TW200524731A - Emboss-designed sheet and metal plate covered with emboss-designed sheet - Google Patents

Abstract

A laminated sheet excellent in the suitability for embossing, which comprises a non-oriented resin layer (A layer)(1) comprising a crystalline polyester based resin as a primary component and having a melting point in the range of 210 to 240 DEG C and, laminated on one side thereof, a non-oriented resin layer (B layer)(2) comprising a substantially amorphous polyester as a primary component, has a total thickness of 65 to 300 mum and a tensile strength at 180 DEG C of 5 MPa or higher; an emboss-designed sheet; and a metal plate covered with the emboss-designed sheet.

Description

200524731

说明 Description of the invention [Technical field to which the invention belongs] The present invention relates to the superiority of coating materials such as exterior appliances for household appliances such as AV equipment, air conditioner housings, plywood furniture, and steel furniture 'building interiors. The resin-coated metal plate covered with the embossed decorative film is added to the laminated film with the appropriate embossing and the embossed decorative film to which the embossing is applied. [Prior technology] The coating materials used in the exterior of home appliances such as AV machines, air conditioners, plywood furniture, steel furniture, and building interiors are soft chlorine suitable for embossing. Vinyl resin film (hereinafter referred to as soft PVC film). As for the characteristics of the flexible PVC membrane, the following points can be cited: 1) Since it is superior to the addition of suitable embossing, a decorative material with rich decoration can be obtained. 2. The balance between workability and surface damage as a general violation element is better. 3. Because it is excellent in compatibility with various additives and has been reviewed for many years to improve the physical properties of the additives, weather resistance, especially light stability is easy to improve. Although the flexible PVC membrane has such excellent characteristics, in recent years -4- 200524731 (2) problems caused by heavy metal compounds caused by stabilizers of vinyl chloride resins, V0C problems caused by plasticizers or stabilizers, and endocrine disruption effects The vinyl chloride-based resins, such as the problem of chlorine gas containing hydrogen chloride gas and the like occurring during combustion, are limited to use. For this reason, users of these products strongly demand not to use vinyl chloride resins. Then, instead of the soft vinyl chloride resin, a polyolefin resin such as polypropylene is used as a main body, and the physical properties of the soft vinyl chloride resin close to the soft component such as styrene or olefin copolymerization system are used. Polyolefin resin film such as polypropylene has a narrower temperature range than embossed PVC film. Although it must be properly temperature-controlled, it has so-called soft PVC film that can almost adapt to the past. Advantages of an additional embossing machine that continuously adds embossing to the sheet. However, with regard to workability and damage resistance, polyolefin resins such as polypropylene are resins which have a problem in terms of workability after lamination on a steel sheet, which is a problem. In order to satisfy processability, increasing the blending ratio of the soft component has adverse effects such as whitening of the processed portion and reduction of surface damage, and there is a problem of designing which one has to be sacrificed. In addition, polyolefin resins are basically resins with poor adhesion. It is necessary to make special efforts to ensure the adhesion of the interface with the laminate or the adhesion of the metal plate over a long period of time. In order to solve these problems, those who are suitable for roll-pressing film, such as lubricants or processing aids, such as the non-crystalline polyester resin represented by PETG, are used. And surface damage-5-200524731 (3) A film made of polyester resin is used as a resin-coated metal plate with embossed decoration. (For example, refer to Japanese Patent Application Laid-Open No. 20-02-29000.) [Summary of the Invention] A film made of a polyolefin resin is used in the same manner as a conventional soft P VC film or a polyolefin film. When embossing is added to the sheet by adding an embossing machine, although embossing can be added, it has a problem with heat resistance of the embossing. When embossed with heat resistance, embossed decorative membrane, or embossed decorative membrane-coated metal sheet is exposed to high heat when it is in use, it will appear embossed or restored to its original size. If it is small, the heat resistance of embossing is good. That is, the additional embossing is an operation in which the warped viscoelastic body is subjected to a warpage process, and the warpage can be frozen by cooling. The warpage that is frozen is due to the existence of residual stress, so when it is reheated to a temperature near the additional warpage, it causes a recovery phenomenon of warpage. Therefore, it is necessary to make a high additional warping temperature when making high embossing heat resistance. However, in order to improve the heat resistance of the embossing, an additional temperature (determining the temperature of the diaphragm and the temperature at which the embossing plate is rolled) to increase the warpage and the reduction in the melt tension of the diaphragm itself are produced. As a result of wide shrinkage, wrinkling, and film breakage, embossed heat resistance comparable to conventional soft PVC film cannot be added. -6-200524731 (4) As a result, even when the environment is used as a surface material of a table, etc., when hot water overflows at high temperature, or when the housing of a household appliance with large internal heat generation is used If the embossing is insufficient in heat resistance, the embossing may be partially light, or the appearance may be lost. In addition, 'for use as a resin-coated metal plate, there is also a problem that the embossing becomes shallower or disappears by the heat of the metal plate when the adhesive is soldered to the metal' board lamination ', and it cannot be widely used. For resin coated metal sheet use. On the other hand, as a method of adding an embossing pattern to a sheet made of a polyester-based resin, there is a method of forming a polyester-based resin film by a press-forming method. At this time, instead of making a casting roll into a normal mirror roll, an embossed plate roll is performed in advance, and embossing is performed on the resin in a molten state flowing out of the T die. In this method, it is easy to obtain high embossing heat resistance 'regardless of the crystallinity of the polyester-based resin, and it has the advantage of a so-called transfer embossing pattern. However, deep embossing or embossing of a complicated pattern is caused by problems such as mold releasability or air inclusion, and so cannot be added. The problem of restricting the embossing pattern arises. In addition, "gluing roll is larger than the diameter of embossing roll of a general additional embossing machine". Having the gluing roll corresponding to the number of patterns becomes a problem from the point of equipment cost or the exchange of man-hours. As another additional embossing method, a molten resin is extruded on a steel sheet, and a method of embossing a pattern roll is used to press the resin before the resin is cooled, and the method of transferring the pattern is to 'reheat a metal plate covered with a resin film and use Embossed pattern roll-7- 200524731 (5) Method of transfer by rolling. Even in these methods, embossing is transferred to the resin in the molten state. Therefore, regardless of the difference between crystalline polyester and non-crystalline polyester, embossing can be added. In the case where the pattern is transferred by the roller milk, the pattern is similarly limited. In addition, there is a danger that the embossed plate may be damaged due to the contact between the embossed plate and the end of the metal plate. A plurality of stocks are prepared for rolling, which becomes a problem that burdens the cost of equipment. In order to solve the above problems, in the first aspect of the present invention, a crystalline polyester resin is used as the main body, and the melting point is 2 1 0 ° C ~ 2 4 0 ° (: Oriented resin layer (In the present invention, this layer is shown as "A layer".), And a non-orientated resin layer composed of an amorphous polyester resin