JP4996831B2 - Laminated sheet for covering metal plate and laminated sheet coated metal plate - Google Patents

Description

  The present invention relates to a laminated sheet for coating a metal plate, and a laminated sheet-coated metal plate coated with this sheet, and in particular, has excellent scratch resistance, workability, and excellent hot water resistance. The present invention relates to a laminated sheet-covered metal plate that can be preferably used for building materials used in a wet heat environment, and a metal sheet-covered laminated sheet constituting the metal plate.

  Conventionally, as a covering sheet for resin-coated metal plates used for interior building materials such as unit baths, a biaxially stretched polyester sheet as a surface layer is laminated and integrated on a base material of a colored soft PVC sheet. The used sheet has been used. In this sheet, since the surface is made of a biaxially stretched polyester resin, it has excellent scratch resistance and detergent resistance, and has a good surface smoothness, and a back print is provided on the back surface of the biaxially stretched polyester sheet. The printing design with a deep feeling was able to be obtained by printing called.

  However, in recent years, the use of soft PVC sheets has been restricted due to environmental problems and the like, and laminated sheets based on resins other than soft PVC and resin-coated metal plates using the same have been required. .

  As a laminated sheet using a resin other than soft PVC as a base material, it was first considered to use a base material made of a polyolefin resin from the viewpoint of cost. However, the resin-coated metal plate coated with the laminated sheet has a problem that the bent portion is whitened due to the crystallinity of the polyolefin-based resin when it is bent. In addition, in order to solve this problem, when a prescription that lowers the crystallinity of the polyolefin resin is used, even in a configuration in which a biaxially stretched polyester sheet is laminated as a surface layer, the surface hardness becomes low and scratch resistance occurs. There was a problem that the property deteriorated.

  Therefore, it has been studied to use a polyester resin sheet having a good balance between workability and surface hardness as a base material. In Patent Document 1, a base material made of an amorphous polyester resin represented by PETG6763 of Eastman Chemical Co., Ltd. A multilayer composite using is described.

  Patent Document 2 describes a polyester resin sheet-like material having a blend composition of a crystalline polyester resin and an amorphous polyester resin as a good result in a boiling water immersion test. .

Patent Document 3 describes a copolymerized polyester sheet and film that prevent deterioration in processability over time by adding a specific methyl methacrylate / butadiene / styrene resin (MBS resin) to the polyester resin. Yes.
JP 2000-071407 A JP 02/092688 A JP 2002-121367 A

  However, in the decorative film described in Patent Document 1, the glass transition temperature (Tg) of the resin forming the base material is in the range of about 70 to 85 ° C. and does not have crystallinity. The boiling water immersion test that is generally included as an evaluation item for such applications cannot be satisfied.

  Furthermore, non-oriented amorphous polyester resins have a problem that mechanical properties such as elongation at break gradually decrease when stored for a long period of time at or below the glass transition temperature of the resin after thermoforming.

  This decrease in mechanical properties is thought to be due to the progress of so-called enthalpy relaxation. For resin-coated metal sheets laminated with a base material layer alone, or resin-coated metal sheets laminated with a laminated sheet of a biaxially stretched polyethylene terephthalate resin layer and a base material layer with a commonly used thickness, these processes However, the mechanical properties were not lowered to such an extent that it became difficult. However, in order to obtain a sense of depth as a case where the problem that the mechanical properties deteriorate is manifested, in addition to the laminated sheet in which the biaxially stretched polyester resin having a thickness is laminated on the surface layer, or the similar purpose, In order to give a sense of design, the adhesive layer interposed between the surface layer and the base material was thickened, and a resin-coated metal plate was created with a laminated sheet in which glittering particles were added to the adhesive layer. If the Erichsen test with a notch is performed after a resin-coated metal plate has been produced for a long time, problems such as partial peeling of the laminated sheet from the metal plate may occur. The workability of the plate could be inferior. Here, the “notched Eriksen test” is a deformation that causes elongation of the resin layer after giving a notch that can be a starting point of peeling to the resin layer, as shown in FIG. 3. Is applied to the resin-coated metal plate, and the peeled state of the resin layer at the cut portion is observed.

  This is because in the processing while the enthalpy relaxation of the substrate does not proceed, the deformation stress of the surface layer made of the biaxially stretched polyester resin in the deformed portion is dispersed and absorbed in the substrate layer, and this deformation stress is Although it did not reach the interface with the metal plate, in the processing after the enthalpy relaxation of the base material progressed, the deformation stress of the surface layer made of biaxially stretched polyester resin was not dispersed and absorbed in the base material layer. It is considered that this is caused by reaching the interface between the base material layer and the metal plate, thereby causing peeling between the base material layer and the metal plate. And especially when the thickness of a biaxially stretched film is increased, or when the thickness of an adhesive layer is increased, it is considered that the influence becomes remarkable.

  Because the cause of the processability deterioration of the resin-coated metal plate described above is enthalpy relaxation, before processing the resin-coated metal plate, by heating the resin-coated metal plate above the glass transition temperature of the coated resin, The workability of the resin-coated metal plate can be recovered. However, such treatment is not preferable because it increases the number of processes, and is not acceptable to processing manufacturers.

  Moreover, also in the polyester-type resin sheet-like material of patent document 2, progress with time of enthalpy relaxation progresses similarly to the case of the decorative film of patent document 1. Accordingly, there is a possibility that a problem may occur in workability after aging in a configuration in which a thick biaxially stretched polyethylene terephthalate resin layer is laminated.

  In addition, the copolymer polyester sheet and film described in Patent Document 3 are effective in preventing a decrease in elongation at break, but since the sheet and film itself are not intended for resin-coated metal plates, Bending whitening when used as a plate cannot be sufficiently prevented. Moreover, in this copolyester sheet and film, since a crosslinked rubber is added, it is considered that void whitening occurs as bending whitening when used as a resin-coated metal plate.

  Therefore, the present invention can withstand boiling water immersion in order to solve the above-mentioned problems, and there is a problem in workability even if secondary processing is performed after a long period of time has elapsed since the laminated sheet-coated metal plate was produced. It is intended to provide a laminated sheet-covered metal plate that does not cause the occurrence of the problem, and a laminated sheet constituting the metal plate.

  The present invention will be described below. In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are appended in parentheses, but the present invention is not limited to the illustrated embodiment.

