as hot-rolled steel plates, cold-rolled steel plates, hot-dip galvanized steel plates, galvanized steel plates, tin-plated steel plates, stainless steel plates, or aluminum plates, aluminum Series alloy plates can also be used after general chemical conversion treatment. The thickness of the base metal plate varies depending on the application of the resin-coated metal plate, etc., but it can be selected from 0.1 mm to 10 in in. <6> Manufacturing method of resin-coated metal plate The manufacturing method of the resin-coated metal plate will be described. When the laminated sheet (A + B, A + B + C) with the embossed pattern formed by the embossing shaping device is used, the adhesive used when the layer 41 200416129 is laminated on the base metal plate can be adhered; Agent, thermosetting adhesive for amino-based adhesives, polyester-based adhesives. The metal plate obtained from the resin-coated metal plate uses a cloth equipment such as a reverse coater and an anastomotic coater. The above-mentioned epoxy-based, amine-based, polyester are laminated on the laminated integrated sheet. The film thickness of the adhesive after isothermal curing is about 2 to 10 μm. Secondly, by using infrared heaters and / or hot air heating surface drying and heating, the surface temperature of the metal plate is kept at a high speed. A roll laminator is used to cover and cool the laminate by knowing the substrate resin. In the resin coating invention, the substrate tree (Tin) located on the side of the adhesive surface with the metal plate is preferably set within a range of 180 ° to 240 ° C. In this case, the surface temperature can be set as it is the case with a conventional soft PVC metal plate, and a strong adhesive force can be obtained. According to the present invention, an embossed heat-resistant metal plate can be obtained. It is best to reduce the occurrence of heat caused by the heating of the sheet during lamination by performing cooling immediately after lamination. <Example> (First invention) In order to explain the first invention more specifically and in detail, it is shown that the first invention is not limited to these examples. In addition, the physical property measurement specifications of resin-coated metal plates shown, test pianos, such as epoxy systems, are generally used methods, which are coated with a type of adhesive on the metal-like coating surface. At any temperature during application, the layers form a metal sheet with an adhesive surface. In the case of the melting point of this fat layer, the metal plate is thinly laminated and covered, and the resin is rapidly embossed and reset by water cooling. The second embodiment, the embodiment and the comparative method are shown in the following 42 200416129. (1) The weight-average molecular weight of the polyester resin is installed on a Dongsu (stock) weight gel permeation chromatography-HLC_8120GPC, and a GPC-8 0 0 CP series of Shini ~ pack series manufactured by Shimadzu Corporation is installed. In the preparation of the sample, a mixed solvent of hexamethylene isopropanol / aerosol = 1/20 (v〇1 / v〇1) was used according to the sample solution concentration of 0.4 7 6 wt / v 1%, and the solution was injected. Amount of 10 μ 丨, and in the mobile phase solvent, using gas imitation, according to the flow rate of the solvent. 2m j / 、, &gt; Cereal temperature 4 0 C measured and then calculated based on polystyrene conversion Weight average molecular weight of the ester resin. The weight average molecular weight of the standard polystyrene used is 2000000, 430000, 110000, 35000, 1 0 0 0 0, 4 0 0, 6 0 0. The measurement was performed on the B layer after the relevant extrusion film formation. (2) Durability (humidity and heat resistance) test After a 60 mm x 60 mm resin-coated metal plate was allowed to stand in an 80 ° C X 98% RH constant temperature and humidity tank for 2 months, the appearance change was visually observed. The person who completely tears the historian is (0) ', and the resin layer is only found to be slightly cracked, or the slightly swollen is found to be (A), and the resin layer will be found to have obvious cracks and obvious swelling. , And the occurrence of peeling between the laminated sheet and the metal plate is denoted as (X). (3) embossing imparts adaptability: proof resistance When embossing is imparted by the embossing knurling machine shown in FIG. 3, those who adhere a sheet to a heating roller (heating roller) are marked as "χ", The occurrence of adhesion was recorded as "0". (4) Embossing imparts adaptability: resistance to fusing. When embossing is imparted by the embossing knurling machine shown in FIG. 3, when the sheet is heated by adding a heater of 20044316129, the fusing of the sheet is recorded as "Χ", and the person who did not break was recorded as "〇". (5) Embossing imparting adaptability: transferability The embossed sheet that has been embossed by the embossing forming machine shown in FIG. 3 is observed visually, and those who transfer the embossed pattern beautifully are marked as "0", and Cases where the transfer is lighter than this are recorded as "△", and those with poor transfer, forming a lighter embossed pattern, or those with unrelated embossed patterns only on the surface are recorded as "x". (6) Choi> Futeng water-based test: 60 mm χ 60 m π resin-coated metal plate was immersed in boiling water for 3 hours, and the surface state of the resin sheet was judged visually. ), The number of disturbances appearing on the surface is recorded as (△), the deformation of the resin layer such as obvious expansion is recorded as (χ). (7) Workability: An impact tight bending test was performed on the resin-coated metal plate, and the condition of the cosmetic sheet surface of the bent portion was judged visually. Those with little change were recorded as (0), and those with some cracks were recorded as (△ ), The person who cracked is recorded as (χ). In addition, the impact tight bending test was performed as follows. From the longitudinal direction and width direction of the coated metal plate, a 50 mm χ 1500 mm in sample was prepared and held for 1 hour at 23t :, and then bent by a bending tester to 1 8 (Γ (inner bending radius 2 mm) ), And then a cylindrical hammer with a diameter of 75 mm and a mass of 5 Kg was dropped on this sample from a height of 50 cm. (A) Production of a laminated film is shown in Table 1 as examples a 1 to a 7 and Composition of “layer B” of Comparative Examples a 1 to a 6. 44 200416129 Table 1 Composition of resin B (% by weight) Pigment with stem parts by weight B layer thickness (net) Weight average molecular weight can be shot blue 5008 can be shot blue 5020S Star 6763 co. PET BK-2180 PET RT-580 Example al 0 100 0 0 0 8 30 97 400 Example a2 0 100 0 0 0 0 30 102000 Example a3 0 80 20 0 0 0 30 95 300 Example a4 0 60 40 0 0 0 30 90 300 Example a5 0 40 60 0 0 0 30 84700 Example a6 0 20 80 0 0 0 30 75 800 Example a7 0 0 0 0 100 0 30 117000 Comparative example al 0 100 0 0 0 0 10 101000 Comparative example a2 0 80 20 0 0 12 30 88 300 Comparative example a3 0 20 80 0 0 8 30 73 100 Comparative example a4 100 0 0 0 0 0 30 59600 Comparative example a5 0 0 100 0 0 0 30 62 300 Comparative example a6 0 0 0 100 0 0 30 61 700