as a main body (in the present invention, This layer is displayed as "B layer".) Among the laminated film composed of at least two layers, the total thickness of the film is in the range of 65 μm to 300 μm, which is 1 800. Laminated diaphragms with a tensile breaking strength of 5 MPa or higher are superior to those with suitable embossing. In the same state, they are composed of a crystalline polyester resin as the main component and have a melting point of 2 1 A printing layer is added to the surface of the non-oriented resin layer (layer a) in the range of 0 ° C to 2 40 ° C (in the present invention, the printing layer is displayed as "c layer"), and on top of it Laminated is a transparent resin layer with a non-oriented polyester resin as the main body (in #weiming, this layer It is displayed as "D layer".) Among the laminated films consisting of at least 3 layers of winter 200524731 (6), the total thickness of the film is in the range of 65 μm to 3 00 μm, at 180 ° C. It has a tensile breaking strength of 5 MPa or more, which is characterized by a laminated film excellent in addition to suitable embossing. In a third aspect, 'the polyester resin having crystallinity is used as a main body'. Resin-free resin layer (Layer A) with a melting point in the range of 2 0 ° C to 2 40 ° C, and Z-orientated resin layer (substantially using an amorphous polyester-based resin as the main body ( In the present invention, this layer is displayed as an "E layer".) A printing layer (c layer) is added to the surface of the E layer side, and an amorphous polyester system is substantially laminated thereon. The total thickness of the laminated film composed of at least 4 layers of the non-oriented transparent resin layer (layer D) made of resin as the main body is 65 μm to 3 00 μm, in the range of 180 ° The tensile breaking strength of C is 5 MP a or more, which is characterized by a laminated film superior to the addition of suitable embossing. The above-mentioned laminated film (that is, the so-called laminated film composed of at least two layers in which layer B is layered on layer a (hereinafter referred to as "A + B") is shown.) Layers are sequentially laminated on layer A. A layered diaphragm composed of at least 3 layers of layer c and layer D (hereinafter referred to as "a + C + D") is used.), Or layer e, layer C, and layer A are sequentially stacked on layer A. A laminated film composed of at least 4 layers of D layer (hereinafter referred to as "A + e + C + D") is displayed. )), After heating to the melting point of layer A-[0] below it, rolling with an embossing plate can make an embossed decorative membrane with an additional embossing pattern on the side surface of layer B or the surface of layer D. The above-mentioned embossed decorative membrane can be 160. (: The above-mentioned laminated film-9-200524731 (7) [A + B ", A + C + D", and "A + E + C + D"), heat to the melting point of the A layer (Tm )-1 〇. (: After the following temperature, embossing is performed by embossing plate rolling on the layer B side surface or the layer D side surface. The embossed decorative film has the surface on the layer A side as the bonding surface. The embossed decorative sheet-coated metal sheet can be made by laminating it on a metal sheet with a thermosetting adhesive. Furthermore, the film of the present invention has a thickness ranging from 65 μm to 300 μm. It is more accurate to describe "film", but even here, it is convenient to use the film even if it is generally referred to as the thickness range of the film. In the present invention, the expression "made as the main body" contains more resin The content of 50% by weight is more than that. The so-called "no-orientation performance" is an orientation processor who does not intend to perform stretching operations, etc., and does not have the so-called "existence" when it is extruded to form a film. In addition, the meaning of the orientation, etc. In addition, as "substantially amorphous polyester resin", other than polyester resins that do not show a clear crystal melting peak at elevated temperature, "is crystallized but crystallized" The speed is slow. In the heating process until the embossing pattern is transferred by the film-forming process and an additional embossing machine, it also means that the polyester resin cannot be obtained in a highly crystalline state. In addition, a patent application is pending In the fifth item of the scope, the surface of the printed layer (C layer) with the D layer and the A layer added; or the integrated layer of the printed layer (C layer) with the d layer and the E layer added The description is that the printing layer (C layer) does not necessarily limit the comprehensive application. In the case of partial additional printing-10-200524731 layer, it is based on D layer and A layer,

It is simply called resin A). The polyester resin in layer A is called polyester resin A (or I. In addition, the polyester resin forming layer B is called polyester resin B (or simply resin b). Similarly, The polyester resin forming the 0 layer and the E layer is referred to as polyester resin D (or resin D alone) and polyester resin E (or resin e alone). [Embodiment] Hereinafter, it is used An embodiment of the present invention will be described with reference to the drawings. (Resin forming layer A) Layer A 1 is used as an energy supply for the anti-adhesion layer of the heated metal roll when the laminated film is passed through an additional embossing machine. In addition, it is designed to add the functions of preventing wide shrinkage, wrinkling, melting and breaking of the laminated film heated to the same temperature as the conventional soft PVC. Therefore, in the third aspect of the present invention, the third aspect The specified tensile breaking strength at 180 ° C is mainly added based on the composition and thickness of layer A. Layer 1 is based on a polyester resin with crystallinity, and contains The polyester resin is more than 50% by weight of the total resin component, and preferably contains 55% by weight or more. It is more preferably 70% by weight or more. The melting point of the resin A is in the range of 2 0 ° C to 24 0 ° C. In this way, the conventional soft vinyl chloride film can be used as it is laminated on a metal plate. -11-200524731 Ο). When the melting point of resin A is lower than this, when laminated on a metal plate, there is a danger of adhesion to heated metal rolls, or it is difficult to obtain a good tensile breaking strength as a laminated film. As a result, there is a possibility that melt fracture may occur. When the melting point of the resin A is higher than this, it is necessary to produce a laminate at a higher surface temperature of the metal plate than the conventional laminate temperature, and the heating conditions of the conventional equipment are insufficient. In addition, problems such as thermal discoloration and thermal discoloration of the back coating material occur, or because the cooling relativity of the end portions becomes significant, the surface temperature of the metal plate tends to become non-uniform in a wide direction, and thereby, the bonding strength of the end portions is liable to occur Insufficient issues. As the polyester resin forming the A layer 1, a polyester resin having various crystallinity can be used. In particular, the polybutylene terephthalate (PBT) resin or the polytrimethylene terephthalate (PTT) resin has a rapid crystallization rate. By appropriately setting the roll temperature of the rubber coating during extrusion, The point at which a film is obtained by extrusion film formation is preferable because comparative high crystallinity can be added to the A layer 1. Since the P B T resin is relatively low in glass transition temperature, it is easy to obtain a crystalline film during extrusion. In addition, the so-called terePhthalic acid or dimethyl ter ephal ate, which is a dicarboxylic acid (dicarboxyHc acid), is used as the alcohol component, and 4-butanol. The melting point of each single-component BT resin is about 2 2 5 ° C. -12- 200524731 (10) In addition to homogeneous PB T resins, PBT resins having a combination of isophthalic acid and a part of acid components may be used. In addition, will the 1st floor in the A layer be? 31 [Resin is used as the main body, and even non-crystalline resin may be used. In this case, in order to obtain A layer 1 having crystallinity that is not adhered to the heated metal rolls or the like during extrusion, 55% or more of the total resin content of layer A] is made into PB T resin. good. Examples of the non-junction resin added to the A layer 1 include