  1st this invention is comprised from the base material layer (A layer) (10) which consists of resin containing a pigment, and transparent stretched polyester-type resin, and the surface layer (B layer) (20) which is 100 micrometers or less in thickness A non-polyester system in which the A layer (10) has 3 to 15% by mass of an epoxy group, where the mass of the entire resin component in the A layer (10) is 100% by mass. Thermoplastic elastomer (component a-1), 21 to 48% by weight of polybutylene terephthalate resin (component a-2), and 42 to 73% by weight of polyester resin (a- This is a metal sheet-covered laminated sheet (100) comprising three components).

  In this laminated sheet, the polyester resin component of the layer A (10) contains a crystalline polybutylene terephthalate resin, thereby improving the boiling water immersion property when the laminated sheet-coated metal plate (200) is used. be able to. And it can be set as the lamination sheet coating | coated metal plate (200) which can maintain a smooth external appearance, even after contacting high temperature water for a long time. Further, since the polyester resin component of the layer A (10) contains a specific amount of a non-polyester thermoplastic elastomer having an epoxy group that can be relatively finely dispersed, the laminated sheet-coated metal plate (200) Even if it is subjected to secondary processing after a long period of time after the production, the possibility of causing problems in workability can be reduced.

  In the above metal sheet-covering laminated sheet (100), the substantially amorphous polyester resin (a-3 component) of the layer A (10) is terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component. Main component, 20 to 80 mol. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining 80-20 mol. % Is preferably a copolyester comprising ethylene glycol. By using a material that is easily commercially available as the substantially amorphous polyester-based resin of the A layer (10), it is possible to obtain the merits of stability of raw material supply and cost.

  In the laminated sheet for metal plate coating (100), the non-polyester thermoplastic elastomer (a-1 component) having an epoxy group of the layer A (10) is an epoxy-modified styrene / butadiene block copolymer. It is preferably a polymer or an epoxy-modified polyolefin resin. It is preferable to use these resins as a non-polyester thermoplastic elastomer (a-1 component) having an epoxy group, which is a material that is easily commercially available, and at the same time affects the physical properties such as durability. This is because there is little effect.

  In the metal sheet-covering laminated sheet (100), the B layer (20) is preferably a biaxially stretched homopolyethylene terephthalate resin. Further, a printed pattern (printed pattern C) (30) and an adhesive layer (D layer) (40) may be arranged between the B layer (20) and the A layer (10). Thereby, what is called a mirror surface design with a smooth surface can be obtained. Moreover, the lamination sheet which has a printing design can be obtained. Further, by making the adhesive layer transparent, the coloring design by the pigment added to the A layer (10) can be improved, and color matching and the like can be facilitated.

  In the metal sheet-covering laminated sheet (100), the total thickness of the B layer (20), the printed pattern C (30), and the D layer (40) is preferably in the range of 35 μm to 115 μm. By making the total thickness of each layer within this range, a deep design feeling can be provided, and the laminated sheet-coated metal plate (200) can have good workability.

  The second aspect of the present invention is a laminated sheet-covered metal plate (200) obtained by laminating the above-mentioned laminated sheet for metal plate coating (100) on the metal plate (50) with the surface on the A layer (10) side as an adhesive surface. It is. In this laminated sheet-coated metal plate (200), boiling water immersion is obtained, and at the same time, it has a deep design feeling, and after a long period of time has passed since the laminated sheet-coated metal plate (200), secondary processing is performed. Even when applied, there is little risk of problems in workability.

  In the above laminated sheet-coated metal plate (200), when the notched Eriksen test was performed at an ambient temperature of 23 ° C. after being left in a constant temperature and humidity chamber of 40 ° C. and 90% relative humidity for 30 days. The peel length (490) of the laminated sheet for metal plate coating (100) from the metal plate (50) is preferably 2 mm or less. Here, the “notched Eriksen test” means a notch (as a starting point of peeling in the laminated sheet (100) portion of the laminated sheet-coated metal plate (200), as shown in FIG. 410), and using an Erichsen test apparatus defined in JIS K6744, the laminated sheet (100) side is projected so that the height (480) is 6 mm, and the cut portion (420) is laminated. This is a test method for observing the peeled state between the sheet (100) and the metal plate (50).

  A third aspect of the present invention is a building interior material selected from the group consisting of a unit bath wall material, a unit bath ceiling material, a door material, a general interior wall material, and a partition material using the laminated sheet-coated metal plate (200). is there.

  The laminated sheet-coated metal plate using the laminated sheet for coating a metal plate according to the present invention is in the progress of enthalpy relaxation in the base material layer (A layer) even after a long period of time has elapsed since the laminated sheet-coated metal plate was produced. It is possible to effectively prevent the deterioration of workability with time, and the problem of deterioration of workability in secondary processing does not occur. In addition, when the transparent surface layer is thickened in order to obtain a design with a sense of depth, the above-mentioned problem of deterioration in workability becomes more prominent, but the laminated sheet covering of the present invention In such a case, the metal plate does not have a problem of deterioration of workability in the secondary processing. Furthermore, since the base material layer (A layer) contains a polybutylene terephthalate resin which is a crystalline polyester resin, the laminated sheet-coated metal plate can be made excellent in hot water resistance. Further, since the surface layer is a transparent stretched polyester resin, it is excellent in scratch resistance and chemical resistance, and can be preferably used for building materials used in wet heat environments such as unit baths.

  Hereinafter, embodiments embodying the present invention will be described.

  In addition, the laminated sheet of the present invention includes a range generally referred to as “film” and a range referred to as “sheet” with respect to the thickness. In the present invention, for convenience, a single designation of sheet is used for these.

  In addition, the expression “non-orientation” means that an orientation treatment such as a stretching operation has not been performed in order to impart some performance to the laminated sheet, such as an orientation generated by take-up by a casting roll during extrusion film formation. It does not mean that it does not exist.

  As shown schematically in FIG. 1 (a), the laminated sheet 100 for coating a metal plate of the present invention comprises at least two layers of a base layer (A layer) 10 and a surface layer (B layer) 20. It is a laminated sheet. Hereinafter, each layer will be described.

<Base material layer (A layer) 10>
The base material layer (A layer) 10 is a non-polyester thermoplastic elastomer (a-1 component) having 3 to 15% by mass of an epoxy group based on the mass of the entire resin component in the A layer 10 (100% by mass). ) 21 to 48% by mass of polybutylene terephthalate resin (component a-2) and 42 to 73% by mass of a substantially amorphous polyester resin (component a-3).

