JP2010006020A - Laminated sheet, embossed design sheet, metal sheet coated with embossed design sheet, prefabricated bath member, building interior material, steel furniture member, and household electric product case member - Google Patents

Abstract

The present invention provides a laminated sheet that has good lamination suitability to a metal plate, can impart a heat-resistant embossed design, and can accurately transfer a precision embossed design.
A laminated sheet 100 having three layers of an A layer 10, a B layer 20, and a C layer 30 from the surface and having a total thickness in a range of 55 μm to 300 μm. A layer: A non-oriented layer having a thickness of 100 μm or less, which is mainly composed of a copolymerized polyester resin composition part that is substantially amorphous. B layer: A layer having a thickness of 40 μm or more, which is mainly composed of a polyester resin that is substantially amorphous and to which a colorant is added. C layer: a polybutylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less and / or a polytrimethylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less, and the mass of the entire resin component in the C layer A non-oriented layer having a thickness of 5 μm or more, comprising 70% by mass or more and 95% by mass or less as 100% by mass.
[Selection] Figure 1

Description

  The present invention is a home appliance housing member such as AV equipment, air conditioner cover, plywood furniture member, steel furniture member, unit bath wall material, unit bath member such as unit bath ceiling material, closet door material, partition material, etc. A laminated sheet excellent in heat resistance of embossing and excellent in metal sheet lamination suitability, which can be suitably used for coating materials having an embossed design such as building interior materials, an embossed design sheet in which embossing is applied to the laminated sheet, The present invention also relates to an embossed design sheet-covered metal plate coated with the embossed design sheet.

Conventionally, a synthetic resin molded product, plywood, wood fiber board, metal plate, etc. are coated with a soft vinyl chloride resin sheet (hereinafter referred to as “soft PVC sheet”) with an embossed design for the above uses. Has been used. As a characteristic of the soft PVC sheet,
(1) Since it is excellent in embossing suitability, a coating material rich in design can be obtained.
(2) The balance between workability, which is generally a contradiction element, and surface scratch resistance is relatively good.
(3) It is easy to obtain a resin film having excellent durability because of excellent compatibility with various additives and studies on improving physical properties with additives for many years.
Etc. can be mentioned.

  As a method for continuously imparting an uneven surface design called embossing to a long sheet of soft PVC, a roll obtained by softening a sheet after film formation by reheating and engraving an embossed pattern (embossed roll) In general, a method of continuously transferring the pattern while suppressing the pattern is used. As a method for heating the sheet, a contact type in which the sheet is heated by being brought into contact with a heated metal roll, a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater, a hot air heater, or the like can be considered. In an actual production line, only either one may be used, but generally both are often used together. An equipment having a series of these steps is called an embossing device or the like.

  In general, the embossing apparatus incorporates a design that makes it easy to replace and remove the embossing plate roll. The embossing plate roll has a smaller diameter than the casting roll of an extrusion film-forming facility. Therefore, it can be said that it is an embossing method suitable for small lot compatibility because it is possible to easily and economically change the embossed pattern by preparing various embossed plate rolls.

  In addition, for a soft PVC sheet having a printing design at the same time as an embossed design, a transparent soft PVC sheet is laminated and integrated after a printed pattern is applied to the surface of a colored soft PVC sheet by a gravure printing method or the like. Was continuously passed through an embossing device. In this case, using the sheet preheating in the embossing device, it is possible to adopt a method of stacking and integrating two layers of sheets by heat fusion, and no special process for stacking integration is required. Productivity was good and cost was excellent.

  As described above, the flexible PVC sheet itself has excellent characteristics, and an embossing technique for the flexible PVC sheet and an application facility have been established. It was manufactured. However, in recent years, the use of vinyl chloride resins has been restricted due to the VOC problem and the endocrine disrupting action, and in particular, for interior building materials that have a long contact with humans, soft PVC is used. There is a need for a resin-coated metal plate that does not use a sheet.

  Therefore, as an alternative to a soft PVC sheet, use of a sheet made of a polyester resin excellent in processability and surface scratch resistance for use in a resin-coated metal plate having an embossed design has been studied. As such a sheet, for example, Patent Document 1 discloses that a base film layer mainly composed of an amorphous polyester resin, a dicarboxylic acid component composed of terephthalic acid, and 25-35 mol% 1,4-cyclohexanedi A decorative sheet in which a transparent protective film layer mainly composed of an amorphous polyester resin obtained by copolymerizing methanol and a diol component composed of 65 to 75 mol% of ethylene glycol has been proposed.

  In Patent Document 2, a substantially amorphous or low-crystalline resin composition or an embossable layer (A layer) containing a large amount of this resin composition, and a substantially crystalline resin composition Or a layer (B layer) that contains a large amount of this resin composition and imparts tension to the laminated sheet during heating in the embossing apparatus and at the same time imparts non-stickiness to heated metal parts such as a heating drum of the embossing apparatus It is disclosed that the present embossing apparatus for PVC is used without causing problems of sheet fusing, sticking to a heating roll or winding.

  However, in the composition in Patent Document 1, since both of the two layers are mainly composed of an amorphous polyester resin, the tension when the sheet is heated by the embossing apparatus is not sufficient. There is a risk of causing shrinkage, wrinkling, breakage, etc., and since the base material layer is mainly composed of an amorphous polyester resin, there is a concern of sticking to the heating drum of the embossing device, It is difficult to produce a sheet having an embossed design stably with an embossing apparatus. Further, an amorphous polyester resin obtained by copolymerizing a dicarboxylic acid component composed of terephthalic acid, a diol component composed of 25 to 35 mol% 1,4-cyclohexanedimethanol and 65 to 75 mol% ethylene glycol, Since the glass transition temperature (Tg) is about 80 ° C., when a laminated sheet made of the composition is laminated on a heated metal plate to form a resin-coated metal plate, the so-called embossed corner becomes shallow. There is a possibility that a phenomenon called wrinkle return or emboss return will occur, resulting in a decrease in design feeling.

In embossing by the embossing device to the thermoplastic resin sheet, since the stress generated in the resin sheet due to pressing by the embossing roll is not sufficiently relaxed, the unevenness by the embossing Has a property of heat-recoverable distortion, and when it is heated in a subsequent process, it recovers the distortion and thus causes emboss return.
As the heating in the subsequent process, in the above, the temperature in the vicinity of the surface of the resin sheet to which embossing has been imparted is increased by heat transfer from the heated metal plate when laminating to the metal plate. In the case of resin-coated metal plates used for unit bath applications, the same emboss return will occur when the boiling water immersion test included in the evaluation items for the applications is generally performed. .

Furthermore, when a resin-coated metal plate is prepared using the laminated sheet of Patent Document 1, the base material layer is mainly composed of an amorphous polyester resin having a glass transition temperature (Tg) of about 80 ° C. For this reason, in the boiling water immersion test, not only the surface embossing return but also the flow deformation of the resin layer accompanying the decrease in the elastic modulus of the base material layer itself may occur, which may cause a remarkable appearance defect.

Patent Document 2 is excellent in non-adhesiveness to a heating roll of an embossing apparatus and a layer mainly composed of a substantially amorphous polyester resin excellent in emboss transferability, and maintains sufficient tension. It is possible to improve the embossing suitability by functionally differentiating into a layer mainly composed of a specific crystalline polyester-based resin, and the embossing can be given by heating the sheet to a higher temperature. . As described above, embossing is imparting heat-recoverable strain, and thus the higher the application temperature, the higher the restoration temperature. This suppresses the occurrence of emboss return when laminating to a heated metal plate.
Further, in Patent Document 2, a specific crystalline polyester resin such as polybutylene terephthalate resin is blended in a layer mainly composed of a substantially amorphous polyester resin serving as an embossing imparting layer. Therefore, it is possible to effectively suppress the embossing return in the boiling water immersion test using the crystallinity, and the resin-coated metal obtained by laminating this laminated sheet has a layer mainly composed of a crystalline polyester resin. With respect to the plate, the flow deformation of the resin layer during immersion in boiling water is also effectively prevented, and the appearance is not defective in the test.

  However, even in such a laminated resin sheet described in Patent Document 2, the so-called precision embossed design is very shallow, and in terms of transferring a fine embossed design by an embossing machine, compared to a soft PVC sheet. It was not good, and there was a need for improvement.

  This is because when embossing is applied to a layer containing a substantially amorphous polyester resin as a main component, the heating temperature of the laminated sheet and the embossing plate roll temperature are set in order to ensure the heat resistance of the embossing. As a result, the temperature of the embossing plate roll becomes higher than the glass transition temperature (Tg) of the amorphous polyester resin of the layer to which embossing is to be applied. This is a cause of poor transferability.