a crystalline resin used as a main body of the B layer 2 described later. In the present invention, as an unsuitable resin, it is a resin having a polyethylene terephthalate (PE T) system. This is because the crystallization rate is slow, and it cannot be stretched or broken. In the case of crystallization in addition to the breaking strength, the melting point is high, so sufficient adhesion cannot be obtained when laminated with gold 6. In the state of high crystallinity of the layer A1, the layer A1 system did not show a temperature and metal properties reaching a temperature close to its melting point by passing through the adder. In addition, as the overall structure of the laminated membrane, it is less likely to cause wide shrinkage, wrinkle, melt fracture, etc. by making it with a breaking strength of 180 ° C or higher at 5 MPa. Can be transferred to embossed patterns with embossed heat resistance. In addition, 1800c is a temperature at which the diaphragm is heated, or a temperature slightly higher than that when a soft diaphragm is pressed. Copolymerization of formic acid makes the weight of the film formation crystalline non-acrylic acid. , The other is a plate embossed and bonded with pleats, excellent P VC slightly high 200524731 (11) in the A layer! Corresponding to the need for additional decorative properties, securing the visually concealing effect of the base metal plate 6, and improving the color development of the printed layer 3, even pigments may be added. In addition, in the case of adding a pigment to the structure shown in Fig. 1, it is possible to add a pigment to the B layer 2 and therefore, it is not necessary to add a pigment to the A layer. When pigment is added to the structure shown in Fig. 2, the D layer 4 added to the print layer 3 needs to have transparency, and a pigment must be added to the a layer i. In the case of adding pigment in the structure shown in FIG. 3, although the printing layer 3 is provided, because the E layer 5 is arranged under the printing layer 3, either one of the pigment system A layer 1 or E layer 5 may be added, or Add on both sides. In this case, the pigment used may be a general one for resin coloring, and it is preferable to add a general amount to the added amount. As one example, the coloring on the white line is based on the use of a titanium oxide pigment with a high concealing effect as a substrate, and the color is adjusted with a colored inorganic or organic pigment. The visual concealment effect of the base metal plate 6 differs in importance depending on the application. The resin-coated metal sheet used for interior building materials is measured based on JIS K5 4 00 7.2 "General test methods for coatings and concealment rate". The concealment rate is preferably 0.98 or more. When the concealment rate is lower than this, the color of the base material that becomes the substrate such as the metal plate 6 is the color reflected in the laminated film, and when these colors change, because the color viewed from the surface of the laminated film-14 -200524731 (12) The change is also seen so it is not so good. However, for this reason, it is possible to change the color, especially in non-problematic applications, even if the concealment ratio is not more than 0.95. The layer A 1 is within a range that does not impair its properties, or in order to further improve physical properties other than the object of the present invention, it is possible to add an appropriate amount of each additive. Examples of additives include those commonly used in actinides. Various oxidation inhibitors, heat stabilizers, and UV absorbers other than phenols, light stabilizers, nucleating agents, impact modifiers, processing aids, and metals A wide range of resin materials such as activators, residual coincident catalyst inactivators, nucleating agents, antibacterial and antifungal agents, @ 电 防 剂, lubricants, flame retardants, fillers, etc., carbodiimide It is commercially available as a terminal carboxylic acid (carboxy 1 icacid) blocking agent other than (carbOdiimide) -based or epoxy (eρOXy) systems, or as a polyester resin such as a hydrolyzation inhibitor. In addition, since the non-adhesiveness to the heated metal of layer A i is further improved, it is possible to add a surface slip additive, a release agent, and the like. When the print layer 3 is provided on the surface of the A layer 1, it is necessary to use the print layer 3 in a range where the printability is not reduced. Only the resin composition and crystallinity of layer A 1 are not dependent on the maintenance of gluten melt tension when heated by an additional embossing machine, even if a processing aid having an effect of increasing melt tension is added. The thickness range of the A layer 1 is necessary to maintain the tensile strength when it is heated to 180. The thickness of the laminated film can maintain a thickness of 5 MPa or more. This is because even with the resin composition and additives of the A layer 1, Group-15- 200524731 (13) The composition of layers other than layer A (layer B 2, or layer B 2 and layer D 4, layer E 5 and layer D 4) is also changed and obtained, It is stipulated that it is more preferable that it is more than 25 μm, and more preferable that it is more than 30 μm. Because it is easy to obtain the necessary tensile strength which is thinner and rarer than this. In addition, from the point of stability of extrusion, it is also preferable to have 2 5 μm or more. In addition, as shown in FIG. 2, it is necessary to add a pigment to ensure sufficient concealment only when the structure is not shown in FIG. 2, and it is preferable to have a thickness of 4 5 μm or more. When the thickness is thinner than this, sufficient concealability of the substrate is added, so that it is necessary to add a large amount of pigment, and there is a possibility of reducing workability and the like. Or, it is necessary to add a special pigment such as a sintered pigment of a composite oxide system, and the cost is increased. The thickness of the A layer 1 is preferably less than 200 μm, more preferably less than 100 pmg, and particularly preferably less than 60 μm. In addition, although the thickness is even thicker, the function of the strength maintaining layer as the heating of the a layer 1 is saturated, and the thickness of the A layer 1 must be made thick and the thickness of the B layer 2 must be made thin. As a result, a deep embossed pattern cannot be transferred to the B layer 2. The total thickness of the laminated film is more preferably 65 μm or more and 300 μm or less, more preferably 70 μm or more and 300 μm or less, and particularly preferably about 150 μm. When the thickness is thinner, the protective effect with respect to the base metal plate 6 becomes insufficient. When the thickness is thicker, the conventional soft PVC resin-coated metal plate is used for forming processing such as bending of a forming mold The processability becomes difficult, for example. 200524731 (14) (Resin forming layer B) Layer 2 and 2 are essentially amorphous polyester resins as the main body, and the laminated film with the structure shown in Figure 1 is softened by heating when it is passed through an embossing machine. The embossed pattern layer is pushed and transferred by embossing plate rolling. Therefore, the B layer 2 series cannot have high crystallinity at the time when the embossing plate is rolled, and essentially uses a non-crystalline or low-crystalline polyester resin as a main body. An embossing machine was used for the B layer 2 system, and the embossing was added after heating to the glass transition temperature (T g) or higher. When heated, the elasticity of the b layer 2 must be sufficiently reduced to the extent that embossing can be added. In the present invention, the laminated film system A layer 1 does not cause wide shrinkage, wrinkles, melt fracture, etc., because the melt tension is maintained. As the polyester resin forming the B layer 2, a polyester resin having substantial amorphous or low crystallinity can be used as a main body, and a differential scanning calorimeter can be used. , DSC), polyester resins that do not show a clear peak of crystalline melting at elevated temperatures, although they have crystallinity but have a slow crystallization rate, a film-forming process, and a heating process in which an embossing machine is used to transfer embossed patterns In the middle, a polyester resin having a low crystallinity can be used. As an example of the amorphous copolymerized polyester resin, the so-called PET-G 'Eastman Chemical Company's "EASTAR" from the stable supply of raw materials or a large amount of production to reduce costs PET-G · 6 7 63 ″ or a resin similar to this is better than -17-200524731 (15). "EASTAR PET-G · 6 763" resin has about 30 m 〇1% of the ethylene glycol (ethy 1 eneg 1 y c ο 1) portion of polyethylene terephthalate with 1, 4 -cyclohexane Substantially non-crystalline polyester resin with a structure replaced by cyclohexanedimethanol, measured by DSC, without being considered as a crystallization change. However, it is not limited to this. Although it exhibits crystallinity under specific conditions, it may be treated as an amorphous resin under normal conditions as "PCTG · 5 4 4 5" by Eastman Chemical Co., etc., Or a polyester resin having a composition in which the ethylene glycol portion of polyethylene terephthalate is substituted with 1, 4-cyclohexanedimethanol, and about 3 0 τη ο 1 may be used in place of the ethylene glycol portion. % ～ approx. 