(A-2 component)
The polybutylene terephthalate resin that is the component a-2 imparts crystallinity to the A layer 10. If the amount of the a-2 component is too small, the crystallinity of the A layer 10 becomes insufficient, and when the laminated sheet-coated metal plate 200 is subjected to a boiling water immersion test, the surface roughness due to the deformation of the A layer 10 itself. Further, it is not preferable because the B layer 20 is peeled off. Conversely, if the amount of the a-2 component in the A layer 10 is too large, the crystallinity of the A layer 10 becomes too high, and is the metal plate 50 heated to a relatively high temperature during lamination with the metal plate 50? If post-heating with a non-contact type heater or the like is not performed immediately after lamination, smoothing of the laminated sheet 100 is not achieved, and it is difficult to obtain a so-called mirror surface appearance.

  A sheet composed of a transparent stretched polyester resin that is the surface layer (B layer) 20 described below, particularly a sheet composed of a biaxially stretched homopolyethylene terephthalate resin, which is a preferred form, has extremely high smoothness. However, when a laminated sheet with the A layer 10 is formed due to uneven application thickness of the adhesive when the laminated configuration with the A layer 10 and uneven thickness of the A layer 10 itself, May be lost and the surface state may be uneven. However, in the case of using the A layer 10 having the composition of the present invention, when laminating the metal-coated laminated sheet 100 of the present invention on the metal plate 50, the normal laminating temperature (used in conventional PVC laminating equipment) is used. The elastic modulus of the A layer 10 is remarkably lowered by the heat from the metal plate 50 heated to about 230 ° C., which is the temperature that has been reached (a state where A is once melted), and the B layer 20 Is released from the restraining force of the A layer 10 for a short time, so that the mirror surface appearance of the surface can be recovered by the elastic recovery force inherent to the B layer 20, and the laminated sheet-coated metal plate 200 of the present invention can be recovered. The mirror surface appearance can be improved.

  On the other hand, if the a-2 component is too much beyond the range of the present invention, the crystallinity of the A layer 10 becomes too high, the surface smoothing due to the mechanism as described above does not occur, and the laminated sheet The coated metal plate 200 cannot have a mirror appearance. Furthermore, the influence of the surface roughness of the metal plate 50 is reflected, which may result in an appearance far from the mirror surface.

  As the polybutylene terephthalate resin which is a-2 component, each single component of terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component and 1.4-butanediol as a diol component (not including an unintended copolymer component) It is preferable to use a so-called homo-PBT resin using the above-mentioned) from the viewpoint of cost and stable supply. When a sheet is prepared by an extrusion film forming method, a PBT resin having a raw material IV value of about 1.0 to 1.4 is generally used, and various grades of PBT resins are commercially available from various companies.

  However, in addition to the homo PBT resin, one obtained by substituting a part of the acid component with a dicarboxylic acid such as isophthalic acid or one obtained by copolymerizing polytrimethylene glycol (PTMG) can be used.

  In contrast, homopolyethylene terephthalate (homoPET) resin is also a crystalline resin, but since the crystallization rate is slow, it is difficult to express boiling water immersion in the blend composition of layer A 10, so It is not preferable to use it. Further, when the PET resin is crystallized in an unoriented state, the crystal phase of the PET resin is less flexible than the crystal phase of the PBT resin, so that the workability is remarkably lowered, and it tends to break when bent. Also from this point, it is preferable to use PBT resin instead of PET resin as the a-2 component.

(A-3 component)
As the polyester resin that is substantially non-crystalline as the a-3 component, a polyester resin that does not show a clear crystal melting peak at the time of temperature rise by a differential scanning calorimeter (DSC) can be used.

  The polyester resin which is substantially amorphous as the a-3 component has terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 20 to 80 mol. % Is preferably a copolymer ester composed of 1.4-cyclohexanedimethanol (1.4-CH and the remaining 80 to 20 mol.% Of ethylene glycol.

  Here, “mainly” means 70 mol. Of terephthalic acid or dimethylterephthalic acid based on the whole dicarboxylic acid component (100 mol.%). % Or more, preferably 80 mol. % Or more, more preferably 98 mol. % Is included.

  When the amount of 1.4-cyclohexanedimethanol, which is a diol component, is too small, the characteristics as a crystalline resin become remarkable, and the processability is reduced as in the case where the above-mentioned homo-PET resin is crystallized without orientation. This is not preferable. On the contrary, when the amount of 1.4-cyclohexanedimethanol is too large, crystallinity becomes remarkable and a very high melting point is exhibited. This is not preferable.

  As an example of a substantially non-crystalline polyester-based resin, there can be mentioned so-called PET-G, which is low in cost because of its stable supply of raw materials and a large amount of production. It is preferable to use “Easter PET-G · 6763” manufactured by the company or a similar resin. This “Easter PET-G · 6763” is about 30 mol. Of the diol component of polyethylene terephthalate resin. % Is a substantially non-crystalline polyester resin having a structure in which 1.4-cyclohexanedimethanol is substituted, and no crystallization behavior is observed by DSC measurement.

However, the present invention is not limited to this, and “PCTG · 5445” (a diol component of polyethylene terephthalate) manufactured by Eastman Chemical Co., which shows crystallinity under specific conditions but can be handled as an amorphous resin under normal conditions. having a substituent structure at about 65 mol.% of 1,4-cyclohexanedimethanol.), or the like can also be used, in addition to this, etc. also name does not exhibit crystallinity neopentyl glycol copolymer PET, co A composition in which crystallization is inhibited by a polymerization component can also be used as a substantially non-crystalline polyester resin as the a-3 component.

(A-1 component)
The purpose of adding the non-polyester thermoplastic elastomer having an epoxy group as the component a-1 is to suppress the deterioration of workability over time accompanying the progress of volume relaxation of the A layer 10, and the initial lamination It is to give more flexibility as physical properties of the sheet and to improve workability after aging.

  Further, as workability, not only the occurrence of cracks and cracks but also whitening of the bent portion is a problem. Therefore, the one that makes the whitening of the bent portion more remarkable by addition is used as the a-1 component. It is not possible.

  For example, a thermoplastic elastomer other than a polyester-based resin having no epoxy group has poor compatibility with a polyester-based resin. This is not preferable because remarkable whitening occurs at the bent portion.

  In addition, as a thermoplastic elastomer other than a polyester-based thermoplastic elastomer having no epoxy group, it is possible to reduce the dispersed particle size in the polyester-based resin to some extent by using a polyolefin resin modified with maleic anhydride. However, even in this case, it is not preferable because the bent portion of the laminated sheet-covered metal plate 200 is also whitened.

  On the other hand, the a-1 component used in the present invention can be finely dispersed in the polyester resin by having an epoxy group. Therefore, whitening hardly occurs at the bent portion of the laminated sheet-coated metal plate 200.