  That is, after the embossed design is applied by contact with the embossed plate roll, the embossed resin is cooled to below the glass transition temperature and the embossed design is fixed. It becomes the point of time when it comes into contact with the cooling roll installed. Therefore, there is a time margin for the occurrence of emboss return. In the case where a fine embossed design is originally provided in which the unevenness of the embossed plate itself is extremely shallow, even if a slight embossing return occurs, the embossed transfer becomes unsatisfactory.

Therefore, in Patent Document 3, for the purpose of improving the transferability of the precision embossing, a blend of a polyester resin and an aromatic polycarbonate resin in which the resin composition of the embossing layer is substantially amorphous. As a composition, the storage elastic modulus at 100 ° C. of the composition is set to a specific value or more to prevent the embossing from returning at the time of lamination or immersion in boiling water.
When such a composition is used, at a temperature lower than the glass transition temperature, the resin layer to which embossing is applied maintains a high elastic modulus, thereby preventing the embossing from returning.

On the other hand, Patent Document 4 discloses a polyester resin for decorative steel sheets, from a copolymer polyester resin having terephthalic acid as a main dicarboxylic acid component, ethylene glycol 85 to 60 mol%, and spiroglycol 15 to 40 mol% as glycol components. A composition obtained by laminating a sheet-like material comprising the composition on a metal plate is said to be excellent in processability, heat resistance, impact resistance, chemical resistance and stain resistance.
JP 2000-233480 A International Publication No. 03/045690 Pamphlet JP 2007-237568 A JP 2004-035633 A

  However, in Patent Document 3, a high temperature of 280 ° C. to 300 ° C. is required for melt kneading of an aromatic polycarbonate resin having a molecular weight that can be used for an extruded film, and kneading load Therefore, there are significant restrictions on the extruder that can be used, and when it is desired to obtain an extruded sheet laminated and integrated with other layers by a coextrusion film forming method, for example, a glass transition temperature of about 80 ° C. In co-extrusion lamination with non-crystalline polyester resin, etc., the difference in melt viscosity becomes large. Therefore, in order to ensure the thickness uniformity of each layer in the width direction, the multi-manifold method is preferable. There are also constraints.

  Furthermore, since the era of soft PVC sheets, the so-called pearl mica pigments with a titanium oxide coating on the surface of scaly mica can be visually recognized on the transparent sheet laminated on the colored base sheet. Although it has been practiced to add a small amount so that it does not disappear, the design is further improved, but in the case of a resin composition containing an aromatic polycarbonate resin, the surface of the pearl mica pigment is coated at the high melt kneading temperature. Titanium oxide exhibits thermal catalysis, accelerates the deterioration of the resin during film formation, and causes poor appearance such as yellowing, streaking, foaming, etc. Add pearl mica pigment to the transparent layer made of the composition It was difficult to do.

With normal pigment titanium oxide, surface treatment with alumina, silica, etc. can effectively suppress the expression of thermal catalysis, and melt kneading at high temperatures like aromatic polycarbonate resins. While it can be used for the required resin types without any problem, it is estimated that pearl mica pigments are less likely to exert their effects even if they are surface treated for reasons such as being susceptible to crushing. The

  Moreover, in patent document 4, when it is going to provide embossing with the embossing apparatus in the single layer sheet | seat which consists of this composition, it is necessary to heat to the temperature more than the glass transition temperature (Tg) of this resin composition. However, since the elastic modulus of the sheet heated above the temperature decreases rapidly, the embossing device adheres to or sticks to the heating drum, the sheet shrinks due to insufficient melt tension of the sheet, wrinkles, and melts the sheet. There is a risk of problems such as breakage. In the embodiment of Patent Document 4, embossing is performed by applying a resin sheet to a metal plate and then pressing it with an embossing roll in the form of a metal sheet as a carrier sheet. However, in this method, although the resin coating is applied to one side, the metal plate is passed between the rolls, and the embossing roll surface may be damaged due to warpage of the end of the metal plate. And scratches on the roll immediately cause a decrease in the surface design of the resin-coated metal sheet.

  In addition, if a metal plate having a considerably high thickness accuracy is not used, there is a possibility that the pressure applied to the resin layer by the embossing plate roll will be uneven from place to place, and as a result, there may be uneven emboss transfer. There is. In this case as well, when precise embossing with relatively shallow irregularities on the plate itself is performed, even if slight transfer unevenness occurs, the difference depending on the location of the design will be significant, and the product value may be impaired. was there. As a solution for this, it is conceivable to increase the thickness of the resin layer so that uneven transfer is less likely to occur. However, the resin composition has a relatively high raw material cost among polyester resins, and the cost is low. It is not preferable from the point.

  Moreover, in patent document 4, regarding the embossing heat resistance, the retention rate of embossing after standing in an oven at 90 ° C. for 5 days is evaluated in the examples, but to suppress the embossing return after immersion in boiling water. , A glass transition temperature (Tg) of 100 ° C. or higher is necessary, and some examples have glass transition temperatures below this.

  The present invention has been made to solve the above-described problems of the prior art, and is suitable for embossing within a range of conditions in which embossing is applied to a soft PVC sheet using a conventional embossing apparatus, in particular. , Laminated sheet that has good embossing applicability and can give an embossed heat-resistant embossed design, embossed design sheet embossed on the laminated sheet, embossed design sheet-coated metal plate, building interior material It is an object of the present invention to provide an embossed design sheet and an embossed design sheet-covered metal plate having high design properties in which a pearl mica pigment is added to a transparent surface layer. Furthermore, since it has the tolerance to a boiling water immersion test, the embossed design sheet coating | cover metal plate which can be used suitably also for a unit bath use is provided.

  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.

The first aspect of the present invention is a laminated sheet comprising three layers of A layer (10), B layer (20) and C layer (30) shown below in order from the surface side, and having a total thickness in the range of 55 μm to 300 μm. (100).
Layer A (10): terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, 45 mol% or less of spiroglycol and 50 mol% or more of the ethylene glycol as the main component of the diol component, heating rate by differential scanning calorimetry A non-oriented layer having a glass transition temperature measured at 10 ° C./min of 100 ° C. or more and a substantially amorphous copolymer polyester resin composition as a main component and a thickness of 100 μm or less.
B layer (20): A layer having a thickness of 40 μm or more, which is made of a substantially amorphous polyester-based resin and to which a colorant is added.
C layer (30): Polybutylene terephthalate resin having a melting point of 215 ° C. or higher and 235 ° C. or lower and / or polytrimethylene terephthalate resin having a melting point of 215 ° C. or higher and 235 ° C. or lower, the entire resin component in the C layer A non-oriented layer having a thickness of 5 μm or more and containing 70% by mass to 95% by mass with respect to 100% by mass.

  The substantially non-crystalline copolyester resin composition in the layer A (10) may be composed of one type of non-crystalline copolyester resin, or two or more types of amorphous polyester resin. It may also be composed of a mixture of a functional copolyester resin. In the case of two or more kinds of resin mixtures, the spiroglycol and ethylene glycol may be in a predetermined range as a whole resin mixture. Reference numeral 100 is used as a superordinate concept of the reference numerals 100A, 100B, and 100C shown in the figure.

  In this laminated sheet (100), the A layer (10) is a layer having good emboss transfer properties including precision embossing, and at the same time, is a layer having good embossing heat resistance, particularly embossing persistence after immersion in boiling water. The layer B (20) is a layer that imparts a colored design to the laminated sheet by adding a coloring pigment, and at the same time, at the time of transferring the embossed pattern to the laminated sheet, the embossed pattern is the same as the layer A (10). It is a layer that is deformed by pressing with a plate, and in each layer of the laminated structure, the total of the A layer (10) and the B layer (20) while the thickness of the A layer (10) having a relatively high raw material unit price is relatively thin. It is a layer that enables transfer of an embossed pattern having a depth corresponding to the thickness.

  In addition, since the B layer (20) has a substantially amorphous polyester resin as a main component, for example, in a configuration in which the B layer (20) alone is laminated on a metal plate, the resin is immersed in boiling water. There is a risk that the layer will undergo significant fluid deformation or blister-like debonding from the metal plate (60). On the other hand, in the present invention, the B layer (20) is present between the upper and lower layers sandwiched in boiling water immersion resistance, and the adhesion between the layers is strong. It can be set as the lamination sheet (100) excellent in water immersion property.