The related examples a 1 to a 7 and comparative examples a 1 to a 6 shown in Table 1 were obtained by using two p 6 5 n m biaxial kneading extruders and co-extrusion using a split method to obtain Table 1 2-layer laminated sheet of layer B of the resin composition shown. The total thickness of the laminated sheet is 120 μm, and the thickness of the layer B is shown in Table 1. Table 1 also shows the weight average molecular weight of the layer B after film formation. The composition of layer A is a blending composition of PBT resin (Nippon Blue 5 0 2 0 S (trade name): 20 parts by weight) and PETG resin (Yasda 6 7 6 3: 80 parts by weight). Titanium oxide Pigment 2 4 parts by weight (resin content is set to 100). This is the same except for Comparative Examples a 7 to a 1 of a single-layer sheet. 45 200416129 Table 2 Single-layer sheet composition (weight ° / 〇) Titanium oxide added weight parts thickness weight average molecular weight can shoot Di Blue 5020S Istar 6763 Comparative Example a7 100 0 20 120 89300 Comparative Example a8 80 20 20 120 82500 Comparison Example a9 60 40 20 120 77400 Comparative example alO 40 60 20 120 70 300 Comparative example a 11 20 80 20 120 66 100 Comparative example a2 20 80 10 120 71700 Comparative example al3 0 100 20 120 57900 Related comparative example a shown in Table 2 7 ~ The a 1 3 series is a single-layer film composed of only a large amount of pigment added. Only a P 6 5 mm biaxial kneading dial-up machine is used for film formation. The thickness is all 120 μm. In all cases, the film-forming system adopts the T-die washing and casting film-forming method. (B) Application of coating layer (D layer) Table 3 shows the composition of Examples a 8, a 9 and Comparative Examples a 1 4 to a 1 9. Table 3 Characteristics of layer B coating resin B composition (% by weight) Titanium oxide added I parts by weight Carbo Pollard ~ added amount parts by weight weight average molecular weight coating thickness (μ in) can be shot blue 5020S Istar 6763 implementation Example a8 20 80 8 0.5 5 76 900 8 Example a 9 20 80 8 1 76 300 8 Comparative example a 14 20 80 8 0. 06 72 900 8 Comparative example a 1 5 20 80 8 0 73 100 8 Comparative example a 1 20 20 80 12 0 68700 8 Comparative Example a 1 7 20 80 12 1 69200 8 Comparative Example a8 20 80 20 0 66100 8 Comparative Example a 1 9 20 80 20 3 67300 8 * 1: Carbodilite, product name shown in Table 4 is Example a 1 0 ~ A 1 5 and the composition of Comparative Examples a 2 0 and a 2 1. 46 3 12 / Instruction of the Invention (Supplement) / 93-03 / 92137012 200416129 Table 4 Features of the outermost layer of the B layer 1 [Type and thickness of the composition of the resin B (% by weight) Oxidation — Addition amount Weight average parts by weight Type of the outermost surface layer Thickness of the outermost layer (μπ 迪) Can shoot Di Blue 5020S Istar 6763 Example alO 80 20 0 95300 Thin film lamination 30 Example all 80 20 0 丨 丨 // 50 Example al2 80 20 0 丨 丨// 80 Example al3 80 20 0 // Cover 4 Example al4 80 20 0 // // 8 Example al5 80 20 0 // // 16 Comparative Example a20 80 20 0 // Thin Film Lamination 120 Comparative Example a21 80 20 0 // Thin film lamination 24 Examples a 8 and a 9 shown in Table 3, comparative examples a 1 4 to a 1 9 and examples a 1 3 to a 1 5 shown in Table 4 are layered A printing layer and a covering layer are provided on the surface of the A layer side of the sheet. The printing method is an ordinary gravure coating method. After the entire surface is printed with a white-based ink on the surface of the layer A, the partial printing of the abstract pattern is performed. In addition, a transparent coating layer was formed by coating a cyanate-crosslinking acrylic polyol on the thickness as shown in Table 4. In addition, the composition of layer B of these coatings is shown in Tables 3 and 4. The ones shown in Table 3 are not in line with item 6 of the scope of patent application for the present invention, so they are not shaped by embossing. The adaptability of the machine for embossing. The thickness of layer B is 30 μηι. The composition of layer A is the same in Examples a 1 to a7 and Comparative Examples a 1 to 3, and the thickness is 90 μm. The coating layer thickness is shown in Tables 3 and 4. (C) The transparent film layer (E layer) is given in Examples a 8, 8 and 9 and Comparative Examples a 1 to 4 1 shown in Table 3, and the printing layer is provided on the side surface of the layer A of the laminated sheet and Transparent film layer. The printing method is a common gravure coating method. After the entire surface is printed with a white ink on the surface of the layer A, the partial printing of the abstract pattern is performed. On top of this, 47 312 / Invention Specification (Supplement) / 93_03 / 92137012 200416129 is used to impart a polyester-based adhesive resin layer by a printing line, and a transparent film layer is designed by thermal fusion lamination. The composition of the transparent film layer is a blending composition of PBT resin (Nippon Blue 5 0 2 0 S: 20 parts by weight) and PETG resin (Isida 6 7 6 3: 80 parts by weight). It does not contain titanium oxide pigments, etc. Inorganic pigment, 50 μm thick. Since those listed in Table 4 satisfy the composition described in item 6 of the scope of patent application, they have adaptability to an embossing shaper. The resin composition of these layers is specifically the following. ΒΒΤ: Can shoot Dilan 5 0 0 8 (brand name) (made by Mitsubishi Engineering Plastics), MW of raw materials = 6 8 0 0 0 PBT: Can shoot Di blue 5 0 2 0 S (brand name) (Mitsubishi Engineering Plastics (Made by the company), MW of raw materials = 113000 PETG: YSD 6 7 6 3 (made by Eastman Chemical Co., Ltd.), the alcohol content is about 3 1 mO. Non-crystalline PET substituted with alcohol, MW of raw material 2 7600 000-? 