  Further, when a polyester elastomer is used, it has compatibility with the polyester resin, so that it can be made into a blend composition that does not cause whitening even if it does not have an epoxy group. However, since the polyester-based elastomer is a polyester-based resin that exhibits a glass transition temperature lower than room temperature due to a copolymerization component, the glass transition temperature of the blend composition is also lowered. Therefore, in a blend composition containing a crystalline polybutylene terephthalate resin as in the A layer 10 of the present invention, crystallization proceeds excessively in the A layer 10 due to storage at room temperature. Thus, the workability of the laminated sheet-covered metal plate 200 after time may be reduced. Therefore, it is not preferable to use a polyester-based elastomer.

  The non-polyester thermoplastic elastomer having an epoxy group as the component a-1 is preferably added in the range of 3 to 15% by mass based on the mass of the entire resin component of the A layer 10 (100% by mass). It is more preferable to add in the range of 5 to 10% by mass.

  If the added amount of the non-polyester thermoplastic elastomer having an epoxy group is too small, the effect of suppressing the deterioration of secondary processability over time is not sufficient. Conversely, if the added amount is too large, how much polyester is added. Although it is finely dispersed in the resin, it is a non-polyester material that is inherently poor in compatibility, so that it tends to cause a problem of bending whitening. Moreover, when there is too much addition amount, the A layer 10 will become excessively flexible, and even when the stretched polyester resin having a relatively large thickness is used for the surface layer 20, the surface hardness of the laminated sheet 100 is sufficient. There is a risk that it will not.

  As the non-polyester thermoplastic elastomer having an epoxy group which is the component a-1 of the present invention, an epoxy-modified styrene / butadiene block copolymer or an epoxy-modified polyolefin resin is preferably used. it can.

  As the epoxy-modified styrene / butadiene block copolymer, a block copolymer comprising a polymer block (a) mainly composed of a styrene compound and a polymer block (b) mainly composed of a conjugated diene compound. What epoxidized the unsaturated carbon double bond in the unit derived from the conjugated diene compound (“ab”, “abba”, etc.) can be preferably used. Specifically, “Epofriend A1020” manufactured by Daicel Chemical Industries, Ltd. can be used.

  As the epoxy-modified polyolefin resin, a random copolymer of glycidyl methacrylate and ethylene can be preferably used. Specifically, “Bond First E” from Sumitomo Chemical Co., Ltd. can be used.

(Other ingredients)
The A layer 10 is provided with a design property, a visual concealing effect for the metal plate 50 to be coated, and a pigment added for the purpose of improving the coloration when the printed pattern 30 is provided on the surface. Is done. The pigment to be used may be one generally used for the above purpose, and the addition amount thereof may be an amount generally added for the above purpose. As an example, it is possible to use a titanium oxide pigment that has a high concealing effect in white-based coloring and has a small influence on the processability of a laminated sheet because the particle size is fine. Further, based on the titanium oxide pigment, the color can be adjusted by adding a small amount of a chromatic organic or inorganic pigment. Furthermore, a metallic pigment, a pearl pigment, or the like may be included for the purpose of improving design properties.

  Regarding the visual hiding effect of the base, the degree of importance varies depending on the application and cannot be specified unconditionally. However, as a guideline, in the laminated sheet-coated metal plate 200 for interior building materials, JIS K5400 7.2 “Paints in general It is often required that the concealment ratio measured in accordance with “Test method / Concealment ratio” is 0.98 or more, and the laminated sheet-covered metal plate 200 of the present invention preferably satisfies this value.

  In addition, various amounts of various additives may be added to the A layer 10 as long as the properties are not impaired. General additives include phosphorus, phenol and other antioxidants, lactones, phenol acrylate and other process stabilizers, heat stabilizers, UV absorbers, hindered amine radical scavengers, and various processing aids. , Metal deactivators, lubricants, antibacterial / antifungal agents, antistatic agents, flame retardants, pigment dispersibility improving agents, filling / extending agents, and the like.

  A preferred thickness of the A layer 10 is in the range of 50 to 200 μm. When the thickness of the A layer 10 is too thin, it is necessary to add a large amount of pigment in order to ensure visual concealment of the base, and as a result, the processability of the A layer 10 may be reduced. On the contrary, when the thickness of the A layer 10 is too thick, the effect required for the A layer 10 is saturated.

<Surface layer (B layer) 20>
The purpose of the B layer 20 is to improve surface physical properties such as scratch resistance and chemical resistance, to give the design sheet 100 a so-called specular surface smooth appearance, and to be transparent and have a certain thickness. The expression of the depth as a design by applying to the surface, and the protection of the printed pattern C30 when the printed pattern C30 described below is provided.

  Conventionally, even when a soft PVC sheet is used as a base material layer, a transparent polyester film has been used as a surface layer for the above purpose. Accordingly, the B layer 20 can be used without limitation as long as it is a transparent polyester film that has been used in the past and can achieve the above-mentioned purpose, but it has been proven to be biaxially stretched since the days when soft PVC sheets were used. Polyester resins, in particular, biaxially stretched polyethylene terephthalate-based transparent resin sheets can be preferably used, and biaxially stretched homopolyethylene terephthalate-based transparent resin sheets can be particularly preferably used.

  The thickness of the B layer 20 is preferably 15 to 100 μm, and may be the same as the thickness of the transparent resin film that has been used to obtain a specular resin-coated metal sheet by overlaying on a conventional soft PVC sheet. Further, it is preferable to use a biaxially stretched homopolyethylene terephthalate sheet having a stretching ratio of 3.5 to 5 times in each direction of the biaxial axis and a heat setting temperature after the stretching treatment of 220 to 240 ° C. Thus, it can be made preferable from the point of acquisition cost by making a draw ratio, heat setting temperature, etc. the same as before.

  When the thickness of the B layer 20 is in the range of 15 to 30 μm and the thickness of the adhesive layer (D layer) 40 described below is in the range of 1 to 3 μm, the enthalpy relaxation of the A layer 10 is achieved. Even when the process proceeds, there are few cases where the secondary workability of the laminated sheet-coated metal plate 200 becomes a problem. However, the thickness of the B layer 20 is more preferably 35 μm or more so that a deep design feeling can be obtained, or the total thickness of the B layer 20 and the D layer 40 is 35 to 115 μm. Is more preferable. In the laminated sheet-coated metal plate 200 of the present invention, even when the thickness of the B layer 20 and / or the D layer 40 is increased, the laminated sheet-coated metal plate 200 is stored for a long time after being produced. Secondary workability can be improved. However, if the total thickness of the B layer 20 and the D layer 40 exceeds 115 μm, the initial workability may not be sufficient, and it becomes difficult to wind the manufactured laminated sheet 100, and the lamination process And this may cause problems in the storage process.