  In the first aspect of the present invention, the layer A (10) is a pearl mica pigment having a surface of scaly mica coated with titanium oxide, and the resin component of the layer A (10) is 100 parts by mass. It is good also as a structure containing 5 to 5 mass parts of mass parts.

  The melt-kneading temperature in the case where the resin composition of the A layer (10) of the present application is formed into a resin sheet by an extrusion film forming method is sufficiently lower than that of a resin composition containing an aromatic polycarbonate resin. Therefore, even when the pearl mica pigment is added, the resin component is not significantly deteriorated by the thermal catalytic action by the titanium oxide coating. Therefore, it is possible to obtain a resin-coated metal plate having transferability of precision embossing and having a pearl design similar to that of a metal plate coated with a soft PVC sheet.

  In the first aspect of the present invention, the substantially amorphous polyester-based resin of the B layer (20) is mainly composed of terephthalic acid or dimethyl terephthalic acid as a main component of the dicarboxylic acid component, and is 25 mol% or more and 75 mol% or less of 1 1,4-cyclohexanedimethanol and a copolymerized polyester resin mainly composed of 25 mol% or more and 75 mol% or less of ethylene glycol as diol components.

  According to this aspect, the merit of stability of raw material supply can be obtained by using a commercially easily available material as the polyester resin. In addition, since the material is cheaper than the resin composition that is the main component of the A layer (10), the cost of the laminated sheet can be reduced. Further, by using a commercially available material as the B layer (20), it is possible to easily obtain a master batch (preliminary kneaded pellet) of various color pigments using the material as a base resin at low cost. It becomes possible.

  The C layer (30) gives sufficient sheet tension when the laminated sheet (100) is heated by an embossing apparatus, and prevents melt breakage and significant elongation of the laminated sheet, wrinkles caused by the same, and the like. The layer is non-adhesive to a heated metal roll such as a heating drum of an embossing apparatus. Moreover, when laminating to the metal plate (60), even if the temperature of the metal plate (60) is the same as the temperature when laminating the conventional soft PVC sheet, it is a layer capable of obtaining sufficient adhesive strength. is there. Therefore, according to 1st this invention, by combining each layer of A layer (10), B layer (20), and C layer (30), embossing applicability and handleability, to metal plate (60) A laminated sheet (100) excellent in laminating suitability can be provided.

  In the first aspect of the present invention, the B layer (20) is a substantially amorphous polyester having a content of 55% by mass or more and 80% by mass or less based on the entire resin component of the B layer (20) (100% by mass). A layer comprising a polyresin, a polybutylene terephthalate resin having a melting point of 210 ° C. or higher and 230 ° C. or lower and / or a polytrimethylene terephthalate resin having a melting point of 210 ° C. or higher and 230 ° C. or lower. It is also good.

  When such a blend resin composition is used for the B layer (20), the resistance to the boiling water immersion test can be further improved, and the thickness of the B layer (20) is set to be relatively thick. Especially effective.

  In the first aspect of the present invention, the A layer (10) is substantially transparent, and the printed pattern D (40) is provided between the A layer (10) and the B layer (20) (100B). Good.

  Thereby, in addition to the embossed design including the precision embossed design, a laminated sheet (100B) having a printed design can be obtained.

  In the configuration having the printed pattern D (40), a polyester resin that is substantially transparent and substantially amorphous is mainly used between the A layer (10) and the printed pattern D (40). It is good also as a structure (100C) using the laminated sheet which the E layer (50) used as a component interposes, and the A layer (10) and this E layer (50) were laminated and integrated by the coextrusion film forming method.

  By adopting such a configuration, the thickness of the transparent resin layer coated on the printed pattern D (40) is compared while reducing the amount of the resin component of the A layer (10), which is relatively expensive. Can be thickened. And the handleability of this transparent resin layer before coating can be made favorable. Moreover, the laminated sheet (100C) which has a deep design feeling is obtained because the transparent resin layer with comparatively thickness can be laminated | stacked on printed pattern D (40).

  2nd this invention is equipped with the uneven | corrugated shape shape | molded by the embossing plate on the A layer (10) side surface of the laminated sheet (100) of 1st this invention, and this laminated sheet (100). , An embossed design sheet (200). Reference numeral 200 is used as a superordinate concept of the illustrated reference numerals 200A, 200B, and 200C.

  Here, the “embossed plate” refers to a plate having an embossed design formed on the surface by a method such as engraving, and embossing is applied to transfer the surface irregularities of the embossed plate to the surface of a heated thermoplastic resin sheet. Call it. The shape of the embossing plate is not particularly limited, and may be a plate-like shape that gives embossing by a batch method, but usually a roll-like shape that gives embossing continuously or a belt-like shape is used.

  The laminated sheet (100) of the present invention is excellent not only in an ordinary deep embossed design but also in an emboss transfer property of a precision embossed design, and also has good embossing heat resistance. For this reason, it can be set as the embossed design sheet (200) excellent in the designability.

  3rd this invention is equipped with the embossed design sheet | seat (200) of 2nd this invention, and the metal plate (60), and the surface of the C layer (30) side of this embossed design sheet | seat (200) is an adhesive agent ( 70) is an embossed design sheet-covered metal plate (300) laminated on the metal plate (60). Reference numeral 300 is used as a superordinate concept of the illustrated reference numerals 300A, 300B, and 300C.

  The embossed design sheet-covered metal plate of the third aspect of the present invention is excellent in design and heat resistance by the embossed design, has high surface hardness, excellent scratch resistance and workability, and has resistance to boiling water immersion. .

  4th this invention is a unit bath member using the embossed design sheet coating | coated metal plate (300) of 3rd this invention.

  The fifth aspect of the present invention is a building interior material using the embossed design sheet-coated metal plate (300) of the third aspect of the present invention.

  The sixth aspect of the present invention is a steel furniture member using the embossed design sheet-coated metal plate (300) of the third aspect of the present invention.

  The seventh aspect of the present invention is a home appliance casing member using the embossed design sheet-coated metal plate (300) of the third aspect of the present invention.

  The embossed design sheet-coated metal plate (300) of the present invention has a high surface hardness and is excellent in scratch resistance and workability. Therefore, the embossed design sheet-coated metal plate (300) is used for various applications such as the fourth to seventh aspects of the present invention. Can do. In particular, not only has excellent emboss transferability, but can also be given a design by printed pattern D (40), so by combining these designs, various members having excellent design properties Can do. In addition, the laminated sheet itself does not cause flow deformation when immersed in boiling water, and also has good embossing heat resistance after immersion in boiling water, so that the heat resistance is required, for example, the fourth invention. The unit bus member can be suitably used. In addition, as a unit bath member, a unit bath wall material and a unit bath ceiling material can be mentioned, for example.

  By providing the A layer (10), the laminated sheet (100) of the present invention can be excellent in emboss transferability in an embossing apparatus. In particular, not only a normal embossed design but also a very shallow unevenness called a precision embossed design, and the transferability of a fine embossed design can be made superior to that of a conventional soft PVC sheet. Further, the embossing design can be made to have good residual properties even when it is immersed in boiling water after being coated on a metal plate.

  Furthermore, since the melt kneading temperature of the resin composition of the A layer (10) of the present application is sufficiently lower than that of the aromatic polycarbonate resin, the resin may be added even when a pearl mica pigment that easily exhibits thermal catalytic action is added. Deterioration of is suppressed. For this reason, in order to obtain the transferability of conventional precision embossing and heat resistance of embossing, it has a pearl design that was difficult to realize when a resin composition containing an aromatic polycarbonate resin was used for the embossing layer. A resin-coated metal plate can be obtained, and more various coloring designs can be obtained.

  Moreover, by providing the C layer (30), when the laminated sheet (100) of the present invention is heated by an embossing apparatus, a sufficient sheet tension can be applied to the laminated sheet. Therefore, a good embossed design can be imparted without causing width reduction, wrinkling, sheet breakage, or the like. Moreover, since C layer (30) shows non-adhesiveness with respect to the heating roll (410) of an embossing apparatus, the laminated sheet of this invention shall be excellent in the emboss provision suitability using an embossing apparatus. Can do. Furthermore, since the C layer (30) is a layer capable of obtaining sufficient adhesive strength even when the temperature of the metal plate (60) is relatively low when laminating to the metal plate (60), It is possible to laminate on the metal plate (60) under the same conditions as those of the soft PVC sheet, and the laminate sheet of the present invention can be made excellent in the suitability for metal plate lamination.