7 0 m ο 1%. When the amount of 1,4-cyclohexanedimethanol is about 30 mol% or less, the characteristics as a crystalline resin become remarkable, and it may be difficult to crystallize while heating with an additional embossing machine, so that additional embossing may be difficult. When it is about 70 m ο 1% or more, the crystallinity becomes significantly unfavorable. In addition, copolymerization of neopentyl glycol (PET) does not show crystallinity, or the crystallinity is low, or the polyethylene terephthalate resin copolymerized with isophthalic acid has low crystallinity. Those can also be used as the resin composition of the B layer 2. The B layer 2 may be a polyester resin having a high crystallinity even if PBT or PTT is mixed. When these mixing ratios are high, the crystallinity of the B layer 2 becomes significant, and it is difficult to add embossing for the reasons described above. Therefore, it is necessary to add 40% by weight or 30% by weight to -18%. -200524731 (16) The amount is preferably less than%. In the B layer 2 series, in order to improve the concealment or decorativeness of the base metal, it is possible to add a color pigment. In this case, as described above, the pigment may be added only to the B layer 2 or even both of the A layer 1 and the B layer 2 may be added. Usable pigments can be used for the coloring of general polyester resins in the same manner as in the case of the A layer 1. Although it is suitable to add the necessary various additives to A layer 1 as well as B layer 2. The preferred thickness of layer B 2 is in the range of 45 μm to 25 0 μm, and the range of 50 μm to 2 0 0 μm is more preferable. When the thickness is thinner, the kinds of possible embossing patterns are greatly restricted. Conversely, when it is thicker, the thickness of the A layer 1 is necessary to be thin, and it is difficult to obtain breakage resistance when the laminated film is heated, which is not good. In addition, if the B layer 2 has a thickness of about 105 μm, the embossing plate used for the conventional embossing of a soft PVC film can be almost rolled. (Resin forming D layer) D layer 4 is a layer used in the structure of Fig. 2 or Fig. 3, which is basically the same as that of layer B. It is heated and softened by an additional embossing machine. The embossed layer is pressed and transferred. Therefore, even for the polyester resin forming the D layer 4, the same one as the β layer 2 can be used. The additive layer and the preferred thickness are the same as those of the β layer 2. -19- 200524731 (17) However, the D layer 4 is a layer laminated on the printing layer 3 (layer C), and it is necessary to make the appearance of the printing layer 3 transparent to the extent that it can be seen through. (Resin forming the E layer) The E layer 5 is also composed of an amorphous polyester resin as a main body. In the structure shown in FIG. 2, in the case of transferring a deeper embossed pattern, it is necessary to apply The thickness of the D layer 4 is set to be sufficiently thick. In this case, although the D layer 4 is a layer having transparency, it is unavoidable that an increase in haze (h a z e) cannot be avoided because of a layer having no orientation, and the visibility of the printing pattern cannot be reduced. In addition, since polyester resins are resins that are relatively easy to be yellowed by light, when the thickness of the D layer 4 is made too thick, the yellowing with time is noticeable. So 'under the printing layer 3 (layer C), a layer of deformation is also added by the pressing of the embossing plate rolling, and the thickness of the layer B 2 is made thin to make a good visibility of the printing pattern, and The E layer 5 is added for the purpose of forming a deep embossed pattern. Therefore, even for the polyester resin forming the E layer 5, the same one as the B layer 2 or the D layer 4 can be used. The same applies to additives. Even if the thickness of the additional embossed layer is 1 2 0 μm or less, a relatively shallow embossed pattern can be added. The E layer 5 is not particularly established, and the thickness of the d layer 4 can be 70 μm to 12 μm. . The total thickness of the laminated film is about 150 μm or more. If necessary, the thickness of the D layer 4 is made -20- 200524731 (18) 100 μm or less, preferably about 70 μm, to prevent printing. The transparency of the layer 3 is reduced. On the other hand, the E layer 5 'having a suitable thickness is set to produce a total thickness of about 150 μm or more. In addition, layer A is based on a non-oriented crystalline polyester resin, and layer E is based on a non-crystalline polyester resin. Therefore, it is also recognized as to its heat-sealing suitability. In order to be better than A layer 1, film formation is performed by pressing A layer 1 and E layer 5 together to form a film, and by printing part 3 of print layer 3, printing is performed on E layer 5 and D layer 4 Strong thermal fusion properties can also be obtained between them, and the risk of peeling between the layers can be reduced. The effects of the additional E layer 5 can also be cited. (Printing layer (C layer)) The printing layer 3 is printed by gravure printing, offset printing, screen printing, or other well-known methods. The drawing pattern of the printed layer 3 is any pattern such as a stone pattern, a wood pattern, a geometric pattern, an abstract pattern, and the like. Since the surface on the side of the layer A or layer E or layer 5 is printed, it can be laminated with layer 0 or layer 4 because it is printed on the surface of layer D or layer 4. Lamination is also available. The surface of the generally crystalline A layer 1 or the surface of the ε layer 5 after the A layer 1 and the E layer 5 are laminated and integrated is more than the non-crystalline d layer 4 except for the additional printing layer 3. The printing layer 3 is added to the surface by back printing, and the handleability on the printing line is good. -21-200524731 (19) When one of A layer 1 and B layer 2, D layer 4, E layer 5 is integrated, or E layer 5 and D layer 4 are laminated and integrated using an adhesive, Although the type of the resin adhesive is not particularly limited, the resin adhesive of the printing layer 3 is made of a heat-bonding material such as a non-bridge or a polyester system having a low bridge, and the stack is heated by an additional embossing machine. In the case of a laminated film, the printed layer 3 functions as a heat-adhesive adhesive layer. Or even if a coating film layer having a heat-welding property is simultaneously added to a printing line, the heat-welding property can be found without adding an adhesive layer. In addition, in addition to the partial printing of the printing layer 3 or the rough printing of dots, A layer 1 and B layer 2, or A layer 1 and D layer 4, or E layer 5 and D layer 4 The non-printed parts are in direct contact, and strong thermal fusion is obtained. The A layer 1 passes through the non-crystalline or low-crystalline state before the additional embossing machine, and is characterized by exhibiting weldability when heated by the additional embossing machine. (Manufacturing method of laminated film (A + B) or (A + C + D), (A + E + C + D)) As a method for forming a laminated film of the present invention, various well-known methods can be adopted. The coating method or inflating method (inf 1 ati 〇nmeth 〇d), etc. are also pushed out. In addition, the B layer 2, the D layer 4, and the E layer 5 'system composed of an amorphous polyester resin as a main body are also used. The calendering (caien (jer) film forming method) can be applied, and it is not particularly limited. In the structure shown in Fig. 1, the film is formed by