  When a design with surface irregularities by embossing is required instead of a surface-smooth design called a mirror-like appearance, what is called an easily workable biaxially stretched polyethylene terephthalate or the like can be used as the B layer 20. . This easily workable biaxially stretched polyethylene terephthalate is a state in which a flexible resin layer is laminated on the lower layer by controlling the orientation without impairing the basic performance as a biaxially stretched polyethylene terephthalate sheet such as chemical resistance. The embossing suitability can be obtained, and examples of such easily processable biaxially stretched polyethylene terephthalate sheets include “Teflex” by Teijin DuPont Films and “New Concept Mirror” by Toray. it can.

  An appropriate amount of various additive components for resin may be added to the B layer 20. Except for additives that significantly reduce transparency or may cause voids during stretching, resulting in a decrease in physical properties, the same additives that can be used for the A layer 10 can be used. .

<Print pattern C30>
As schematically shown the layer configuration in FIG. 1B, in the present invention, a printed pattern C30 can be provided. The printed pattern C30 can be applied by a known printing method such as gravure printing, offset printing, or screen printing. The pattern of the print pattern C30 is arbitrary, such as a stone pattern, a grain pattern, a geometric pattern, and an abstract pattern. The printed pattern C30 may be partially printed or entirely solid printed, and both the partially printed pattern and the solid printed may be applied.

  The printed pattern C30 may be applied as a so-called back print on the side of the B layer 20 with the A layer 10, or may be applied to the surface of the A layer 10 on the side of the B layer 20 laminated, You may provide to both the B layer 20 side and the A layer 10 side. However, in the case where a back print is applied to the layer surface side of the B layer 20 with the A layer 10 and the thickness of the adhesive layer (D layer) 40 described below is increased to give a sense of depth ( In the form shown in the schematic diagram of the layer structure in FIG. 1D, it is preferable that the printed pattern C30 is a partial print having a relatively large light-transmitting portion or a printing ink having a low concealability. In addition, in FIG.1 (f), the layer structure which provided the printing pattern C30 to both the A layer 10 side and the B layer side 20, and has arrange | positioned the adhesive bond layer (D layer) 40 between them was shown typically.

<Adhesive layer (D layer) 40>
As shown schematically in FIG. 1 (c) to FIG. 1 (f), in the laminated sheet 100 for covering a metal plate of the present invention, between the A layer 10 and the B layer 20 (FIG. 1 ( c)), or when the printed pattern C30 is provided, between the printed pattern C30 and the A layer 10 (form of FIG. 1D), between the printed layer C30 and the B layer 20 (FIG. 1). (Form (e)), an adhesive layer (D layer) 40 is disposed between the print layer C30 and the print layer C30 (form (f) of FIG. 1).

  As the D layer 40, it is preferable from the viewpoint of workability to use what is generally called an adhesive for dry laminating which is cured with an isocyanate crosslinking agent using a polyester resin or a polyether resin as a main component. Among these dry laminate adhesives, it is more preferable to use an aliphatic adhesive because there are few problems of yellowing due to ultraviolet rays.

  The thickness of the D layer 40 is preferably in the range of 1 to 20 μm in terms of dry film thickness. If the thickness of the D layer 40 is too thin, adhesion failure due to uneven application tends to occur. On the other hand, if the thickness of the D layer 40 is too thick, the workability of the laminated sheet 100 may be reduced. Further, it is difficult to form an adhesive layer having a thickness exceeding 20 μm uniformly in the dry lamination method.

  The total thickness of the B layer 20, the printed pattern C30, and the D layer 40 is preferably set to a thickness of 35 to 115 μm in order to obtain a deep design feeling, but as described above, the thickness of the D layer 40 is Since the upper limit is 20 μm, the remaining thickness is preferably secured by the transparent stretched polyester resin sheet of the B layer 20. When this total thickness is too thin, the progress of enthalpy relaxation of the A layer 10 is unlikely to lead to a decrease in actual workability, but it becomes difficult to obtain a deep design feeling. On the contrary, when this total thickness is too thick, it becomes difficult to obtain good processability regardless of the composition of the A layer 10, which is not preferable.

  The D layer 40 may be colored with a transparent colorant such as a dye system, a fluorescent agent, a bluish imparting agent, etc. for imparting design properties, and metal powder such as surface-modified mica powder, aluminum fine powder, Hologram foil, surface-modified glass flakes and the like may be added. Furthermore, various additives generally added to the curable adhesive may be included in appropriate amounts.

  However, the D layer 40 is not limited to the one described above, and an ultraviolet curable adhesive, an electron beam / radiation curable adhesive, or the like may be used. Alternatively, as the transparent stretched polyester resin sheet of the B layer 20, a so-called easy-adhesive stretched polyester sheet provided with a hot-melt adhesive resin layer by a method such as coextrusion is used, so that the D layer 40 can be omitted. Good. Alternatively, a resin layer having adhesiveness may be formed by co-extrusion with the A layer 10 and the D layer 40 may be omitted.

  In order to impart a deep design to the laminated sheet 100, it is necessary to increase the thickness of the B layer 20 or the D layer 40. Conventionally, forming such as bending processing of a flexible PVC resin-coated metal plate In order to make it possible to use a molding die used for processing, the total thickness of the metal sheet-covering laminated sheet 100 is preferably 300 μm or less.

<Metal plate (E) 50>
FIG. 1 (g) schematically shows the layer structure of the laminated sheet-coated metal plate 200 of the present invention. As the metal plate 50 used for the laminated sheet-coated metal plate 200 of the present invention, a hot-rolled steel plate, a cold-rolled steel plate, a hot-dip galvanized steel plate, an electrogalvanized steel plate, a zinc / aluminum alloy-based steel plate, a zinc / aluminum / magnesium alloy-based material Various steel plates such as plated steel plates, tin-plated steel plates, stainless steel plates, aluminum plates, aluminum alloy plates, titanium alloy plates, nickel alloy plates, and the like can be used.

  Moreover, you may use these metal plates 50, after giving a normal chemical conversion treatment. The thickness of the metal plate 50 varies depending on the use of the laminated sheet-covered metal plate 200, but can be selected within a range of 0.1 to 10 mm. Moreover, in the use of an elevator interior material, it is common to use a hot-dip galvanized steel sheet having a thickness in the range of 1 to 2 mm.

<The manufacturing method of the laminated sheet 100 for metal plate coating, and the laminated sheet coating metal plate 200>
As a manufacturing method of the A layer 10 of the present invention, various known film forming methods can be employed without any particular limitation. For example, a T-die film forming method or an inflation method using an extruder can be employed. In addition, if there is a calendar facility capable of heating the kneading roll above the melting point of the polybutylene terephthalate resin used for the A layer 10, the sheet of the A layer 10 can be obtained also by a calendar film forming method.