  In addition, when the A layer (10), the B layer (20), and the C layer (30) are constituted by three layers, the A layer (10) is a single layer or the A layer (10) and the B layer. Compared with the case of (20) consisting of two layers, emboss transfer at a higher temperature is possible. Thereby, the embossed design sheet | seat (200) of this invention which transcribe | transferred the embossed design can be made excellent in embossing heat resistance. Moreover, when the laminated sheet (100) composed of the A layer (10), the B layer (20), and the C layer (30) is produced by coextrusion, the laminated sheet is less likely to warp and has good handleability. Can do.

Hereinafter, embodiments embodying the present invention will be described.
<Laminated sheet 100>
The structure of the lamination sheet 100 of this invention is typically shown to Fig.1 (a)-(c). FIG. 1A shows a laminated sheet 100A in which three layers of an A layer 10, a B layer 20 and a C layer 30 are laminated in order from the surface, and FIG. 1B shows the A layer 10 of the laminated sheet 100A. The lamination sheet 100B which has the printed pattern D40 between B layers 20 is shown. FIG.1 (c) shows the laminated sheet 100C using the coextruded sheet | seat which consists of A layer 10 and E layer 50 as a surface layer by the structure which has the printed pattern D40. Hereinafter, these structures and manufacturing methods will be described in detail.

  The laminated sheet 100 of the present invention has a thickness in the range of 55 μm or more and 300 μm or less, and hence is more correctly described as “film and sheet”. For convenience, the single name “sheet” is used. Further, in the present specification, the expression “non-oriented” means that an orientation treatment such as a stretching operation has not been performed in order to impart some performance to the laminated sheet. This does not mean that there is no orientation or the like that occurs when the film is taken up by a casting roll.

<A layer 10>
The A layer 10 is a layer that becomes the surface of the laminated sheet 100, and when the laminated sheet is passed through an embossing apparatus, the embossed pattern is transferred by being softened by heating and pressed by an embossing roll. Therefore, when the A layer 10 is pressed by the embossing roll, the melting point (Tm) exceeding about 190 ° C., which is the upper limit of the sheet heating temperature in the embossing apparatus generally used for embossing the soft PVC sheet. And a resin composition having high crystallinity as shown in FIG. In the case of an amorphous resin, it should not be constituted by a resin composition having a glass transition temperature exceeding about 190 ° C.

  Further, the A layer 10 may not be a layer made of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. Even when such a resin is used, the transferability itself of the precision embossed design can be made good, but the glass transition temperature is too low and the elasticity retention effect due to crystallinity is not manifested. This is because the embossing is inferior in heat resistance, and the embossed return after immersion in boiling water becomes remarkable, or the A layer 10 itself undergoes fluid deformation in all layers during immersion in boiling water, resulting in a markedly poor appearance. .

  From the above viewpoint, in the present invention, the A layer 10 is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 45 mol% or less of spiroglycol and 50 mol% or more of ethylene glycol are used as the diol component. The main component is a copolyester resin composition having a glass transition temperature (Tg) measured by differential scanning calorimetry at a heating rate of 10 ° C./min of 100 ° C. or more and substantially amorphous. Layer.

Here, the “main component” in the dicarboxylic acid component is based on the whole dicarboxylic acid component (100 mol%), and terephthalic acid or dimethyl terephthalic acid is at least 70 mol%, preferably 80 mol% or more, more preferably It means containing 98 mol% or more. The “main component” in the diol component is preferably 85 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol%, based on the total amount of the diol component (100 mol%). Saying that it contains more than mol%.
In addition, the “main component” is 70% by mass or more, preferably 80% by mass or more of the substantially amorphous copolyester resin composition based on the whole A layer (100% by mass). More preferably, 90% by mass or more is included.
In the A layer 10, the substantially amorphous copolymer polyester resin composition may be composed of one type of amorphous copolymer polyester resin, or two or more types of amorphous copolymer resins. It may be composed of a mixture of polymerized polyester resins. In the case of two or more kinds of resin mixtures, the spiroglycol and ethylene glycol may be in a predetermined range as a whole resin mixture.

  Examples of dicarboxylic acid components other than terephthalic acid and dimethylterephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, dimethylisophthalic acid, and 2,6-naphthalenedicarboxylic acid, adipic acid, succinic acid, sebacic acid, 1,4 -Various dicarboxylic acids used for polymerization of polyester resins such as aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, or used as a copolymerization component. Further, a polyfunctional carboxylic acid component may be contained in an amount of several mol% or less. Among these, when 2,6-naphthalenedicarboxylic acid is used as a copolymerization component, an effect of further increasing the glass transition temperature of the resin composition can be obtained, but when the ratio of the copolymerization component is increased too much, The raw material price becomes expensive, making it difficult to adapt to the use of the design resin-coated metal sheet in terms of cost.

  Examples of diol components other than spiroglycol and ethylene glycol include diethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, 1.3-propanediol, 1,4-butanediol, hexamethylene glycol, and polytetramethylene glycol. Examples thereof include various diols used for polymerization of polyester resins or used as copolymerization components. In the present invention, it is not necessary to specifically include these. Diethylene glycol is often included as an unintended copolymer component as a few mole percent of the diol component. Further, a polyfunctional alcohol component may be contained in an amount of several mol% or less.

  The resin composition constituting the A layer 10 can be a polyester resin composition having a high glass transition temperature due to the rigidity of the molecular chain by using spiroglycol as a copolymerization component. However, when spiroglycol in an amount exceeding 45 mol% is included as the diol component, the glass transition temperature (Tg) of the resin composition is even higher, but the tear resistance of the resin sheet is reduced, The notch sensitivity when applying tensile stress becomes sharp, and the properties of the sheet for resin-coated metal sheets such as breaking the sheet just by applying a slight elongation at the minute scratched part are undesirable characteristics. May develop.

  Conversely, when the copolymerization ratio of spiroglycol is too low, the glass transition temperature (Tg) of the copolymerized polyester resin composition may be less than 100 ° C. However, since the glass transition temperature of the copolymerized polyester resin composition can be changed by other copolymerization components as in the case where the above-mentioned 2,6-naphthalenedicarboxylic acid is included as a copolymerization component, in the present invention, Does not specifically limit the lower limit of the copolymerization ratio of spiroglycol, but has decided to limit the lower limit of the glass transition temperature of the composition.

  In the case of a composition in which the dicarboxylic acid component is only terephthalic acid and the diol component is composed only of spiroglycol and ethylene glycol, the copolymer polyester obtained when the copolymerization ratio of spiroglycol is less than about 25 mol% of the diol component. The glass transition temperature (Tg) of the resin is lower than 100 ° C. From this point, it is preferable that the lower limit of the copolymerization ratio of spiroglycol in the diol component is 25 mol% or more.

  When the glass transition temperature of the copolyester resin composition constituting the A layer 10 is lower than 100 ° C., the heat resistance of the emboss is insufficient, and the emboss return after immersion in boiling water is particularly remarkable. The glass transition temperature of the copolymerized polyester resin composition constituting the A layer 10 is more preferably 105 ° C. or higher.

  Examples of the copolymer polyester resin having a preferable composition range of the monomer component and having a glass transition temperature of 100 ° C. or higher include “Altester 45” and “Altester 30” manufactured by Mitsubishi Gas Chemical Company, Inc. it can. “Altester 45” has a glass transition temperature (Tg) of 111 ° C. measured at a heating rate of 10 ° C./min by differential scanning calorimetry (DSC), and has no crystallization or crystal melting behavior. Polyester resin. “Altester 30” is an amorphous polyester resin having a similarly measured glass transition temperature of 104 ° C. and no crystallization behavior or crystal melting behavior.

(Additive)
When the printed pattern D40 does not exist under the A layer 10, a coloring pigment may be added to the A layer 10 for designability or visual concealment of the base metal. In the present invention, the A layer No. 10 has a high concealing property, and therefore it is preferable to use a transparent layer without coloring by adding a high concentration of pigment. This is because it is more convenient to use various commercially available pigment master batches when the later-described B layer 20 is the main colored layer.

  However, after adding a coloring design and a pigment for obtaining a visual concealing effect on the base to the B layer 20, the A layer 10 has a pearl mica pigment having an appropriate particle size, aluminum powder, silver powder, Various metallic powders such as gold powder, glass flakes, surface-modified glass flakes, and so-called glitter pigments such as ceramic powders are added to give the metallic layer a design feeling while ensuring the transparency of the A layer 10 Further, a design may be applied such that the particles are dispersed in the form of dots and express glitter.