co-pressing, which is more integrated than the original -22- 200524731 (20). In the structure shown in Figure 3, it is also better to integrate the A layer 1 and E layer 5 to form a film more integrated than before. About D layer 4 is because it has a layer A or E! It is necessary to add a printing layer 3 (layer C) after layer 5 is laminated, so it is necessary to form a film in advance. As described above, in order to make the printing layer 3 have thermal fusion, it is based on the film of an embossing machine. In the heating process, it is better to thermally bond the printed layer 3 side of the A layer 1 and the D layer 4 or the printed layer 3 side of the E layer 5 and the D layer 4 to reduce the number of man-hours. (For laminated film (Additional embossing) In Fig. 5, an example of an additional embossing machine generally used is shown in order to add an embossing pattern to a conventional soft pv C film. The laminated film of the present invention can be added with an embossing machine. It has the same embossing pattern as the conventional soft PVC membrane. The melting point (Tm) of layer a is in the range of 210 ° C ~ 24 ° C. Because layer A is crystallized, it will be under additional pressure. Even if the heating temperature of the laminated film of the flower machine is set above 16 ° C, and the melting point (T m)-1 0. (: The following, that is, 2000 to 2 3 0, it does not cause the heating metal to roll. In addition, the tensile breaking strength at 180 ° C is 5 MP a or more, and the wide shrinkage of the laminated film does not occur, such as wrinkle measurement, melt fracture, etc., can be obtained by adding an embossing machine. It has the same or higher embossed heat resistance than the soft PVC membrane with embossed decoration. (Metal sheet?) -23- 200524731 (21) The metal sheet 6 series which is the object of the present invention can use hot rolled steel sheet, cold Various steel plates such as rolled steel, hot-dip galvanized steel, galvanized steel, tin-plated steel, and stainless steel The aluminum plate and aluminum alloy plate can be used even after being subjected to a normal chemical treatment. Although the thickness of the metal plate 6 varies depending on the application of the resin-coated metal plate, etc., it can be selected from 0.1 mm to 10 mm. (Production method of embossed decorative film-coated metal plate) Next, a method of manufacturing the embossed decorative film-coated metal plate of the present invention will be described. The laminated film to which an embossed pattern is added by an embossing attachment Sheets (A + B, A + C + D, or A + E + C + D) are laminated on the metal plate 6 as an adhesive to be used, and examples thereof include epoxy-based adhesives and urethane-based adhesives. And polyester-based adhesives are generally used as the thermosetting adhesive 7. As a method for obtaining a resin-coated metal plate, a metal plate 6 is coated with a coating device generally used such as a reverse coater and a kiss coater, and the layers are integrated. The heat-curable adhesive 7 having a thickness of about 2 μm to 10 μm after the coating and drying of the adhesive on the metal surface of the laminated film is applied. Next, the coating surface is dried and heated by an infrared heater and / or a hot air heating furnace, the surface temperature of the metal plate 6 is maintained at an arbitrary temperature, and a roll laminator is immediately used to laminate the layers. The A layer 1 side of the diaphragm is covered and cooled so as to be an adhesive surface. Thereby, a resin-coated metal plate as shown in Fig. 4 -24-200524731 (22) is obtained. According to the present invention, the melting point (Tm) of the resin A located on the side of the bonding surface with the metal plate 6 is in the range of 2 0 to 24 0t. Therefore, the surface temperature of the metal plate 6 is made from the conventional soft PVC. The case where the film sheet is coated with a metal plate is the same, and a strong adhesive force can be obtained. According to the present invention, although it is a resin-coated metal sheet which has relatively good heat resistance in embossing, after lamination, water cooling is performed immediately after lamination, and embossing recovery is reduced by heating the film during lamination. Better. [Examples] Examples are provided to explain the present invention more specifically and in detail. The invention is not limited to these embodiments. In addition, the measurement methods of the physical properties of the diaphragms and resin-coated metal plates shown in the examples and comparative examples are as follows. (1) The tensile breaking strength at 180 ° C: a universal material tester with a constant temperature tank type 010 ((strand) made by INTESCO) was used, and the temperature in the tank was maintained at 180 ° C. A tensile test was performed on an L-shaped test piece (based on the shape of the test piece of ASTMD-1 8 22-L) to determine the tensile breaking strength. The measurement is performed in the MD direction (longitudinal direction of the film) of each laminated film. (2) Applicability of additional embossing: adhesion resistance-25- 200524731 (23) When embossing is performed by the additional embossing machine shown in Fig. 5, the adhesive film is displayed on the heating roller 8 (heated rolling) The film is "x", the unattached one is 1 ". (3) Applicability of additional embossing ·· Elongation resistance and fusing resistance When the embossing is performed by the additional embossing machine shown in Fig. 5, when the film is heated by the heater, the film is shown as "X . ”, Those who have not reached the point of fusing to cause significant stretching or wrinkling of the diaphragm are“ △ ”, and those who do not cause such problems are“ 0 ”. (4) Applicability of additional embossing: transferability The embossed film is added by an additional embossing machine as shown in FIG. 5 and visual observation shows that the person who transfers the beautiful embossed pattern is "0". Compared with this, the case where the transfer is slightly shallow is "△", and those who have a poor transfer, form a shallow embossed pattern, or have no relationship with the embossed pattern, and only have a rough surface, are "v ... (5) embossed" Heat resistance After the metal plate 6 laminated with the embossed diaphragm by the additional embossing machine shown in FIG. 5 was left in a hot air circulation oven at 105 ° C for 3 hours, it was visually observed. Compared with the case where the embossed shape shows little change compared with the case before putting it in the oven, it is "0". Compared with this, the case where the embossing returns slightly is "△", the case where the embossing returns is significant, or the embossing Figure -26- 200524731 (24) Completely disappeared and the surface roughness is only ^ x ″ ° (6) Workability of resin-coated metal plate The impact tight bending test was performed on the resin-coated metal plate, and the bending processing portion was determined visually The state of the face of the cosmetic film, and the one with little change is (〇). The number of cracks is (△), and the number of cracks is (X). The impact tight bending test was made as follows. Samples of 50 mmxl50 mm were prepared from the lengthwise direction and the widthwise direction of the coated metal plate, and were maintained at a temperature of 2 3 ° C for 1 hour or more, and then subjected to 180 using a bending tester. For the preliminary bending (inner radius of bending 2 mm), the sample was dropped from a height of 50 cm with a cylindrical hammer having a diameter of 75 mm and a mass of 5 kg in the shape of a crushed preliminary bending portion. (Production of laminated films of Examples 1 to 19 and Comparative Examples 5 to 10) As shown in Table 1 or Table 2, A layer 1 and B layer 2 'were combined with a resin composition and each layer thickness using 0 65 mm. Two biaxial kneading and extruding machines were co-extruded by a feed block method to obtain two layers of moon-moon tablets. The film is formed in accordance with a general method of obtaining resin flowing out of a T die by a rubber roll. (Creation of single-layer diaphragms of Comparative Examples 1 to 4) A biaxial kneading extruder using 0 6 5 coffee was used to produce a film by using a τ mold. The resin composition shown in Table 1 or Table 2 was used. , To make single -27- 200524731 (25) layer diaphragms. The film formation of the diaphragm is performed according to a general method of obtaining resin flowing out of a T die by a rubber roll. The composition and thickness are listed in the column of the A layer 1 in Table 1.