丁: 13 丨 (-2180 (Mitsubishi Chemical Polyester Corporation), acid content 7% is isophthalic acid MW of polymerized PET and raw materials = 6 5 8 0 0 PET: RT- 5 8 0 (manufactured by Nibide in Japan) MW of raw materials = 1 34 0 0 0 Carr Pogillard HCM-8V: (manufactured by Nisshinbo Corporation) ) Carbodiimide-based anti-hydrolytic decomposition agent (D) embossing pattern imparting The soft PVC sheet shown in FIG. 3 is also used to impart embossing pattern using an embossing shaper 10 in accordance with the conventional method. The outline of the device is firstly performed pre-heating of the sheet 2 by contact heating using a metal heating roller 1, and then by non-contact heating using an infrared heater 3, 48 3 12 / invention Book (Supplement) / 93-03 / 9213 7012 200416129 The sheet is heated to an arbitrary temperature, and the embossed pattern is transferred to the sheet by the embossing plate roller 4. All the sheets that have been given embossment are attached to the sheet The embossing is performed at a heating temperature of 180 ° C and an embossing plate temperature of 60 ° C. (E) Production of resin-coated metal plates Secondly, the general polyester used for gasification of ethylene-coated metal plates The adhesive is applied on the metal surface according to the thickness of the dried adhesive film in the range of 2 ~ 4 μη, and then the hot-air heating furnace and infrared heater are used to dry and heat the coated surface. The surface temperature of the galvanized steel sheet (thickness 0.45 mm) before lamination was set to 2 3 5 ° C. The laminated sheet was immediately coated with a laminator and then cooled with natural air to produce a resin-coated steel sheet. Items. Types of adhesives and coating conditions are the same in all Examples and Comparative Examples. (F). Evaluation of printed pattern design resin-coated metal plate The above evaluation was performed on the obtained printed pattern design resin-coated metal plate. Table 5 shows the evaluation results of Examples a 1 to a 7 and Comparative Examples a 1 to a 1 3. 49 3 12 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 Table 5 Durability (Damp and Heat Resistance (Properties) Processability Boiling water impregnability embossing imparts adaptability and if bonding f fuses fusing resistance transferability Example al 10000 Example a2 10000 Example a3 0000 Example a4 0000000 Example a5 000X — — Example a6 000X — — Example a7 00XX — Comparative Example al X 00000 Comparative Example a2 X 〇〇〇〇〇〇 Comparative Example a3 Δ 〇〇X — — Comparative Example a4 X 〇〇〇〇〇〇 Comparative Example a5 X 〇〇X — — Comparative Example a6 X 〇XX — — Comparative Example a7 Δ 〇〇〇〇〇 Comparative Example a8 Δ 〇〇〇〇X Comparative Example a9 X 〇〇〇〇〇X Comparative Example al ◦ X 〇〇X — — Comparative Example al 1 X 〇〇X — — Comparative Example al 2 X 〇〇X — — Comparative Example al3 X 〇XX — — Table 6 shows examples a 8, a 9, and comparative example a Evaluation results of 1 4 to a 1 9. Table 6 Durability (damp heat resistance) Processability Boiling water impregnation resistance Example a8 0000 Example a9 〇〇 Comparative example al4 Δ 〇 Comparative example al5 Δ 〇 Comparative example al 6 X 〇〇 Comparative example al 7 X 〇〇Comparative example al8 X 〇Comparative example al9 X 〇 Table 7 shows the evaluation results of Examples a 1 0 to a 1 5 and Comparative Examples a 2 0 to a 2 1. 3 12 / Invention Specification (Supplement) / 93-03 / 92137012 50 200416129 Table 7

| Durability (Moisture and Heat Resistance) Orthogonal Lifetime resistance to water-resistant immersion embossing imparts adaptability Example alO Example all 1OO〇 Adhesion resistance | ± And the fuse transferability — _ r \ Example al2 〇〇〇〇vJ 〇 Example al3 〇 ′ ^ _ 〇 Example al4 〇〇 ^ —2-_ _ r \ 〇〇 ~ ----———— 〇 Example al5 ~ δ ~~-~~乂-〇 Comparative Example a20 〇X ---- "〇- ~ 8- Comparative Example a21 〇 ^ 〇 ~ δ ~ r \ &quot; 〇 ~ From this result, the following matters are known. 〇X Example a 1 ~ a 7, and Shi ^, and comparative examples al ~ al3 (Table 5). Comparative example a 7 ~ a 1 3 is a single-layer thin film colored with a titanium oxide pigment laminated on a metal plate 9 ', but all are The durability results are inferior. Comparative Examples a 7 to a 9 have right ^

It is stated that the average weight of eight knives of the same weight that should be possessed by item B in the scope of patent application of item 3, but most of the blister-like expansions were found after the heat and humidity test. With the addition of titanium oxide and the addition of titanium oxide pigments, the thickness of the flakes penetrates through the water and rises in the thickness direction, which will promote the corrosion of the surface of the metal sheet, resulting in partial peeling between the sheet and the metal sheet. In Comparative Examples a 1 0 to a 1 3, most cracks were found in the grid ^ & ^ J in the tree moon layer, and the adhesion with gold also showed a decrease. Zhuang Low evil. Compared to Comparative Example a7, it is considered that the thin film layer maintains a strong strength of 轫% y. However, the blister phenomenon occurs only in the adhesive part, and the resin layer itself of Comparative Examples alO ~ al3 shows a ratio of / nm. Deterioration and cracking. Nai