  The B layer 20 can also be formed by an extruder equipped with stretching equipment, but various thicknesses for overlay use of conventional PVC resin-coated steel sheets are commercially available. Is convenient.

  As an example of the manufacturing method of the laminated sheet 100 for covering a metal plate of the present invention, a back print is applied to the laminated surface side of the B layer 20, and then a dry lamination adhesive is applied thereon using a coater, followed by hot air drying. The solvent is volatilized and dried using a machine, etc., and simultaneously laminated with the A layer 10 obtained above, and at the same time, a laminated sheet is obtained by passing between a pair of heated crimping rolls at 40 to 80 ° C. The method of curing until it dries can be mentioned.

  Next, a method for manufacturing the laminated sheet-coated metal plate 200 will be described. Using the commonly used coating equipment such as reverse coater, kiss coater, etc. on the above-mentioned various metal plates 50, the adhesive film thickness after drying is about 2 to 10 μm on the metal surface where the laminated and integrated sheets are bonded together The thermosetting adhesive 60 is applied so that it becomes. Examples of the thermosetting adhesive 60 include commonly used thermosetting adhesives such as an acrylic adhesive, an epoxy adhesive, a urethane adhesive, and a polyester adhesive.

  Next, the coated surface is dried and heated by an infrared heater and / or a hot air heating furnace, and the surface temperature of the metal plate 50 is maintained at a temperature of about 190 to 250 ° C., and immediately, using a roll laminator, for coating the metal plate The laminated sheet 100 is coated so that the A layer 10 side is the adhesive surface. Thereafter, forced cooling such as natural cooling, water cooling, and air cooling is performed to obtain the laminated sheet-coated metal plate 200.

In order to describe the present invention more specifically and in detail, the following examples are given, but the present invention is not limited to these examples.

(Formation of layer A)
A base layer (A layer) having a thickness of 80 μm by a T-die film forming method, which is a general method for forming a polyester sheet, using a vented same-direction biaxial kneading extruder with the resin composition shown in Table 1. (“A-1” to “a-24”) were formed. In addition to the resin composition of Table 1, the layer A is added with a titanium oxide white pigment and an organic green pigment, and light green (L value = 76, a value = −34 in Lab color coordinates, It is colored b value = 9). The amount of pigment added is the same for all A layers. In addition, the value in Table 1 is mass%.

Each raw material used in Table 1 is as follows.
“Novaduran 5020S” is a polybutylene terephthalate (homo PBT) resin manufactured by Mitsubishi Engineering Plastics. I. V. A standard grade for extrusion film formation with a value = 1.2. The melting point is 225 ° C.

  “Easter PETG • 6763” is manufactured by Eastman Chemical Company, the dicarboxylic acid component is terephthalic acid, and about 30 mol. % Is 1.4-cyclohexanedimethanol, about 70 mol. It is an amorphous copolymerized PET resin in which% is ethylene glycol. The glass transition temperature is 78 ° C., and no melting point is observed.

  “PCTG 5445” is manufactured by Eastman Chemical Company, the dicarboxylic acid component is terephthalic acid, and the diol component is about 65 mol. % Is 1.4-cyclohexanedimethanol, about 35 mol. % Is a substantially non-crystalline copolymerized PET resin having ethylene glycol. The glass transition temperature is 86 ° C. and no melting point is observed.

  “Dianite / DN-124” is a low crystalline polyester elastomer manufactured by Mitsubishi Rayon Co., Ltd. The glass transition temperature is 19 ° C. and no melting point is observed.

  “Epofriend A-1020” is an epoxy-modified styrene / budadiene / styrene / triblock copolymer manufactured by Daicel Chemical Industries.

  “Bond First E” is an ethylene / glycidyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd.

  “Dynalon 1320P” is a styrene / hydrogenated butadiene rubber block copolymer manufactured by JSR.

  “Hibler 7125” is a styrene / vinyl / polyisoprene / triblock copolymer manufactured by Kuraray.

(Preparation of layer B, printed pattern C and layer D)
A partial print of an abstract pattern was printed on one side of a commercially available biaxially stretched polyethylene terephthalate film (B layer) (layer B) (Teijin Tetron SG: manufactured by Teijin DuPont Films) with the thickness shown in Table 2 by a back print (print pattern) C) A cyanate-curable polyester-based adhesive (main component is TM-K51: manufactured by Toyo Morton Co., Ltd.) having a thickness shown in Table 2 was applied to the printed surface, and preliminary drying for volatilizing the solvent was performed. Thereby, the printing pattern C was provided and the B layer ("b-1"-"b-8") in which the contact bonding layer (D layer) was formed was obtained. The type of printing ink and the printing pattern (ink application amount) are the same for all the B layers.

(Examples 1 to 23)
The A layer of the type shown in Table 3 and the B layer on which the printed pattern C is applied and the adhesive layer (D layer) is formed are overlapped, and this is passed between a pair of rolls heated at 80 ° C. Thus, the laminated sheet for metal plate coating according to the present invention was obtained. The adhesive film thickness after drying a commercially available polyester adhesive for a polyvinyl chloride coated metal sheet is about 2 to 4 μm on the surface of the laminated sheet in the galvanized steel sheet having a thickness of 0.45 mm. Then, the adhesive coating surface was dried and heated with an infrared heater and a hot air heating furnace, and the surface temperature of the galvanized steel sheet was maintained at 235 ° C. and immediately using a roll laminator. The laminated sheet coated metal sheet of the present invention was obtained by coating the metal sheet-coated laminated sheet and cooling. In addition, the surface heating by the non-contact-type heater etc. with respect to the lamination sheet coating metal plate after lamination, the press with the mirror surface roll in this heating state, etc. are not implemented in particular.

(Comparative Examples 1-15)
Laminate for covering a metal plate in the same manner as in Example 1 except that the A layer of the type shown in Table 4 and the B layer to which the printed pattern C was applied and the adhesive layer (D layer) was formed were overlaid. Sheets and laminated sheet-coated metal plates were obtained.

<Evaluation method>
An evaluation method of the laminated sheet-coated metal plate produced in the above examples and comparative examples is shown below. The results of evaluation according to each evaluation method are shown in Table 3 and Table 4. In addition, Examples 1-12 and Comparative Examples 1-12 are the examples which used the same thing as B layer and D layer.