  Among these luster pigments, pearl mica pigments are obtained by applying a titanium oxide coating to the surface of scaly mica, and even on a resin-coated metal plate using a soft PVC sheet, It has been practiced to further improve the design by adding a small amount to the transparent sheet to be laminated so that the visibility of the color of the base sheet is not hindered. Although intense metallic reflection as in the case of adding metallic powder or the like cannot be obtained, it is possible to impart a calm design feeling together with a moderate increase in haze (cloudiness).

  However, when the A layer 10 is formed from a resin composition containing an aromatic polycarbonate resin for the purpose of ensuring the embossing heat resistance of the A layer 10 or the like, due to the high melt kneading temperature of the aromatic polycarbonate resin, Titanium oxide coated on the surface of the pearl mica pigment exhibits a thermocatalytic action, promotes deterioration of the resin during the film forming process, and causes poor appearance such as yellowing, streaking, and foaming. Therefore, when the A layer 10 is formed from a resin composition containing an aromatic polycarbonate resin, it has been difficult to add a pearl mica pigment to the transparent layer made of the resin composition.

  The melt kneading temperature of the resin composition constituting the A layer 10 of the present invention can be sufficiently lower than that of a resin composition containing an aromatic polycarbonate resin. Therefore, even when a pearl mica pigment is added to the A layer 10, the resin component is not significantly deteriorated due to the thermal catalytic action by the titanium oxide coating, and it has the transferability of precision embossing and is a metal plate coated with a flexible PVC sheet. A resin-coated metal plate having the same pearl design can be obtained. The preferred addition amount of the pearl mica pigment is 0.5 parts by mass or more and 5 parts by mass or less based on the total amount of the resin component of the A layer 10 (100 parts by mass). In the transparent layer of the conventional flexible PVC-based laminated sheet, It is the same as the case of adding. The particle diameter of the preferred pearl mica pigment is the same as that of the prior art, and those having a size of about 5 μm to 80 μm can be appropriately selected and used depending on the design feeling desired.

  Various additives may be added to the A layer 10 in an appropriate amount in order to further improve the physical properties other than the object of the present invention within a range not impairing the properties of the present invention. Additives include phosphorous and phenolic antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, impact modifiers, processing aids, hydrolysis inhibitors, chain extenders, metals Examples generally include resin materials such as inactivating agents, residual polymerization catalyst inactivating agents, antibacterial / antifungal agents, antistatic agents, lubricants, flame retardants, fillers, and matting agents.

(Thickness)
The thickness of the A layer 10 is preferably 100 μm or less, more preferably 20 μm or more and 75 μm or less, and particularly preferably 30 μm or more and 60 μm or less. Even if the thickness of the A layer 10 is thin, a relatively deep embossed pattern can be transferred together with the thickness of the B layer 20, but if the thickness is thinner than this, the A layer 10 is manufactured as a single-layer sheet. In the case of forming a film, it is easy to cause a problem in its handleability. In addition, when the A layer 10 and the B layer 20 or the A layer 10, the B layer 20 and the C layer 30 are laminated by coextrusion film formation, the A layer is also formed in the width direction of the laminated sheet. The thickness distribution of 10 tends to be unstable. On the contrary, if the thickness of the A layer 10 is too thick, the upper limit of the total thickness of the laminated sheet 100 is determined. In addition, since the raw material price of the resin constituting the A layer 10 is higher than the raw material price of the resin constituting the other layer, the price of the laminated sheet and consequently the laminated sheet-covered metal plate is increased. .

<B layer 20>
The purpose of providing the B layer 20 in the laminated sheet 100 of the present invention is to enable the transfer of a relatively deep embossed pattern by combining the thickness of the A layer 10 and the thickness of the B layer 20, and by adding a colorant. Giving a colored design and ensuring the visual concealment effect of a metal plate as a base material. Moreover, in the structure which has the printed pattern D40 between the A layer 10 and the B layer 20, the coloring property of the printed pattern D40 is improved by the B layer 20 being colored.

  Therefore, when the B layer 20 is also pressed by the embossing roll, a high crystal exhibiting a melting point (Tm) exceeding about 190 ° C. which is the upper limit of the sheet heating temperature in a commonly used embossing apparatus. It must not be made of a resin having properties. Further, it should not be made of a resin that requires a relatively high temperature for melt kneading.

  Therefore, in the present invention, the B layer 20 is composed mainly of a polyester resin that is substantially amorphous. Here, “substantially amorphous” means that it has no crystallinity that makes embossing difficult in an embossing apparatus, and is limited to a polyester resin that is completely amorphous. It is not a thing. The “main component” is at least 55% by mass, preferably 70% by mass of the substantially amorphous polyester resin, based on the mass (100% by mass) of the entire resin component of the B layer 20. % Is included.

(Substantially amorphous polyester resin)
The substantially non-crystalline polyester resin constituting the B layer 20 is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 1,4-cyclohexanedimethanol having a content of 25 mol% to 75 mol%. And a copolymerized polyester-based resin mainly composed of 25 mol% or more and 75 mol% or less of ethylene glycol as a diol component can be preferably used.

Here, the “main component” of the dicarboxylic acid component is based on the total amount of the dicarboxylic acid component (100 mol%), and terephthalic acid or dimethyl terephthalic acid is at least 70 mol%, preferably 90 mol% or more. Preferably it means 98 mol% or more.
The “main component” of the diol component is preferably 1,4-cyclohexanedimethanol and ethylene glycol, preferably 70 mol% or more, more preferably 80 mol% or more, based on the total amount of the diol component (100 mol%). More preferably, 90 mol% or more is included.

  When the copolymerization ratio of 1,4-cyclohexanedimethanol is less than the above range, the characteristic as a crystalline resin becomes remarkable, and it functions as a layer that is crystallized at the time of embossing and is deformed by pressing with an embossing plate. There is a risk that it will not be possible to obtain. On the other hand, when the amount of 1,4-cyclohexanedimethanol is larger than the above range, the influence of crystallinity becomes remarkable and the same problem may occur.

  As the copolyester resin in the above preferred composition range, the cost can be reduced because of the stable supply of raw materials and the production volume, and various color pigment master batches using the resin as a base resin. In addition, so-called PETG resin can be preferably used because a large number of additive master batches are commercially available. Examples of the PETG resin include “Easter PETG • 6763” manufactured by Eastman Chemical Company. “Easter PETG • 6763” is a copolyester having terephthalic acid as the main component of the dicarboxylic acid component, about 31 mol% of the diol component is 1,4-cyclohexanedimethanol, and about 69 mol% is ethylene glycol. It is an amorphous polyester-based resin in which crystallization behavior is not recognized by measurement with a differential scanning calorimeter (DSC).

  In addition, it is necessary to handle it as a crystalline resin in kneading with a hot roll and calender film formation, but Eastman Chemical Company can handle it as an amorphous polyester resin in ordinary extrusion film formation. "Easter PCTG 5445" manufactured by the company and "Easter PCTG 24635" manufactured by Eastman Chemical Company are also copolyester resins within the above composition range.

  However, the present invention is not limited thereto, and PET that is copolymerized with neopentyl glycol as a diol component does not exhibit crystallinity (for example, “COSMOSTER SI-173” manufactured by Toyobo Co., Ltd.) As a dicarboxylic acid component, depending on the copolymerization component, such as polyethylene terephthalate resin copolymerized with isophthalic acid, polybutylene terephthalate resin copolymerized with isophthalic acid, and those that do not exhibit crystallinity or have low crystallinity Copolyester resins having a structure that inhibits crystallization can also be used as the main component of the B layer 20. Further, the same resin as that used for the A layer 10 may be used for the B layer 20, but as described above, it is disadvantageous in terms of raw material price.

  Since the B layer 20 has a substantially amorphous polyester resin as a main component, the resin-coated metal plate coated with a single-layer sheet made of the resin of the B layer 20 is resistant to boiling water immersion. It is scarce and causes significant flow deformation. On the other hand, in this invention, since it was set as the structure which sandwiches the upper and lower sides of the B layer 20 with the layer which has boiling-water immersion resistance, the boiling water immersion test in the state used as the resin-coated metal plate as a structure of the lamination sheet 100 whole. It is possible to impart resistance to.

  In order to further ensure boiling water immersion resistance of the laminated sheet 100, the B layer 20 is 55% by mass or more and 80% by mass based on the total resin component constituting the B layer 20 (100% by mass). A layer containing the following substantially amorphous polyester resin, 20% by mass or more and 45% by mass or less of polybutylene terephthalate (PBT) resin and / or polytrimethylene terephthalate (PTT) resin Good. This is particularly preferable when the B layer 20 has a thickness of 75 μm or more for the purpose of improving the transfer of deep embossing.