Furthermore, the comparative examples a 7 to a 9 because the shaking, 丄, and R are tree moons, and the composition is within the scope of the B-layer composition of the present invention. When embossing was promoted, although no adhesion or fusion &amp; y B 戍 fly farming phenomenon occurred, but because of the crystallinity | 土 珣 巧 的 缘 3 12 / Invention Manual (Supplement) / 93-03 / 92137012 51 200416129 Therefore, embossing cannot be transferred. In contrast, in Comparative Examples a 1 0 to a 1 3, because the resin layer composed of a single layer is of low crystallinity, the heating roller phenomenon of the embossing and forming machine will occur, making it difficult to pass the sheet to the embossing plate roller. . Although Comparative Examples a 1 to a 6 were composed of two layers of A layer and B layer, in Comparative Examples a 3 to a 6, the weight average molecular weight of layer B was lower than the range of the present invention, and good moisture and heat resistance could not be obtained. Comparative example a1 is thinner than the thickness required for layer B of the present invention, and comparative example a2 has a relatively large amount of pigment added to layer B. These kinds of results show poor results. In contrast, the resin layer was set to two layers, and the examples of the invention a to a 7 where the addition of the pigment to the layer on the side of the surface to be bonded to the metal plate was restricted, all obtained good durability (humidity and heat resistance). In addition, the resin composition of layer B is in accordance with Examples a 1 to a 4 of the sixth item of the patent application scope of the present invention. By applying embossing to the sheet using an embossing shaper, a resin-coated metal having a good embossed appearance is obtained. board. Although Example a7 had good wet heat resistance, the layer B was set as a PET resin with a relatively slow crystallization rate, so it could not be crystallized during extrusion film formation, and it was not possible to provide adaptability to an embossing shaper. Examples a 8, a 9 and comparative examples a 1 4 to a 1 9 (Table 6) The composition of the B layer is a composition that does not have adaptability to the embossing forming machine. Although printing and coating are used to design the pattern, However, in Comparative Example a 15, although the resin composition was the same as layer B of Example a 6 but the weight average molecular weight after extrusion film formation by adding a titanium oxide pigment was lower than that of Example a 6. This result will result in cracking after the humidity and heat resistance test due to the deterioration of the resin layer itself. As for Comparative Example a 1 4 in which a carbodiimide-based anti-water decomposition agent was added, the addition amount was too small to obtain an effect. 52 312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 Comparative Example a 1 6 ~ a 1 9 is the case when the oxide pigment is added to the B layer beyond the scope of the present invention. It is the effect of the two-layer structure. Comparative examples a 1 7 and a 1 9 are those in which a carbodiimide-based antihydrolytic agent in the range shown in item 4 of the scope of patent application of the present invention is added, but when added to the same layer as the titanium oxide pigment, The effect of addition will be reduced, and the effect of sufficiently suppressing the decrease in molecular weight will not be obtained when the film is extruded. In contrast, when the pigment addition amount of layer B in Examples a 8 and a 9 is set within the scope of the present invention, and the case of using a carbodiimide-based anti-hydrolytic decomposition agent, the reduction in molecular weight during film formation can be suppressed. At the same time, good fishing heat resistance can be obtained. Example a 1 0 to a 1 5 and Comparative Examples a 2 0, a 2 1 (Table 7) Laminated sheet is a printing layer, a covering layer, or a case where a printing layer and a transparent resin layer are provided, because of any circumstances Both the A layer and the B layer are within the scope of the present invention, so there is no problem in damp heat resistance. (First invention) In order to explain the second invention more specifically and in detail, a second embodiment is shown, but the second invention is not limited to these examples. In addition, the physical property measurement specifications and test methods of the sheets and resin-coated metal plates shown in the examples and comparative examples are shown below σ. (1) Crystal melting peak temperature (T m) DSC-7 manufactured by Parkin Elma (company name) is used for sample 10 mg according to JIS-K 7 1 2 1 "Method for measuring plastic transfer temperature-calculation of melting temperature Method ", measured and determined at a heating rate of 10 ° C / min. When the temperature was raised once, 53 312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 :, and the crystal melting peak top temperature was set to Tm. At the same time, the heat of crystal melting ΔHm was obtained. In addition, the base resin layer produced by extrusion filming is measured before being fed into the embossing machine. (2) The crystallization peak temperature (Tc) is dsc_7 made by Parkin Elma (company name), and the sample lGmg is based on JIS_K7121 "Method for measuring plastic transfer temperature_method for obtaining melting temperature" ' Measure and find it. The crystallization peak top temperature at the time of increasing the temperature was set to Tc. At the same time, the heat-up crystallization heat ΔHe was obtained at the same time. The test system is the same as in the case of the above Tm measurement. (3) Adaptability by embossing: resistance to adhesion When embossing is imparted by the embossing forming machine 10 shown in FIG. 3, those who cannot be peeled off by sticking a sheet to a heating roller (metal roller υ) are recorded as " "X", the producer who cannot be stabilized due to adhesion is denoted as "△", and the non-adhesion is denoted as "0". (4) Embossing gives adaptability: the case where the resistance to fusing arises from pardon or shrinkage is denoted as Γ △ "(5) Embossing imparting adaptability: transferability When embossing is imparted by the embossing forming machine 10 shown in FIG. 3, when the sheet is heated by the heater 3, the sheet is melted as 4 ", and those who did not break were recorded as" 0 ". Although not broken, it was clearly observed that the embossing was visually imparted by the embossing forming machine 10 shown in Fig. 3, and beautifully transferred. The case where the embossed pattern is slightly shallower is referred to as "△", and the case where a shallower embossed pattern is formed only on the surface is disordered, and the sheet is referred to as "χ". Or without 312 / Invention Specification (Supplement) / 93_03 / 92〗 37〇12 54 200416129 (6) Heat resistance of embossing: high temperature and