(Processability evaluation (1): bending workability test)
Evaluation of the V bending method prescribed | regulated by "JIS Z-2248" was performed to the laminated sheet coating metal plate of 40 mm x 60 mm. In the V-bending method, a screw bending test apparatus 300 whose entire view is shown in FIG. The screw bending test apparatus 300 includes an upper mold lifting handle 310, an upper mold lifting screw 320, an upper mold installation portion 330, and a lower mold installation portion 340. By manually turning the upper die lifting handle 310 provided on the upper portion of the upper lifting screw 320, the upper lifting screw 320 is moved in the vertical direction, and accordingly, provided at the lower end of the upper lifting screw 320. The upper mold installation part 330 moves in the vertical direction. Further, as shown in the enlarged view of the V-bending portion in FIG. 2B, the upper die installation portion 330 is provided with a V-bending upper die 350, and the lower die installation portion 340 is provided with a V-bending lower portion. A mold 360 is provided. Then, by operating the upper mold lifting handle 310, the V bending upper mold 350 provided in the upper mold installation portion 330 is moved downward, and the test piece 380 is sandwiched between the V bending lower mold 360. As a result, the test piece 380 is deformed into a V shape.

  Specifically, a flat test piece 380 is placed on a metal lower mold 360 on which a V-shaped groove 370 having an angle of 90 degrees is formed, with the laminated sheet covering side in contact with the lower mold 360, and the tip The metal upper die 350 formed in the shape of a 90-degree V-shape corresponding to the V-groove 370 of the lower die 360 is manually turned down by the screws 310 and 320 and the test piece 380 is pushed into the V-groove 370. 90 degree bending is performed.

  This workability evaluation was performed at an ambient temperature of 23 ° C. For initial workability evaluation where enthalpy relaxation has not progressed, measurement was carried out within 24 hours after laminating the laminated sheet to the metal plate, and for workability evaluation after time, 40 ° C. × 90% RH. The sheet was allowed to stand for 30 days in a kept constant temperature and humidity chamber and then taken out, left in a room at 23 ° C. for 24 hours, and then subjected to measurement. The surface state of the laminated sheet for covering the metal plate in the bent part after processing is judged by visual observation. “○” indicates that there is almost no change, the surface layer is slightly cracked, and the surface is slightly bent and whitened. Was evaluated as “C”, and those with cracks in the surface layer or those with significant bending whitening were evaluated as “x”.

(Processability evaluation (2): Eriksen test with notch)
Using a commercially available cutter knife on the surface of the laminated sheet-coated metal plate 200 of 60 mm × 60 mm as shown in FIGS. A cut 410 extending to the interface between the laminated sheet 100 and the metal plate 50 was made to form a cut portion 420 having a width of 5 mm. Then, using an Erichsen test apparatus defined in “JIS K-6744”, a projecting process with a height (H) of 6 mm was applied so that the coated side of the laminated sheet 100 was convex, and the resin layer was cut. The peeling state of the part 420 was observed. FIG. 3C shows a front view of the laminated sheet-covered metal plate 200 in a state where the overhang processing is performed, and FIGS. 3D and 3E show side sectional views.

  Regarding the initial workability evaluation in which enthalpy relaxation has not progressed, the measurement was performed within 24 hours after laminating the laminated sheet to the metal plate, and regarding the measurement of workability after time, 40 ° C. × 90% RH. The sheet was allowed to stand for 30 days in a constant temperature and humidity chamber maintained at room temperature, then taken out and left in a room at 23 ° C. for 24 hours, followed by measurement.

  As shown in FIG. 3 (d), the case where no separation is observed, and the case where the separation length (L) is less than 1 mm is “◯”, and the case where significant separation occurs is “x”, and the middle A film having a peel length (L) of 1 to 2 mm was evaluated as “Δ”. The peeling length (L) refers to a linear distance from the notch 410a to the boundary line 450 at the portion where the metal plate 50 and the laminated sheet 100 are peeled off as shown in FIG. The measurement of peel length is 2 samples, and the average value is obtained by measuring at 4 locations per sample. If there is a peel length exceeding 2 mm even at one location, it is evaluated as “x”. did.

(Boiling water immersion test)
Using an Erichsen test device specified in “JIS K-6744” on a 60 mm × 60 mm laminated sheet-coated metal plate, a 6 mm overhang is provided so that the laminated sheet coating side is convex, and then immersed in boiling water for 3 hours. Then, the surface state of the resin sheet was visually determined. “○” indicates that there was no change at all, and “Slightly roughened surface” or “Slight peeling” occurred between the transparent biaxially stretched polyethylene terephthalate resin layer laminated on the surface layer and the base material layer. Evaluation was made as “C” where “Δ” or a resin layer with significant deformation such as blistering occurred.

(Specularity: Sharpness and glossiness value (Gd value))
Using the <PGD> portable sharpness gloss meter PGD-IV developed by the Japan Color Research Institute, the specular reflectivity of each laminated sheet-coated metal plate of Examples and Comparative Examples was determined by the measurement method prescribed by the same corporation. Measured and used as a criterion for specularity. The measurement was performed at five locations in the same sample, and the average value was defined as a sharpness value (Gd value). The case where the Gd value was 0.9 or more was evaluated as “◯”, the case where it was 0.8 or more and less than 0.9 was evaluated as “Δ”, and the case where it was less than 0.8 was evaluated as “x”.

<Evaluation results>
Comparative Example 1 is a case where only an amorphous polyester resin was used for the A layer. At the same time, a remarkable change in appearance was observed in the boiling water immersion test, and at the same time, the laminated sheet was significantly removed from the metal plate in the notched Ericksen test. It was peeling.

  In Comparative Example 2 and Comparative Example 3, the PBT resin, which is a crystalline polyester resin, is added to the A layer, so that there is almost no problem in immersion in boiling water, but significant peeling occurs in the notched Eriksen test after time. As a result. Moreover, in the comparative example 3 with much addition amount of PBT resin, the result of the mirror surface property of the resin coating metal plate was a little inferior.

  In Comparative Example 4 in which the addition amount of PBT was further increased, the workability deterioration after aging was not so much observed. This is considered to be due to the fact that the A layer has high crystallinity and the amorphous volume is small, so that the influence of enthalpy relaxation is small. However, the specularity was inferior.

  Comparative Example 5 is also the case where the non-polyester thermoplastic elastomer component was not added to the A layer as in Comparative Examples 1 to 4, but the results of the notched Ericksen test after aging were inferior. .

  Comparative Example 6 and Comparative Example 8 are cases where the amount of the non-polyester thermoplastic elastomer having an epoxy group added to the A layer is small, and the result of the notched Ericksen test after the lapse of time is that the thermoplastic elastomer was added. The result was not much different from the case of not doing it.