  When the mixing ratio of the crystalline polyester resins such as PBT and PTT exceeds 45% by mass, the crystallinity becomes excessive, and the amorphous film at the time of the extruded film-forming sheet is heated by the embossing device. When crystallization proceeds and is pressed with an embossing roll, emboss transfer may become difficult, which is not preferable. Conversely, when the mixing ratio of these crystalline polyester resins is less than 20% by mass, as compared with the case where only the polyester resin that is substantially amorphous is used as the resin composition of the B layer 20, There is no significant difference in the immersion in boiling water.

(Color pigment)
The B layer 20 is a layer mainly responsible for the visual hiding effect of the colored design and the base, and is added with a colorant. The colorant used for coloring the B layer 20 may be one generally used for coloring a polyester resin, and the addition amount thereof may be an amount generally added for the above purpose. For example, in the case of a light color, a white coloring pigment, based on a titanium oxide pigment having a high visible light hiding effect, a color adjustment is performed with a chromatic inorganic or organic pigment or dye. be able to. Moreover, as an addition amount of a coloring agent, it is preferable to set it as 2 to 50 mass parts on the basis (100 mass parts) of the whole quantity of the resin component which comprises the B layer 20, for example. As described above, there are abundantly commercially available pigment-kneaded pellets whose dispersibility is improved by applying preliminary kneading, such as a color masterbatch using PET-G as a base resin. Thus, the B layer 20 can be easily made into a colored layer. In addition to the pigments, the B layer 20 can be added with various additives exemplified in the description of the A layer 10 in an appropriate amount in the same manner as the A layer 10.

(Thickness)
The thickness of the B layer 20 is 40 μm or more, preferably 50 μm or more and 250 μm or less, and more preferably 75 μm or more and 200 μm or less. If the thickness is too thin, it is difficult to develop the coloring design required for the B layer 20 and the visual concealing effect of the base metal. Conversely, if the thickness is too thick, the upper limit of the total thickness of the laminated sheet 100 is increased. Since it is determined, there is a possibility that the function that the A layer 10 or the C layer 30 should be responsible for may not be developed. When embossing with a normal depth is applied, the total thickness of the A layer 10 and the B layer 20 is preferably 60 μm or more, and more preferably 80 μm or more.

  The visual concealment effect of the base metal plate due to the addition of the color pigment varies depending on the application. However, in the case of an embossed design sheet-coated metal plate for interior building materials, JIS K5600-4-1 “Paint General Test It is preferable that the concealment ratio measured according to “Method / Concealment ratio” is 0.95 or more in the configuration of the laminated sheet 100.

  When the concealment rate is lower than this, the color of the base material, such as a metal plate, is reflected in the color of the surface of the laminated sheet 100, and when the color changes due to the difference in the treatment of the metal plate surface, etc. Since the color observed from the sheet surface also appears to change, it is not preferable. However, in applications where color change due to this reason does not pose a particular problem, the concealment rate need not be 0.95 or more.

<C layer 30>
Even when the layer C 30 is heated to the same temperature as that of the conventional soft PVC when the laminated sheet 100 is passed through an embossing apparatus, the laminated layer 100 is adhered to the heated metal roll, reduced in width, It has the role of preventing entry and melt fracture. Therefore, when an embossing pattern is transferred by an embossing device, the sheet should not exhibit adhesiveness to metal at a temperature up to about 150 ° C. heated by a heating roll, and the sheet has no support. In the resin composition, the elastic modulus should be remarkably lowered at a heating temperature of about 160 ° C. to 190 ° C., which is the temperature heated by the heater. On the other hand, when laminating to the metal plate 60, it is necessary to obtain a strong adhesion to the metal plate heated to the same temperature as the conventional soft PVC, so that the state heated to about 235 ° C. However, it must not maintain a high elastic modulus, and therefore should not be a crystalline polyester resin in a crystallized state having a melting point exceeding 235 ° C.

(PBT resin, PTT resin)
For the above purpose, the C layer 30 of the present invention comprises a polybutylene terephthalate (PBT) resin having a melting point of 215 ° C. or higher and 235 ° C. and / or a polytrimethylene terephthalate (PTT) having a melting point of 215 ° C. or higher and 235 ° C. or lower. ) Containing a predetermined amount of a resin.

  The melting point of 215 ° C. or higher is required when the embossing design is transferred to a conventional soft PVC sheet by an embossing apparatus, while the temperature at which the sheet is heated by a heater without a support is about 160 ° C. to 190 ° C. This is because when a PBT resin or PTT resin having a melting point of less than 215 ° C. is used as the resin component of the C layer 30, it is difficult to obtain sufficient tension at a heating temperature of 160 ° C. to 190 ° C. The upper limit of the melting point is 235 ° C., which is made of a polyester resin composition having a higher melting point. In the C layer 30 in a crystallized state, a sheet of conventional soft PVC is laminated to the metal plate 60. This is because it is difficult to obtain a strong adhesion with the metal plate 60 at a temperature up to 235 ° C., which is the upper limit of the heating temperature of the normal metal plate, as in the case of performing.

  The reason why the C layer 30 is a layer containing a predetermined amount of PBT-based resin and / or PTT-based resin is not only because these resins are in the preferable melting point range, but also because the crystallization rate is relatively high. Since it is fast, it is easy to obtain the C layer 30 having high crystallinity in the film forming process without providing a special curing process or the like between the film forming process and the embossing process, that is, in the embossing process. This is because non-adhesiveness to the heated metal and resistance to melt fracture are easily obtained.

  Also in the polyethylene terephthalate (PET) resin, a resin having a melting point in the above range can be obtained by substituting a part of terephthalic acid which is a dicarboxylic acid component with isophthalic acid. However, the PET resin in this case has a very low crystallization rate, and it is difficult to obtain a sufficiently crystallized C layer 30 in a normal extrusion film forming line, and it is necessary to provide a curing step or the like separately. Therefore, it is not preferable for use in the C layer 30.

  Another reason for using the PBT resin or the PTT resin is that better processability can be obtained even in a crystallized state compared to the PET resin. Thereby, even if it is a resin-coated metal plate coated with the laminated sheet 100 having the crystallized C layer 30, secondary workability such as bending workability can be improved.

  The content ratio of the PBT resin and / or the PTT resin in the C layer 30 is based on the mass of the entire resin component in the C layer 30 (100% by mass), and the PBT resin and / or the PTT resin. The lower limit of the content ratio is preferably 70% by mass or more, and more preferably 80% by mass or more. If the amount of PBT is less than this, the crystallization rate will be slow, so a special curing process will be required to crystallize to the extent that it is non-sticky to the heated metal. In addition, even if a crystallized sheet is obtained, it is difficult to obtain a preferable melt tension.

  Further, the upper limit of the content ratio of the PBT resin and / or the PTT resin is preferably 95% by mass or less, and more preferably 90% by mass or less. When the amount of PBT-based resin and / or PTT is larger than this, the crystallinity of the C layer 30 which is the adhesion laminated surface side when the laminated sheet 100 is laminated on the metal plate 60 becomes too high, which is conventional. This is because it is difficult to obtain adhesion strength with the metal plate 60 under heating conditions. In addition, when the C layer 30 is obtained by two-layer coextrusion with the B layer 20 or by a three-layer coextrusion film forming method with the A layer 10 and the B layer 20, warpage of the laminated sheet after film formation becomes significant. This is because there is a risk of hindering handling.

  As a PBT resin having a melting point of 215 ° C. or more and 235 ° C. or less, the acid component is terephthalic acid or dimethyl terephthalic acid, and the diol component is a polycondensation of each single component of 1,4-butanediol. The obtained homopolybutylene terephthalate resin (which may contain an unintended copolymerization component) can be used. Examples of the PBT resin having such a composition include “Novaduran 5020H” manufactured by Mitsubishi Engineering Plastics. When this is used, merits such as cost merits and supply stability can be obtained.

  In addition, as a PTT resin having a melting point in the range of 215 ° C. or more and 235 ° C. or less, a homo-polytrimethylene terephthalate resin can be used, and examples thereof include “Cortera CP509200” manufactured by Shell.