heat resistance The metal plate laminated with the embossed sheet 10 embossed by the embossing forming machine 10 shown in FIG. 3 was laminated in a hot air circulation oven of 105 ° C for 3 hours, and then visually observed and put into the oven. Those with almost no change in the front embossing shape are recorded as "0". Compared with this, the embossing reset is slightly occurred as "△", the embossing reset is obvious, or the embossing pattern completely disappears, and only the surface is disordered. It is denoted as "X". &Lt; A &gt; The resin composition of the patterned sheet (A + B, or a + c + b) for the resin-coated metal plate, which is used to make the embossed forming layer, is based on Eastman Chemical Company. "Yesda-PETG 6 7 6 3" (trade name), and the fatty acid cool lubricant "P0-8" of Daikkyo Chemical Co., Ltd. is used. 0.75 parts by weight (the amount of the resin component is set to 100), Mitsubishi Leiying (Company Name) acrylic lubricant "Metabrian L_1OO00" (trade name) 0.5 parts by weight of 'Tokyo Ink (Company Name) ρΕτ (the green base of the primer) (Master batch) mixture, formulated to a pigment concentration of 16 parts by weight, and then rolled into a film An embossed forming layer with a thickness of 120. Base resin layer (base resin layer, or c + base resin layer) Show the resin composition and thickness to make a laminated sheet (A + B, or A + B + Ch The film-forming sheet is extruded by a T-die casting method. When a layer consisting of a non-crystalline polyacetate resin is substantially applied together, a co-extrusion method is used to separate the Non-light Bebe is formed with a thickness of 10 μm from a layer made of non-crystalline polyester resin. Casting rolls are used to draw the bow | The 'by non-contact heating application In addition, the sheet of the related example b9 is introduced into the infrared rays after use' Heater inside the heating furnace 312 / Invention Specification (Supplement) / 93-03 / 92137012 55 200416129 Line 16 60 ° C x 30 seconds post-heating treatment. The base resin layer (ΔΗηι-ΔΗ (:) / ΔΗηι) of the post-heating treatment is 0.76. Table 8 The substrate wood fibrous resin layer (tree ...) DSC measurement value Istar PCTG can shoot Co-PET Tm ΔΗυι AHm-AHc / _6763_ 5445 5020S ”ττ — BK-218Q (° C) (J / g) ΔΗπι (-) B-1 0 100 δ ~ ^ == _ 223 ™ = ^ === s— 49.8 1.00 B-2 20_ 0 80 0 0 222 45.6 0.95 B-3 0 65 __0_ 0 223 39.8 0. 52 B-4 45 0 55 — 0 224 34.6 0.39 B-5 65 0 35 0 0 223 23.7 0.24 B-6 0 0 0 _〇_ 100 245 33. 3 0.17 B-7 0 0 0 100 〇 224 53 1 0. 96 B-8 0 35 0 0 Γ223_ 41.2 0. 64 Blue 5 0 2 0 S (trade name): homogeneous ρΒΤ manufactured by Mitsubishi Engineering Plastics (glass transition point; 45 ° C crystal melting peak temperature; 2 2 〇c) c〇-PET BK-2180 (trade name). pg #) • Copolymerized PET resin of methanediphosphonic acid manufactured by Mitsubishi Chemical Polyester Co., Ltd. (glass transition point: 7 6 t, crystal melting peak temperature: 24 6 ℃) Kerdella CP5 0 9 2 0 0 (product Mody,): Made by Homogeneous Resin Shell Company (glass transition point: 4 9 C, crystal melting point, + ^ Degree: 2 2 5 ° C) Istar 6 7 6 3 (trade name): the polyglycol part of the diethylene glycol diethyl glycolate is about 3 1% '1,4-cyclohexane &Amp; —Amorphous polyester resin substituted with methanol, manufactured by Eastman Chemical Co., Ltd. (glass break point: 81t, crystal melting peak temperature: not observed) diethyl formate The non-crystalline polyester resin that is replaced by the ethylene glycol part ^ Eastman Chemical Co., Ltd. (glass transition point: 8 8 ° C, crystalline PCTG 5 4 4 5 (trade name): will be polymerized About 70% for stupidity, according to the melting peak temperature of 1,4-cyclohexanedimethylformaldehyde: No 312 / Instruction of the Invention (Supplement) / 93-03 / 92137012 56 200416129 Table 9 Presence or absence of layer A or C layer B Level B crew layer thickness (μπι) 敝 Example bl with or without B-1 40 beneficial example b2 with or without B-2 40 without example b3 with or without B-2 40 without example M with or without B-2 20 no Example b5 With or without B-3 40 Without Example b6 With or without B- 2 100 Without Example b7 With or without B-7 40 Without Example b8 With or without B- 8 40 Without Example b9 With or without B-5 40 Yes Comparative example bl no B-1 40 no comparative b2 no no B-3 40 no comparative example b3 no B-4 40 no comparative b4 yes or no. B-5 40 no comparative example b5 no B-6 40 no comparative example b6 Presence or absence — Comparative example b7 Presence or absence of B-2 15 None Comparative example b8 Presence or absence of B-2 15 None &lt; B &gt; The embossed pattern imparted to the soft vinyl chloride-based sheet is also used in the continuous method in general use The embossing and shaping machine 10 (refer to FIG. 3) applies the embossing pattern. The heating roller was set at 100 ° C. In related example b: 1 to b 9 and comparative examples b 1 to b8, the sheet before being contacted with the embossing pattern roller was heated to 16 5 ° C by a heater. In addition, a fine mesh Ikun with an embossing plate temperature of 70 ° C and an average surface roughness Ra = 10 μm. In the related examples b 1 0 to b 1 3 and the comparative examples b 9 to b 1 4, the heating roller (metal roller 1) was set to 100 ° C., and the sheet temperature was changed by heating with a force heater. In this case, the temperature of the embossing plate roll 4 and the pattern of the embossing plate are also the same, which are the same in Examples bl to b9 and Comparative Examples bl to b8. In addition, the type and thickness of the base resin layer are the same when the base tree layer is used. &lt; C &gt; Production of resin-coated metal plates Secondly, polyester resins commonly used for vinyl chloride-coated metal plates are used. 57 312 / Invention Manual (Supplement) / 93-03 / 92137012 200416129 Mixture, then dried After the adhesive film thickness is 2 ~ 4 μη〗, apply it on the metal surface (adhesive layer (E)), and then use a hot air heating furnace and infrared heater to dry and heat the coated surface. Zinc steel plate (metal plate (F): thickness 0.45 mm) The surface temperature is set to 2 3 5 ° (:, immediately use a roll laminator to cover the polyester resin sheet, and then use water cooling to make a resin-coated metal plate &Lt; D &gt; Evaluation