-28- 200524731 (26) &lt; Table 1 &gt; Examples 1 to 19, Comparative Examples 1 to 10 A layer composition and thickness A layer resin composition (% by weight) Pigment EASTAR PCTG NOVADURAN CORTERRA Additive thickness. 6763 5445 5020S PTT (weight) (μηι) Example 1 20 0 80 0 0 45 Example 2 10 0 90 0 0 30 Example 3 0 0 100 0 0 45 Example 4 30 0 70 0 0 30 Example 5 30 0 70 0 0 60 Example 6 0 20 80 0 0 35 Example 7 0 0 0 100 0 45 Example 8 20 0 80 0 0 45 Example 9 20 0 80 0 0 45 Example 10 30 0 70 0 0 25 Example 11 40 0 60 0 0 45 Example 12 45 0 55 0 0 45 Example 13 20 0 80 0 0 45 Example 14 20 0 80 0 0 25 Example 15 20 0 80 0 0 50 Example 16 20 0 80 0 0 50 Example Π 0 0 100 0 0 45 Example 18 20 0 80 0 0 45 Example 19 20 0 80 0 0 45 Comparative Example 1 100 0 0 0 16 150 Comparative Example 2 80 0 20 0 16 150 Comparative example 3 0 0 100 0 16 150 Comparative example 4 20 0 80 0 16 150 Comparative example 5 20 0 80 0 0 45 Comparative example 6 20 0 80 0 0 15 Comparative example 7 20 0 80 0 0 15 Comparative example 8 0 55 45 0 0 45 Comparative Example 9 65 0 35 0 0 45 Comparative Example 10 20 0 80 0 30 45-29- 200524731 (27) <Table 2 &gt; Examples 1 to 19, Comparative Examples 1 to 10 Composition and thickness of layer B, tensile strength B layer Laminated diaphragm Before embossing diaphragm temperature (0 resin composition (% by weight) pigment addition (weight portion) thickness (μηι) 180 ° C tensile strength (Mpa) EASTAR 6763 NOVADURAN 5020S Example 1 80 20 24 105 13.8 170 Example 2 80 20 20 120 11.7 170 Example 3 80 20 24 105 13.7 170 Example 4 80 20 20 120 7.9 170 Example 5 80 20 26 90 16.2 170 Example 6 80 20 21 115 11.4 170 Example 7 80 20 24 105 17,9 170 Example 8 70 30 24 105 13.1 170 Example 9 100 0 24 105 12.8 170 Example 10 100 0 20 125 5: 4 170 Example 11 80 20 24 105 9.2 170 Example 12 80 20 24 105 6.8 170 Example 13 80 20 36 50 13.3 170 Example 14 80 20 36 45 7.1 170 Example 15 70 30 12 200 14.5 170 Example 16 70 30 10 250 14.2 170 Example Π 60 40 24 105 16.2 170 Example 18 80 20 24 105 13.8 200 Example 19 80 20 24 105 13.8 160 Comparative Example 1 — — — Cannot measure 170 Comparative Example 2 — — — — Cannot measure 170 Comparative Example 3 — — — — 41.9 170 Comparative Example 4 — — — — 35.8 170 Comparative Example 5 50 50 24 105 23.7 170 Comparative Example 6 80 20 18 135 4.6 170 Comparative Example 7 80 20 18 135 4.6 140 Comparative Example 8 80 20 24 105 Unable to measure 170 Comparative Example 9 80 20 24 105 Unable to measure 170 Comparative Example 10 80 20 30 15 12.7 170 Unable to measure was judged to be 5 MP a or less. -30- 200524731 (28) (Creation of laminated films of Examples 20, 21, 25) Using a biaxial kneading extruder of 0 ό 5 _, the film was formed by extrusion using a τ die, and The A layer 1 and the D layer 4 are each formed as a single-layer film. The film formation of the diaphragm is carried out according to a general method of obtaining the resin flowing out of the T die by a rubber roll. Next, a pattern of an abstract pattern was printed on the surface of the A layer 1 by gravure printing. The composition and thickness combinations of the layers are shown in Table 3 or Table 4. In the additional embossing machine shown in Fig. 5, these films are supplied from two unwinding shafts, and the contact portions with the heating drum 8 are integrated by thermal fusion lamination. (Creation of a single-layer film in Comparative Example 11) Using a biaxial kneading extruder of 0 6 5 mm, the film was formed by extrusion using a τ mold using the resin composition shown in Table 3 or Table 4. Monolayer diaphragm. The film formation of the diaphragm is performed according to a general method of obtaining resin flowing out of a T die by a rubber roll. Next, the surface of the single-layer diaphragm was printed with an abstract pattern by gravure printing. In addition, the composition and thickness are described in the column of the A layer 1 in Table 3, but they are simply described (the production of the laminated film of Examples 22 to 24, 26 to 28, and Comparative Example 12). Table 3 Or as shown in Table 4, as the resin composition of a layer 1 and E layer 5 and the thickness of each layer, use two biaxial kneading-out -31-200524731 (29) machine of 0 6 5 mm to feed the oil jacket. Co-extrusion in a tube manner yielded a two-layer laminated film. The composition of the E layer 5 is the same as that of the resin composition of the d layer 4 shown in Table 4. In addition to this, a biaxial kneading extruder of 0 65 mm was used, and the d layer 4 with the composition and thickness shown in Table 4 was used as a single-layer film by extrusion filming using a T die. Filming. The film formation of these diaphragms is carried out in accordance with a general method of obtaining resin flowing out of a T die by a rubber roll. Next, a pattern of an abstract pattern was printed on the surface of the E layer 5 by gravure printing. In the additional embossing machine shown in Fig. 5, these film sheets are fed from two winding shafts, and the contact portions with the heating drum 8 are integrated by thermal fusion lamination. -32- 200524731 (30) &lt; Table 3 &gt; A layer composition and thickness of Examples 20 to 28, Comparative Examples 1 and 12, and presence or absence of E layer A layer E layer resin composition (wt%) Pigment E layer Pigment E layer EASTAR PCTG NOVADURAN CORTERRA Adding amount Thickness is added. Thickness 6763 5445 5020S PTT (weight part) (μηι) None (weight part) (μηι) Example 20 0 80 0 36 60 te — — 20 Example 10 0 90 0 36 45 Μ j \ \\ — — 21 Examples 0 0 100 0 24 30 There are 24 70 22 Examples 30 0 70 0 24 30 There are 24 70 23 Examples 40 0 60 0 24 60 There are 24 70 24 Implementation Example 20 0 80 0 36 45 Μ j \ w — 25 Example 20 0 80 0 0 45 Yes 30 80 26 Example 0 20 80 0 0 30 Yes 34 70 27 Example 30 0 70 0 24 80 Yes 24 120 28 Comparative example 30 0 70 0 16 150 M — — 11 Comparative example J 30 0 70 0 24 20 Yes 24 80 12

-33- 200524731 (31) <Table 4 &gt; Example 2 0 ~ 2 8, Comparative Example 1 1 and 12 D layer composition and thickness, tensile strength resin composition (weight%) of D laminated film 180 ° C EASTAR NOVADURAN added amount thickness tensile strength 6763 5020S (weight part) (μm) (Mpa) Example 20 80 20 0 90 16.3 Example 21 80 20 0 105 19.7 Example 22 80 20 0 50 14.9 Example 23 80 20 0 50 6.8 Example 24 80 20 0 50 13.4 Example 25 70 30 0 105 11.9 Example 26 60 40 0 50 13.6 Example 27 80 20 0 50 10.7 Example 28 80 20 0 50 19.3 Comparative Example Π — — — 30.3 Comparative Example 12 80 20 0 50 4.3 As the resin composition of each of these layers, the following were specifically used. • NOVADURAN 5 020 S: Homogeneous PBT resin, Mltsubishi Engineering-Plastics 〇rp〇ratl〇n㈣, glass transition point; 45 "c] 'crystallization dissolution peak-34-200524731 (32 ) Temperature; 2 2 3 [° C] • CORTERR A CP509200: homogeneous PTT resin, made by Shell (she 11) Co., Ltd., glass transition point; 4 9 [° c], peak melting temperature of crystal; 225 [° C ] EASTARPET-G 6763: 1,31-cyclohexanedimethanol replaced about 3 1 m of the ethylene glycol portion of polyethylene terephthalate. Iran's amorphous polyester resin, Iran Made by