(PBT resin, resin components other than PTT resin)
As the resin component other than the PBT resin and the PTT resin added to the C layer 30, a substantially amorphous polyester resin is preferably used. As the substantially amorphous polyester-based resin, the same resin as the main component of the B layer 20 described above can be used. For example, “Easter PETG • 6763” of Eastman Chemical Company, Inc. And “Easter PCTG 5445”. The reason why amorphous is preferable is that when a highly crystalline resin is used, for example, a resin such as homo-PET, although the crystallization speed is slow, the crystallization progresses with time, so the crystalline phase of the PBT resin This is because the crystal phase of the PET-based resin, which is inferior to the workability of, may adversely affect the workability of the C layer 30 over time, and as a result, the workability of the laminated sheet and the metal plate 300 covering it may be lowered. is there. However, since the compounding amount of resin components other than PBT-based resin is limited, homo-PET or the like may be used when special consideration is not required for deterioration in processability over time.

(Thickness)
The C layer 30 preferably has a thickness of 5 μm or more, more preferably 10 μm or more, and particularly preferably 20 μm or more. When the thickness is thinner than this, the function as a tension applying layer in the embossing apparatus tends to be insufficient. Further, the upper limit of the thickness is preferably 200 μm or less, and more preferably 100 μm or less. Even if it is thicker than this, the function that the C layer 30 should be responsible for is saturated, and since the upper limit of the total thickness of the laminated sheet is determined, the failure of the function that the A layer 10 or the B layer 20 should be responsible for is brought about. There is a fear.

  Further, the C layer 30 includes, for example, a layer that shares the tension imparting function of the embossing device and a layer that shares the function of preventing the adhesion to the heating roll, as described in “JP 2006-095892 A”. It may consist of two layers. In this case, even if the lamination temperature to the metal plate 60 is further lowered, an effect of ensuring a good adhesion can be obtained.

(Additive)
Although pigments for coloring may be added to the C layer 30, since the B layer 20 exists as a target layer for expressing the coloring design, only the coloring of the B layer 20 provides a visual concealment effect on the foundation. It is preferable to supplementarily add a pigment, for example, in the case where the above cannot be obtained.

  Moreover, in order to make the non-adhesiveness with the heating metal which is one of the purposes to which the C layer 30 is provided more firmly, an appropriate amount of lubricant may be added. As the lubricant, those commonly used for addition to a polyester resin can be used. For example, “LICOWAX (registered trademark) OP” (manufactured by Clariant Japan), which is a montanic acid-based lubricant, can be mentioned. Can do. The addition amount of the lubricant may be a general amount of about 0.2% by mass or more and 3% by mass or less based on the total resin amount of the C layer 30 (100% by mass).

  Further, in order to make the tension at the time of heating the laminated sheet 100 in the embossing apparatus stronger, the C layer 30 has a linear ultrahigh molecular weight acrylic resin (for example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., Ltd. ) P-531 "and the like, and processing aids such as polytetrafluoroethylene that has been subjected to an easy dispersion treatment that expands into a fibril form (for example," Metblene (registered trademark) A-3000 manufactured by Mitsubishi Rayon Co., Ltd.). In this case, the amount added is generally 0.2% by mass to 3% by mass based on the total resin amount of the C layer 30 (100% by mass). The right amount.

  Furthermore, an organic or inorganic crystal nucleating agent is added in order to sufficiently impart the crystallinity necessary for obtaining non-adhesiveness and melt fracture resistance in the embossing apparatus to the C layer 30 in the extrusion film forming line. It may be added to improve the crystallization speed. In addition, various additives described in the A layer 10 and other general-purpose resins may be included in a small amount.

<Print pattern D40>
In the laminated sheet of the present invention, the A layer 10 is set as a substantially transparent layer, and the design of the color of the B layer 20 that is a colored layer is made visible through the transparent layer in terms of design. preferable. In this case, a printed pattern D40 may be provided between the A layer 10 and the B layer 20 to have a configuration having a printing design. The printed pattern D40 is applied by a known method such as gravure printing, offset printing, planographic screen printing, rotary screen printing, printing with an inkjet printer, flexographic printing, letterpress printing, electrostatic printing, and the like. The picture pattern is arbitrary, and examples thereof include a pattern imitating natural materials such as a stone pattern and a wood grain pattern, a geometric pattern, an abstract pattern, and the like. The printing may be partial printing or full printing, and both partial printing and full printing may be performed.

  As the resin binder type of the printing ink, those usually used for printing on a sheet-like material made of a polyester resin can be used without limitation. Examples thereof include acrylic, acrylic / urethane, polyester, polyester / urethane, alkyd resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / urethane, and the like. By appropriately selecting the binder type, even in the configuration having the printed pattern D40, the lamination and integration between the A layer 10 and the B layer 20 can be made by heat fusion lamination. Or at the time of provision of printing pattern D40, a heat adhesion application layer can be provided simultaneously, and heat fusion lamination nature can also be given.

  The printed pattern D40 may be formed by printing on the surface of the B layer 20 to be laminated with the A layer 10, or the surface of the A layer 10 to be laminated with the B layer 20 is printed. May be formed.

<E layer 50>
When producing a laminated sheet provided with the printed pattern D40, the A layer 10 is not formed alone, but the two layers of the A layer 10 and the E layer 50 are formed by coextrusion to form a laminated sheet. The laminated sheet and the B layer 20 and the C layer 30 containing a color pigment separately produced by a co-extrusion film forming method may be laminated and integrated through a printed pattern D40. The E layer 50 is a layer mainly composed of a polyester resin that is substantially transparent and substantially amorphous, and is a colored pigment using the same resin component as the resin component constituting the B layer 20. It is a substantially transparent resin layer that does not contain. The “main component” here has the same meaning as in the B layer. When the E layer 50 is used, it is possible to obtain a transparent resin layer having a thickness with no problem in handleability and the like while reducing the raw material price as compared with the case where the A layer 10 is formed alone.

  In the case of obtaining a single-extrusion film-forming sheet of A layer 10 with a configuration having a printed pattern D40, or when obtaining a co-extruded laminated sheet of A layer 10 and E layer 50, the thickness of these sheets is It is preferable that it is 30 micrometers or more. As long as the resin composition of the E layer 50 is within the range of the resin composition that can be used for the B layer 20, it may be different from the B layer 20 that is actually used or may be the same. FIG. 1C shows a laminated sheet 100 </ b> C having an E layer 50.

<The manufacturing method of the lamination sheet 100>
As a method for producing the laminated sheet 100 of the present invention, various known methods such as an extrusion cast film forming method or an inflation method using an extruder equipped with a T die can be employed. Especially, it is preferable to depend on the extrusion casting film forming method by the extruder provided with T die from the point of film forming stability.

  In order to produce the laminated sheet 100 of the present invention, three layers of A layer 10, B layer 20 and C layer 30 are formed by coextrusion film formation using three extruders and a feed block, and a single layer T die, Alternatively, it is most efficient and preferable to form a film integrally by a coextrusion film forming method using three extruders and a multi-manifold type T die. Alternatively, the A layer 10 is formed alone, and two layers of the B layer 20 and the C layer 30 are separately formed by a coextrusion film forming method using two extruders, and these are formed by an embossing apparatus. Heat fusion lamination may be performed at the introduction portion to the heating roll.

  In the present invention, since each layer is composed of a composition having heat-fusibility with each other, after each layer is formed alone, it may be laminated and integrated in a later step to form a laminated sheet 100. Since the C layer 30 is formed in a state where crystallization has progressed, it is possible to obtain good interlayer adhesion with the B layer 20 by heating at 160 ° C. to 190 ° C. with an embossing apparatus. It may not be easy, and the B layer 20 and the C layer 30 are preferably laminated in a die by a coextrusion method.

  However, the lamination integration of the A layer 10 or the A layer 10 and the E layer 50 and the B layer 20 or the lamination integration of the B layer 20 and the C layer 30 is not necessarily performed by the above method. Heat fusion lamination may be performed in the process. Further, lamination with dry laminating adhesive or the like, or heat fusion lamination by sandwiching a hot melt film may be performed, but since the object of the present invention is to obtain a high-design laminated sheet at low cost, these man-hours The method of stacking and integration with increasing number of materials and increasing materials is not necessarily a good method.

  The total thickness of the laminated sheet 100 of the present invention is 55 μm or more and 300 μm or less, and preferably in the range of 80 μm or more and 200 μm or less. When the thickness of the laminated sheet 100 is too thin, it is necessary to add a large amount of pigment to the colored layer mainly composed of the B layer 20 in order to ensure visual concealment of the base, and as a result, the processability may be lowered. is there. In addition, it becomes difficult to transfer a relatively deep embossed pattern. On the other hand, when the thickness of the laminated sheet 100 is too thick, there is a problem in secondary workability such as difficulty in using a molding die that has been conventionally used for forming processing such as bending of a soft PVC resin-coated metal plate. In addition, there is a possibility that abnormalities such as cracks occur in the resin layer in the bent portion.