of the pattern design sheet (A + B) for resin-coated metal plates, and evaluation of each of the above items. Relevant Example b:! ~ B 9, Comparative Example b 1 ~ b 8 The results are summarized in Table 10. In Table 10, those who have adhered to the heating roller of the embossing forming machine have not been evaluated as follows. In addition, when heating with a heater, obvious wrinkles occur on the sheet. , Shrinkage, melt fracture, etc. Evaluation of embossing heat resistance after lamination was not performed. Table 10 1 Embossing applicator adaptability embossing for heat resistance 1 and inch adhesion fusing resistance ten pattern transfer property Example bl 〇〇 Example b2 〇 Example b3 Example 000 b4 Example ΔΔ Example b5 Example 000 b6 Example b7 000 Example b8 Example b9 Example b9 〇〇 Comparative Example bl 〇〇X — Comparative Example b2 〇〇X — Comparative Example b3 Δ X — — Comparative Example b4 X — — — Comparative Example b5 X — — — Comparative Example b6 Δ X — — Comparative Example b7 〇X — — Comparative Example b8 〇X — — 312 / Explanation of the Invention (Supplement) / 93-03 / 92137012 58 200416129 Comparative Example b 3, b 4, and b 5 series base resin layers "(△ Η η-△ △ H "m" is lower than the scope of the patent application of the present invention, and the laminated sheet phenomenon occurs on the heating roller of the embossing sheet. Therefore, the sheet cannot be given an embossing pattern. Among these, the comparative example with a larger value b3 is in the slightest condition and can be found on the heating roller However, the elasticity of the sheet is reduced due to the heating of the heater, which will cause the sheet to stick to the roller in succession, which will cause the sheet to crack. Comparative Example b 6 is a substrate resin layer that is not used. The case where the forming layer passes through the embossing forming machine, but with the addition of more agents, the phenomenon of sticking to the heating roller is reduced. However, the reduction in elasticity when heating the hot sheet will be obvious, and eventually the phenomenon of fusion cracking will occur. . Comparative examples b 1 and b 2 were obtained when only a substrate tree suitable for the scope of the present invention was passed through an embossing shaper. Although the melting and rupture phenomenon did not occur due to the heating by sticking to the heating roller heater, it was caused by crystallization. Sexual bias cannot form an embossed shape of emphasis. Although Comparative Example b7 has the properties suitable for the range of the substrate resin layer of the present invention, the thickness is thinner than the preferred range. Although the situation of sticking to the heating roller is prevented, the strength of the sheet when the heater is heated is sufficient. As a result, a melt fracture phenomenon occurs. By co-extruding a layer made of a substantially non-polyester resin, the thickness of the hanging sheet was thicker than that of Comparative Example b8 of the Comparative Example. The same result was obtained. It was learned that in order to prevent cracking caused by the heating of the heater, The crystalline substrate resin layer of the present invention needs to have a specific thickness or more. 312 / Invention Specification (Supplement) / 93-03 / 92137012

He) / Shape machine's affection for thin bonding 丨 Mo's slider with melted fat-breaking layer or Yinan, 丨 Ji Jinghe is suspected of not crystallizing b7 heat required 59 200416129 Example b9 is used as the substrate The composition of the resin layer is the same as that of Comparative Example b4, and a heat treatment is performed after extrusion. With the implementation of the heat treatment, the substrate resin layer will be crystallized without sticking to the heating roller or the heater. The cracking phenomenon of the sheet caused by heating will obtain a good embossing transfer property. Example b 9 does not meet the 15th or 16th of the scope of the patent application, but meets the 14th and 17th of the scope of the patent application, even if the crystallinity of the substrate resin layer is uneven during film formation In the low state, if heat treatment is performed before the embossing is applied, the adaptability for providing the resin layer provided with the base material of the present invention can be formed. Examples b 1 to b 8 are when the composition and thickness of the substrate resin layer are in the preferred range of the present invention, and have the preferred crystallinity of the present invention at the time of extrusion film formation, and no crystallization treatment is required in the subsequent steps. Good embossing imparts adaptability and good embossing heat resistance. Table 11 Types of layer B Layer thickness (μηι) Sheet temperature before compression ΓΟ Example b10 B-2 50 165 Example bll B-2 50 175 Example b12 B-2 50 185 Example b13 B-2 50 195 Comparison Example b9 B-2 50 145 Comparative example blO B-2 50 155 Comparative example bll B-2 50 210 Comparative example bl2 None — 145 Comparative example bl3 None — 155 Comparative example bl4 None — 165 60 3 12 / Invention specification (Supplements) ) / 93-03 / 92 丨 37012 200416129 Table 12 Examples of embossing forming machine adaptability, property, adhesion, fusing resistance, pattern transfer, embossing, heat resistance Example bl. .000 Example bll 〇〇〇〇 Example bl2 〇〇〇〇 Example bl3 〇Δ 〇〇 Comparative Example b9 〇〇〇X Comparative Example blO 〇〇〇Δ Comparative Example bl 1 〇X — — Comparative Example bl2 〇〇〇X Comparative Example bl3 〇Δ Δ Δ Comparative Example bl4 〇X — — Examples b 1 0 to b 1 3 and Comparative Examples b 9 to b 1 4 shown in Table 1 1 and Table 12 above, related to the cases with and without the substrate resin layer, change the pass pressure. The temperature of the sheet before the pattern roller, which has the substrate resin layer and the lowest sheet temperature before embossing Comparative Example b9, insufficient heat resistance embossing will too. In Comparative Example b 1 0 in which the sheet temperature was increased, the embossing heat resistance was slightly improved, but it was hardly sufficient. On the other hand, in Examples b 1 0 to b 1 3 in which the sheet temperature is further increased, sufficient heat resistance for embossing can be obtained. Among them, in