  Comparative Example 7 and Comparative Example 9 are cases where the amount of the non-polyester thermoplastic elastomer having an epoxy group added to the A layer is large, and good results have been obtained in the notched Eriksen test after aging. The 90-degree bending test has a bad result from the beginning. This is because, even if the thermoplastic elastomer having an epoxy group is finely dispersed in the polyester-based resin, if it is added in a large amount, it will be bent and whitened from the beginning.

  Comparative Example 10 and Comparative Example 11 are cases in which a thermoplastic elastomer having no epoxy group was added. In this case as well, although an improvement effect was observed for the notched Ericksen test after aging, a 90-degree bending test Has a bad result from the beginning. It is considered that bending whitening occurs when the elastomer component is dispersed in a relatively large size in the polyester resin.

  Comparative Example 12 is a case where a polyester-based elastomer was added, but both the 90-degree bending test and the notched Eriksen test showed poor results after aging. In this case, the progress of enthalpy relaxation was not the cause, and the glass transition temperature of the blend composition of the A layer was lowered, so that crystallization progressed in an environment of 40 ° C. × 90% RH and the workability was lowered. It is considered a thing. The difference from Comparative Example 4 which is inherently highly crystalline is that a large spherulite is formed when crystallization proceeds under conditions of low temperature and long term with a composition having many amorphous components as in Comparative Example 12. It is thought that it depends. It should be noted that the blend ratio of the PBT resin of the A layer is the same level as in Comparative Example 12, but no polyester-based elastomer is added, and therefore the Tg of the blend composition is not so low in Comparative Example 3 and Comparative Example 5 The result of the 90-degree bending test is not worse.

  Comparative Examples 13, 14 and 15 use the same A layer as Examples 7, 8 and 12 of the present invention, but bend 90 degrees from the beginning because the B layer is too thick. The test and notched Eriksen test cannot be satisfied.

  On the other hand, with respect to Examples 1 to 23 of the present invention, the PBT addition amount of the A layer is Example 1 close to the lower limit of the range of the present invention, and the appearance after immersion in boiling water is somewhat deteriorated. In Example 6, in which the amount of the thermoplastic elastomer having a group is the lower limit of the present invention, the results of the notched Eriksen test after aging are slightly worse, but both are judged to be at a level that is not problematic in practice. It was done. In addition, in Example 18 and Example 23 in which the thickness of the B layer + D layer is the upper limit in the preferred range of the present invention, the result of notched Erichsen is somewhat bad from the beginning, but this is also a problem in practical use. It was judged that there was no level. For the other examples, good results have been obtained for these evaluations.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can also be appropriately modified within the scope of the invention that can be read from the claims and the entire specification without departing from the spirit or concept of the invention, and a laminated sheet for covering a metal plate and a laminated sheet-covered metal plate accompanying such a change are also included in the present invention. Should be understood as being included in the technical scope of

It is the schematic diagram which showed the layer structure of the laminated sheet 100a for metal plate coating. It is the schematic diagram which showed the layer structure of the lamination sheet 100b for metal plate coating. It is the schematic diagram which showed the layer structure of the lamination sheet 100c for metal plate coating. It is the schematic diagram which showed the layer structure of the laminated sheet 100d for metal plate coating | covers. It is the schematic diagram which showed the layer structure of the lamination sheet 100e for metal plate coating. It is the schematic diagram which showed the layer structure of the laminated sheet 100f for metal plate coating | covers. 4 is a schematic diagram showing a layer configuration of a laminated sheet-coated metal plate 200. FIG. It is a general view (Drawing 2 (a)) of a screw bending test device, and an enlarged view (Drawing 2 (b)) of a V bending part. It is explanatory drawing which shows the outline | summary of the Eriksen test method with a notch.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Laminated sheet for metal coating 200 Laminated sheet coating metal plate 10 Base material layer (A layer)
20 Surface layer (B layer)
30 Print Pattern C
40 Adhesive layer (D layer)
50 Metal plate 60 Adhesive 300 Screw bending test device 310 Upper mold lifting handle 320 Upper mold lifting screw 330 Upper mold installation part 340 Lower mold installation part 350 V Bending upper mold 360 V Bending lower mold 370 Lower mold V-shape Mold groove part 380 Test piece 410, 410a Notch 420 Notch part 450 Boundary line

Claims (8)

A laminated sheet having at least two layers of a base layer (A layer) made of a resin containing a pigment and a surface layer (B layer) having a thickness of 100 μm or less, composed of a transparent stretched polyester resin,
The non-polyester thermoplastic elastomer (a-1 component) having 21 to 48% by mass of the A layer is 3 to 15% by mass with respect to 100% by mass of the entire resin component in the A layer. A laminated sheet for covering a metal plate, comprising a butylene terephthalate resin (a-2 component) and a polyester resin (a-3 component) that is 42 to 73% by mass of substantially amorphous.   The substantially amorphous polyester-based resin (a-3 component) of the A layer is mainly composed of terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component, and 20 to 80 mol. % Is 1.4-cyclohexanedimethanol, and the remaining 80 to 20 mol. The laminated sheet for metal plate coating according to claim 1, wherein% is a copolymerized polyester made of ethylene glycol.   The non-polyester thermoplastic elastomer (a-1 component) having the epoxy group of the layer A is an epoxy-modified styrene-butadiene block copolymer or an epoxy-modified polyolefin resin. Item 3. The laminated sheet for covering a metal plate according to Item 1 or 2.   The B layer is a biaxially stretched homopolyethylene terephthalate resin, and a printed pattern (printed pattern C) and an adhesive layer (D layer) are disposed between the B layer and the A layer. Item 4. A laminated sheet for covering a metal plate according to any one of Items 1 to 3. The laminated sheet for metal plate coating according to claim 4, wherein the total thickness of the B layer, the printed pattern C, and the D layer is in a range of 35 μm to 115 μm.   A laminated sheet-covered metal plate obtained by laminating the metal sheet-covered laminated sheet according to any one of claims 1 to 5 on a metal plate with the surface on the A layer side as an adhesive surface.   Detachment length of the laminated sheet for covering a metal plate from a metal plate when the Erichsen test with a notch was performed at an ambient temperature of 23 ° C. after being left in a constant temperature and humidity chamber of 40 ° C. and 90% relative humidity for 30 days. The laminated sheet-coated metal sheet according to claim 6, wherein the thickness is 2 mm or less.   A building interior material selected from the group consisting of a unit bath wall material, a unit bath ceiling material, a door material, a general interior wall material, and a partition material using the laminated sheet-covered metal plate according to claim 6 or 7.

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