Shiman Chemical Co., Ltd., glass transition point; 8 i [1], peak melting temperature of crystals; unobservable [t] • PCTG 5 44 5: Polyethylene terephthalate was replaced by 1 '4-cyclohexanedimethanol About 70 mol% of the ethylene glycol portion of the ethylene glycol is processed as a substantially amorphous polyester resin, made by Eastman Chemical Co., Ltd., glass transition point; 8 [° C], peak melting temperature of crystals; Unobservable [t:] (Embossing die is added to the diaphragms of Examples 1 to 2 and Comparative Examples 1 to 12 (Sample) Even in general, the soft vinyl chloride film shown in Figure 5 is used, and the embossing pattern is added by the continuous embossing machine. Part of the printed film is as described above. The heating roller 8 of the additional embossing machine is laminated by thermal fusion. As a strategy of the embossing additional device by the continuous method, the pre-heating of the diaphragm is first performed by contact-type heating using a metal heating roll, and then The non-contact heating using the infrared heater 9 is used to heat the film to an arbitrary temperature, and the embossing roll is rolled by 10 to transfer the embossed pattern. The heating roller 8 is set to 100 ° C. -35- 200524731 (33) The heater is used to heat the membrane before contacting the embossed pattern to the appropriate temperature shown in the table. In addition, the temperature of the embossed pattern is 80 ° C, and the surface is rough on average. The smooth finish with a degree of Ra = ic ^ m has been rolled. In addition, the 11-series takeoff roller, 12-series pinch roll, and 13-series cooling roll are shown in Fig. 5. (Resin Production of coated metal plates) For metal-clad plates, a polyester-based thermosetting adhesive 7 that is generally used is applied to a state where the thickness of the adhesive film after drying on the metal surface is about 2 μm to about, and then heated by a hot air heating furnace and infrared rays The coated surface is dried and heated by the device 9 and the surface temperature of the galvanized steel sheet (metal sheet 6: thickness 0.45 mm) is set to 23 5 t: AA is a polyester resin film coated with a roll laminator. The sheet was coated with a metal plate by embossing a decorative membrane by cooling with water. (Evaluation of embossed decorative film and embossed decorative film-coated metal plate) Each of the above items was evaluated. The results are shown in Table 5 or Table 6. In Table 5 or Table 6, "the adhesion to the heating drum 8 of the additional embossing machine is not evaluated in the future, the k-state of the stretcher of the diaphragm of the additional embossing machine, or the melting of the diaphragm." Breakers were not evaluated in the future. -36- 200524731 (34) &lt; Table 5 &gt; Evaluation results of Examples 1 to 19 and Comparative Examples 1 to 10 Additional embossing suitability embossing heat-resistant resin-coated metal sheet processability adhesion resistance elongation Fusing-resistant pattern transferability Example 1 000 000 Example 2 000 000 Example 3 000 000 Example 4 4 000 000 Example 5 000 000 Example 60000 Example 70000 Example 80000 Example 90000 Example 10 △ △ Example 11 △ △ Example 12 Δ Δ 〇 Example 13 0000 Example 14 Δ Δ 〇 Example 1500 〇 Example 16 〇 〇 △ Example 17 〇 Δ 〇 Example 18 〇 〇 〇 Example 19 〇〇〇〇 Comparative Example 1 X — — — — Comparative Example 2 X — — — — Comparative Example 3 〇X — 〇 Comparative Example 4 〇OX — 〇 Comparative Example 5 〇〇 × — 〇 Comparative Example 6 〇X — — — ratio Comparative Example 7 〇〇〇 × 〇 Comparative Example 8 Δ X — — — Comparative Example 9 X — — — — Comparative Example 10 〇Δ X — — 200524731 (35) <Table 6 &gt; Example 2 0 to 2 8 and comparison Evaluation results of Examples 1 and 12 Addition of embossing suitable embossing heat-resistant resin-coated metal Adhesion resistance Elongation resistance Fusing pattern transferability sheet_ Example 20 2000 Example 21 0000 Example 22 0000 Example 23-20,000 Example 24 △ △ △ Example 25 20,000 Example 26 _ 〇〇〇〇 Example 27- — 〇〇〇〇 Example 28 〇〇.〇 Comparative Example 11 — — — 〇 Comparative Example 12 X — — 〇

In Comparative Examples 1 and 2, the amorphous polyester resin was used as the main component. @ 'But the tensile breaking strength of 1 8 (rc was low, which caused the adhesion to the heating roller 8 with an additional pressure pad. Subsequent operations will become difficult. &Amp; ^ Examples 3 and 4 are single-layer diaphragms with a crystalline polyester resin as the main body, and &amp; ^ 'At the time of forming the film, it is in a state of high crystallinity. Although y | \ r _ $ The adhesion of the heating roller 8, but even if the film is heated to 170-38- 200524731 (36) C High elasticity can be maintained depending on crystallinity, and embossed pattern cannot be transferred. Comparative Example 5: The composition of layer A is consistent with the scope of the present invention. The composition of layer B is not amorphous polyester The main body is crystallized by the heating of an additional embossing machine, and the embossing pattern cannot be transferred. Comparative Example 6 Although the composition of A layer 1 □ B layer 2 is consistent with the scope of the present invention, The thickness is thin and the tensile breaking strength of 8crc is beyond the scope of the present invention. As a result, when the diaphragm is heated, Significant wrinkling or wide shrinkage, which does not allow a good transfer of embossed pattern. Comparative Example 7 uses a film with the same composition and structure as Comparative Example 6, and the film is heated at the temperature of an additional embossing machine. It is limited to 14 °. (: The problem of wrinkles and the like of the membrane is not caused. Although a good transfer of the embossed pattern can be obtained, the heat resistance of the embossed pattern is low, and it is judged that it cannot be practically endured. Comparative Examples 8 and 9 series Although the composition of layer B 2 is consistent with the scope of the present invention, the composition of layer A 1 is not a crystalline polyester resin main body, and the tensile breaking strength at 180 ° C is low, resulting in In order to adhere to the heating drum 8 of the additional embossing machine, the subsequent work becomes difficult. Comparative Example 10: Although the composition of the A layer 1 and the B layer 2 are consistent with the scope of the present invention &gt; Therefore, a better transfer of the embossed pattern cannot be performed. On the other hand, in Examples 1 to 19 of the present invention, no adhesion to -39- 200524731 (37) of the heating roller 8 or heating of the heater is caused. The diaphragm is broken, and a good embossed pattern can be obtained. In addition, the heat resistance of the embossed pattern and the workability of the resin-coated metal plate are also good. Comparative Example 1 The film is applied to the surface of a single-layer film because the composition of the film is from the system and the comparative example. 