Example b 1 3, in which the sheet temperature approaches the upper limit temperature specified in Item 22 of the patent application range (T m b-20) ° C, it will be found that the sheet width shrinks slightly as the heater heats up. In Comparative Example b 11, which has a base resin layer and the sheet temperature is higher than that specified in Item 22 of the patent application scope, the sheet will melt and crack. When there are no three layers of comparative examples b 1 2 to b 1 4, the embossing forming layer will also contain a large amount of lubricant because it is formed by the calendering method, so it is completely non-adhesive to 100 ° C The problem of the heating roller, but it is raised as the heater heats up. 61 3 12 / Invention Manual (Supplement) / 93-03 / 92 丨 37012 200416129 When the temperature of the sheet is raised, the sheet will wrinkle, melt and crack. The embossing cannot be imparted at a sheet temperature required to obtain embossed heat resistance obtained from 1 to b 1 3. (Industrial Applicability) The resin-coated metal plate and the pattern-designed sheet for resin-coated metal plate of the present invention are made of two polyester resin layers, and the amount of pigment added to the resin layer on the side of the bonding surface with the metal plate. It has a specific value or less, and by setting the molecular weight to a specific range, a resin-coated metal plate with good durability (moisture and heat resistance) can be formed. When an embossed pattern design is given to a sheet, melt cracking or wrinkling is reduced Phenomenon, stable production can be achieved at low cost. In addition, by specifying the composition of the A layer and the B layer, it is possible to obtain a resin-coated metal plate having a good embossing appearance by using an embossing shaper used in conventional soft PVC sheets to impart embossing. [Brief description of the drawings] Figs. 1 (a) to (d) are schematic views of a resin-coated metal plate having a basic structure of the first invention. 2 (a) to (1d) are schematic views of a laminated resin sheet having a basic structure of the second invention. Fig. 3 is a schematic view of an embossing shaping device for a general soft PVC sheet. (Explanation of component symbols) 1 Metal newspaper 2 Sheet 3 Orifice heater 4 Embossing plate roll 62 3 12 / Invention manual (Supplement) / 93-03 / 92137012 200416129 5 Press roll 10 Embossing shaper A Resin layer B resin layer C printing layer c-1 pattern printing layer c-2 whole surface printing layer D transparent coating layer E transparent resin coating layer F adhesive layer G base metal plate A embossed shape formed by the rolling film method Layer B The base resin layer C formed by the extrusion film-forming method. Co-extrusion method, which gives layer B the non-crystalline layer D. The metal non-adhesive coating layer E The thermosetting adhesive layer F The metal Board 63 312 / Invention Specification (Supplement) / 93-03 / 92137012

Claims (1)

200416129 Scope of patent application: 1. A resin-coated metal plate that uses at least two layers of a polyester-based resin as the main component of an unstretched layer (A layer and B layer) as the B layer side The structure is used as an adhesive surface and laminated on a metal plate through an adhesive; It is characterized in that the total thickness of the above-mentioned laminated sheet is 65 μm to 300 μm, and it is added to the A layer for coloring and concealment The above-mentioned layer A has a thickness of 50 μm to 250 μm; the above-mentioned layer B has a thickness of 15 μm to 80 μm, and the pigment component added to the above B layer is 100 parts by weight relative to the resin component, It is less than 10 parts by weight. 2. For the resin-coated metal sheet as described in the first item of the patent application scope, wherein the B layer is substantially free of pigment components. 3. For example, the resin-coated metal plate of the first patent application scope, wherein the above-mentioned layer B after film formation is converted to a weight-average molecular weight of styrene by gel permeation chromatography (GPC) of 7 5 0 0 0 to 1 4 0 0 0 0 range. 4. For the resin-coated metal plate of the first scope of the application, when the resin component of the B layer is set to 100 parts by weight, 0.1 part by weight or more and 5 parts by weight are added to the B layer. The following carbodiimide compounds. 5. The resin-coated metal sheet according to item 1 of the scope of patent application, wherein said layer B contains a polybutylene terephthalate resin having a resin content of more than 20% by weight. 6. The resin-coated metal sheet according to item 1 of the patent application scope, wherein the above-mentioned 64-312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 said the B layer system contains poly-p-phenylene with a resin content exceeding 55% by weight. In the dibutyl dicarboxylic acid dicarboxylic acid resin, the A layer is mainly composed of a non-crystalline or low-crystalline polyS resin. 7. The resin-coated metal sheet according to item 6 of the patent application scope, wherein the substantially non-crystalline or low-crystalline polyester resin of the above-mentioned layer A is made of terephthalic acid or dimethyl terephthalate. It is the main body of the acid component, and 20 to 80 mol.% Of the alcohol component is 1,4-cyclohexanediethanol, and the remaining 80 to 20 mol.% Of the alcohol component is ethylene glycol. 8. The resin-coated metal sheet according to item 7 of the scope of the patent application, wherein a printing layer (layer C) is provided on the back surface of the side in which the layer A is laminated with the layer B, and a thickness is further provided on the surface. A transparent coating layer (layer D) in a range of 2 μm to 20 μπΐ. 9. The resin-coated metal sheet according to item 6 of the scope of patent application, wherein the integrated sheet (A layer + B layer) or (D layer + C layer + A layer + Layer B), after heating to a temperature above the glass transition temperature (T ga) of the layer A and below the melting point (T mb) of the layer B, embossing is applied to the side surface of the layer A by using an embossing report, and then Then, the side of the B layer is used as an adhesive surface through an adhesive and laminated on a metal plate. 10. The resin-coated metal sheet according to item 1 of the scope of the patent application, wherein the C layer is provided on the back surface of the side where the A layer and the B layer are laminated, and a substantially non- A crystalline or low-crystalline polyester resin is a main body, and a transparent resin layer (E layer) having a thickness in a range of 25 μm to 100 μm without pigment is added. 1 1. The resin-coated metal sheet according to item 10 of the scope of patent application, wherein 65 312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 The substantially non-crystalline or low-crystalline polyester of the above-mentioned E layer Resin, based on terephthalic acid, or dimethyl terephthalate as the main acid component, and 20 to 80 mol of the alcohol component.% 1,4-cyclohexanedimethanol, the remaining 80 to 20 mol of the alcohol component. % Is ethylene glycol. 12. The resin-coated metal sheet according to item 10 of the scope of patent application, wherein the integrated sheet (E layer + C layer + A layer + B layer) is laminated in the crystallization state of the above B layer to the above After the glass transition temperature (Tga and Tge) of the layer A and the above E is higher than the temperature above the melting point (Tmb) of the layer B, the embossing plate roller is used to After embossing, the layer B is used as an adhesive surface through an adhesive, and then laminated on a metal plate. 1 3. The resin-coated metal sheet according to item 1 of the scope of patent application, wherein the A layer and the B layer are integrated by a co-extrusion film forming method. 1 4. A pattern design sheet for a resin-coated metal plate, which is a polyester-based resin having at least two layers of an embossing forming layer and a base resin layer; wherein the embossing layer is performed by a calendering method The film is made of polyester resins that are colored with pigments to various shades and are substantially non-crystalline. The base resin layer is non-stretched by extrusion and has a thickness of 20 μm ~ 3 0 0 The substrate resin layer in the range of μm is crystallized to such an extent that it does not cause adhesion even when it contacts a metal roller heated to a temperature below the melting point Tmb. 15. The pattern design sheet for a resin-coated metal plate according to item 14 of the patent application scope, wherein the base resin layer contains 60% by weight or more of polybutylene terephthalate (PBT) resin . 66 312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129 1 6. For example, the pattern design sheet for resin-coated metal plate in item 14 of the patent application scope, wherein the base resin layer contains 60% by weight The above polypropyl terephthalate (PTT) resin. 1 7. The pattern design sheet for a resin-coated metal sheet according to item 14 of the scope of patent application, wherein in the sheet before embossing, the substrate resin layer is heated once with a differential scanning calorimeter (DSC) The heat of crystallization at this time is △ Hc (J / g), and the heat of crystallization melting is △ Hm (J / g), the following formula will be established: 0.5 &lt; (Δ Hm- Δ He) / Δ Hm relationship. 18. The pattern design sheet for a resin-coated metal plate according to item 14 of the scope of patent application, wherein the resin component of the embossing forming layer is terephthalic acid or dimethyl terephthalate It is the main body of the acid component, and 20 to 80 mol of the alcohol component,% is 1,4-cyclohexanediethanol, and the remaining 80 to 20 mol ·% of the alcohol component is ethylene glycol. 19. The pattern design sheet for a resin-coated metal plate according to item 14 of the scope of patent application, wherein the surface of the substrate resin layer laminated with the embossed forming layer is set on the surface on the side where the layer is laminated with the embossing forming layer by a coextrusion method. A layer composed of a substantially amorphous polyester resin. 20. The pattern design sheet for a resin-coated metal sheet according to item 14 of the scope of the patent application, wherein the side surface of the embossing forming layer of the pattern design sheet for the resin-coated metal sheet of the polyester resin is laminated On the other hand, a non-adhesive coating layer with a thickness of 1 to 10 μm is provided to the heated metal. 2 1. If the pattern for resin-coated metal sheet No. 14 in the scope of the application for patent is 67 312 / Invention Specification (Supplement) / 93-03 / 92137012 200416129, the above-mentioned embossing forming layer and the above-mentioned base material are counted. The resin layer is laminated and integrated by thermal fusion. 2 2. A kind of resin-coated metal plate is obtained by heating the pattern design sheet of item No. 14 of the patent application range to more than 160 ° C (the melting point of the above-mentioned substrate resin layer-2 0) ° C. By designing a sheet for a resin-coated metal plate with an embossing pattern on the side of the embossing forming layer by passing between the embossing plate roller and the pressing roll engraved with the embossing pattern, the resin-coated metal plate The side surface of the substrate resin layer of the pattern design sheet is used as an adhesive surface, and the metal plate is laminated with a thermosetting adhesive. 2 3. — A method for manufacturing a resin-coated metal plate, the pattern design sheet of item 14 of the patent application range is heated to more than 160 ° C (the melting point of the above-mentioned base resin layer-2 0) ° C Hereinafter, a pattern-designed sheet for a resin-coated metal plate is provided with an embossing pattern on the embossing forming layer side between the embossing plate roller and the pressing roll engraved with the embossing pattern, and the resin is coated. The side surface of the base resin layer of the pattern design sheet of the metal plate is used as an adhesive surface. After the metal plate coated with the thermosetting adhesive is imprinted and laminated, it is immediately cooled. 2 4. —A kind of building interior material is a resin-coated metal plate with the scope of patent applications Nos. 1 and 22. 68 312 / Invention Specification (Supplement) / 93-03 / 92137012