3, and 4 are also made of PBT resin as the main body, so the tensile breaking strength at 180 ° C shows strong 値, although there is no adhesion to the heating roller 8 or stretch of the diaphragm, However, the embossed pattern cannot be transferred. Comparative Example 1 Although the composition of layer A]., E layer 5 and D layer 4 is inconsistent with the scope of the present invention, the thickness of layer A is 1 to 80 t. The tensile breaking strength is beyond the scope of the present invention. As a result, when the film is heated, significant wrinkles or wide shrinkage are generated, and a better transfer of an embossed pattern cannot be performed. On the other hand, in Examples 20 to 28 having the structure of the printing layer 3 of the present invention, the adhesion to the heat roller 8 or the film breakage when the heater is heated are not generated, and good results can be obtained. Embossed pattern transferability. In addition, the heat resistance of the embossed pattern and the workability of the resin-coated metal sheet were also good. In addition, in Example 21 in which the thickness of the D layer 4 is thick, although the transparency of the printed layer 3 is slightly deteriorated, the E layer 5 is added to reduce the thickness of the D layer 4 in Examples 22 and Examples. 23. The transparency of the printed layer 3 was good, and the transferability with respect to embossing was not different from that of Example 20. 200524731 (38) [Brief description of the drawings] Fig. 1 is a schematic cross-sectional view of a laminated film in the first state of the present invention. Fig. 2 is a schematic sectional view of a laminated membrane of a second aspect of the present invention. Fig. 3 is a schematic sectional view of a laminated membrane of a third aspect of the present invention. &gt; Fig. 4 is a schematic cross-sectional view showing an example of a metal plate coated with an embossed decorative film laminated on a metal plate through a thermosetting adhesive and an adhesive on the laminated film shown in Fig. 3. φ Figure 5 is a schematic diagram showing an example of an additional embossing machine that adds an embossing pattern to a conventional soft PVC membrane. [Description of main component symbols] 1 ... A layer 2 ... B layer 3 ... printed layer (C layer) 4 ... D layer 5 ... E layer 6 ... metal plate 7 ... thermosetting adhesive 8 ... heating roller 9 ... infrared heater '10 ... Embossed roll 11 ... Eliminated roll 12 ... Clamped roll 13 ... Cool roll -41-

Claims (1)

200524731 拾 Pick up and apply for patent scope 1. A polyester resin which is superior to laminated properties with suitable embossing as the main body. It is a non-oriented resin layer (layer A crystalline polymer layer) in the lamination range of 24 ° C. An ester-based resin is used as a main body without a layer) of a laminated film composed of at least two layers, and the total thickness of the film is 65 μm to 3 00 μm, and the tensile breaking strength is 5 MPa or more. 2. — A kind of polyester resin that is superior to the laminated property of adding suitable embossing as the main body, and has a non-directional resin layer (layer A) (layer C) in the melting range, and is laminated on it. A laminated film composed of three non-oriented transparent resin layers consisting essentially of a fat, which is characterized in that the total thickness of the film is a tensile breaking strength of 65 μm to 300 μm. It is 5 MPa or more. 3. — A polyester-based resin that is superior to laminated properties with appropriate embossing as the main body, and a non-oriented resin layer in the lamination range of 240 ° C (A-layer crystalline polyester-based resin is used as the main body) Layer), and a printing layer is added to the surface of the E layer side, and at least a film is formed by laminating a transparent resin layer (layer D) having a substantially amorphous polyester tree without orientation, which is characterized by: :: Membrane, which will have a crystal &amp; a melting point of 2 1 0 ° c ~), and a substantially non-directional resin layer (B, which is characterized by a range of, a membrane at 180 ° C, will have Crystallinity occupies at least 2100 ° C ~ 2400 ° C. At least the range of the amorphous polyester tree (layer D) with a printed layer on the surface. The film at 180 ° C will have crystals. It has a multilayer with a melting point of 210 ° C ~), and a non-directional resin layer (E (C layer)), and 4 layers consisting of fat as the main body -42- 200524731 (2) Making a film The total thickness is 6hm ~ 30 (^ m in the range of 180 ° C and the tensile breaking strength is 5 MP a or more. The recorded laminated film is superior to the attached embossing, in which the A layer, the B layer, or the integration with the E layer are made by laminating in the mold of the co-extrusion method. The surface of the laminated film with superior embossing as described in item 2 or 3 of the scope, in which the printing layer of D layer and A layer is added), or the printing layer of layer D and E layer (c layer) ) The integration of lamination is by heat welding lamination. 6. As described in any one of the scope of patent application No. 丨 ~ 3, the lamination membrane with additional embossing is added, in which layer B, layer D, and E Substantially non-crystalline polyester resin with 1, 4-. Cyclohexanedimethanol to replace 70% of the ethylene glycol portion of polyethylene terephthalate. 7 m · As described in any of claims 1 to 3, the laminated film with appropriate embossing is added, in which the total resin of layer A is 55.5% by weight or more. Polybutylene terephthalate (PB T) Shuyuezhi 8. A kind of embossed decorative membrane, which is characterized in that the scope of patent application is 1 to 3 at 160 ° C or higher The laminated film described in any of the following is heated to a temperature of (Tm)-10 ° C or lower of layer A, and then embossed with a roll to add a pattern on the surface of layer B or the surface of layer D. The surface 9. A method for manufacturing an embossed decorative membrane, characterized in that: a suitable die layer is added with a methanol diester of 30 (excellent layer on the surface of c), and an excellent melting point embossing -43- 200524731 (3) The laminated film described in any one of the scope of patent application] to 3 at 160 ° C or higher is heated to the melting point (Tm) of layer A — 10 ° C After the following temperature, an embossing pattern was added to the surface of the B layer side or the surface of the 0 layer side by rolling with an embossing plate. 10, an embossed decorative membrane-coated metal sheet, characterized in that the embossed decorative membrane described in item 8 of the patent application has a surface on the side of layer A as a bonding surface, and a thermosetting adhesive is used to Laminate on top of a metal plate. 1 1. A building interior material, characterized in that: a door plate, a prefabricated bath, a prefabricated bath ceiling material, and a prefabricated bathroom ceiling material are coated with a metal plate covered with an embossed decorative membrane as described in item 10 of the scope of patent application. , Partition materials, sheet materials for building interior materials.