<Embossed design sheet 200>
FIG. 1D shows an embossed design sheet 200A having an embossed design on the surface of the laminated sheet 100A, and FIG. 1E shows an embossed designed sheet 200B having an embossed design on the surface of the laminated sheet 100B. FIG. 1 (f) shows an embossed design sheet 200C in which an embossed design is applied to the surface of the laminated sheet 100C.

  The laminated sheet 100 manufactured by the above method can be used as the embossed design sheet 200 by providing the surface of the A layer 10 side with an uneven shape using an embossed plate. Here, reference numeral 200 is used as a superordinate concept including reference numerals 200A, 200B, and 200C. The laminated sheet 100 of the present invention has an embossed design at the same temperature conditions and processing speed as a conventional soft PVC sheet by various embossing apparatuses generally used for imparting an embossed pattern to the soft PVC sheet. Can be granted.

  In FIG. 2, an example of the embossing apparatus 400 generally used in order to give an embossed pattern to a flexible PVC sheet is shown. The illustrated embossing apparatus 400 includes a heating roll 410, a take-off roll 420, an infrared heater 430, a nip roll 440, an embossing roll 450, and a cooling roll 460. In the embossing apparatus 400, a metal roll-shaped embossing roll 450 is used as the embossing plate. However, the shape of the embossing plate is not particularly limited as long as it is a plate on which an embossed design is formed. Further, even a plate-like shape for embossing in a batch system, a roll shape for continuously embossing, a belt shape, a long sheet shape, or the like may be used.

  In the embossing apparatus 400 shown in FIG. 2, the A layer 10 formed as a single layer and the two-layer coextruded sheet of the B layer 20 and the C layer 30 subjected to the printed pattern D40 are supplied. Heat fusion lamination is performed by the heating roll 410.

  The laminated sheet 100 of the present invention has non-adhesiveness to the heating roll 410 heated to about 100 ° C. to 140 ° C. by having the C layer 30, and the sheet heating temperature by the infrared heater 430 Even at 160 ° C. to 190 ° C., the laminated sheet can maintain a sufficient tension and does not cause width shrinkage, wrinkles, breakage, or the like. Moreover, the embossed design sheet 200 to which the embossed design of the favorable external appearance was provided by having the A layer 10 can be obtained. In particular, by appropriately adjusting the temperature of the embossing plate roll to a temperature slightly lower than the glass transition temperature of the resin composition of the A layer 10, when the laminated sheet 100 comes into contact with the embossing plate roll, the embossing is applied and cooled at the same time. Since the embossing is immediately fixed by this, it is difficult for the embossing to return in the embossing process, and good transferability can be obtained even for precision embossing.

  A coloring design by so-called wiping printing may be given to the concave portion on the surface of the A layer 10 formed by embossing, or a glossy wiping ink may be used to give a glossy design feeling only to the concave portion. . The colored ink layer formed in the embossed concave portion by wiping printing is preferably formed from a colored transparent ink having a vehicle such as a two-component curable urethane resin, a colored concealing ink, etc. from the viewpoint of durability, You may form using 1 liquid ink which uses a polyester resin, a vinyl chloride resin, a vinyl chloride / vinyl acetate copolymer resin, an acrylic resin, etc. as a vehicle. As pigments and dyes used in the color ink, pigments and dyes used for ordinary printing inks can be used. The wiping embossing itself has been carried out since the era of embossed design sheets using a soft PVC sheet, and can be applied by various known methods such as a doctor blade method and a roll coating method.

<Embossed design sheet coated metal plate 300>
FIG. 1 (g) shows an embossed design sheet-covered metal plate 300 </ b> A in which the C layer 30 side surface of the embossed design sheet 200 </ b> A (the back surface of the embossed design sheet 200 </ b> A) is laminated on the metal plate 60 via the adhesive 70. FIG. 1 (h) shows an embossed design sheet-covered metal plate 300B laminated on the metal plate 60 in the same manner as the embossed design sheet 200B. FIG. 1 (i) shows a metal plate in the same manner as the embossed design sheet 200C. An embossed design sheet-coated metal plate 300C laminated on 60 is shown.

  As the metal plate 60 used for the embossed design sheet-coated metal plate 300 of the present invention, hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, tin plated steel plate, aluminum / zinc alloy plated steel plate, high aluminum Various steel plates such as zinc alloy plated steel plate, aluminum / magnesium / zinc alloy plated steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, aluminum alloy clad plate, titanium alloy plate, nickel alloy plate, magnesium alloy A board etc. can be used and you may use these, after giving a normal chemical conversion treatment. The thickness of the metal plate 60 varies depending on the application of the resin-coated metal plate and the like, but can be selected in the range of 0.1 mm to 10 mm. As a resin-coated metal plate used for a unit bath, a sheet having a thickness of about 0.3 mm to 0.6 mm such as a hot dip galvanized steel sheet is generally used.

  The method for laminating the embossed design sheet 200 on the metal plate 60 is not particularly limited, but the same method as that used when laminating the conventional soft PVC sheet on the metal plate 60 is preferable from the viewpoint that existing equipment can be used. That is, a heat laminate using an adhesive 70 is preferably used. As the adhesive 70, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, or the like, which is generally used, is used. A mold adhesive can be mentioned. Among these, since the laminated sheet of the present invention is made of a polyester-based resin, it is preferable to use a polyester-based adhesive.

  As a method for obtaining the embossed design sheet-covered metal plate 300, for example, a commonly used coating facility such as a reverse coater or a kiss coater is used on the metal plate 60, and after drying on the metal surface to which the embossed design sheet is bonded. After applying the thermosetting adhesive so that the film thickness of the adhesive becomes 0.5 μm or more and 10 μm or less, the metal plate 60 is subjected to solvent drying and heat baking of the coated surface with an infrared heater and / or a hot air heating furnace. While maintaining the surface temperature of 220 ° C. or more and 250 ° C. or less, immediately using a roll laminator, the embossed design sheet 200 is coated so that the C layer 30 side becomes an adhesive surface, and then water is added to the water tank. The method of cooling by cooling or water injection is mentioned. In general, the surface temperature of the metal plate when the soft PVC sheet is coated is about 220 ° C. or more and 235 ° C. or less.

  The embossed design sheet-coated metal plate 300 of the present invention can have various designs by combining the design by the printed pattern D40 and the embossed design. Further, in order to ensure the heat resistance of the emboss, when a resin composition containing an aromatic polycarbonate resin is used as the resin composition of the A layer 10, a pearl mica pigment can be added to the A layer 10. However, in the present invention, the pearl mica pigment can be added to the A layer 10 without any problem, and the embossed design sheet-coated metal plate 300 having a calm pearl-like design feeling can be obtained. Furthermore, since it has good workability and surface hardness, it can be widely applied to various applications. Specifically, unit bath members such as unit bath wall materials, unit bath ceiling materials, closet door materials, partition materials, panel interior materials such as panel materials, steel furniture members, home appliances such as AV equipment and air conditioner covers It can be suitably used as a casing member.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless the gist of the present invention is exceeded.

[Production of laminated sheet]
<Examples 1-15, Comparative Examples 1-14>
As Examples 1 to 15 and Comparative Examples 5 to 14, two 65-mm vented concentric twin-screw extruders and one vented φ65 mm single-screw extruder were used. A non-oriented laminated sheet consisting of A layer, B layer, and C layer is formed by a general method in which the resin flowing out from the T die is drawn by a casting roll by a co-extrusion method using a layer type T die. Produced.
For melting and kneading of the A layer, a φ65 mm single screw extruder having one vent suction hole was used, and the set temperature of the cylinder was 230 ° C. on the feed side and 240 ° C. on the base side. When using a blend composition as the resin component of the A layer, rather than preparing a pre-kneaded blend master batch in advance, each raw material pellet is mixed with the mass of the composition ratio, and directly from a single quantitative feed feeder to the extruder I put it in. For melting and kneading of the B layer and the C layer, φ65 mm same-direction twin screw extruders having two vent suction holes were used. The cylinder set temperatures of the extruders for the B layer and the C layer are 230 ° C. on the feed side and 240 ° C. on the base side. The connecting pipe and the three-layer confluence feed block were set at a set temperature of 240 ° C. and finely adjusted according to the conditions of film formation. The set temperature in the width direction of the T-die is also set to 240 ° C., and fine adjustment is appropriately performed according to the film forming situation. Regarding the B layer and the C layer, when using the blend composition as a resin component, the mixed pellets were directly charged.

As a take-up roll (casting roll), a 500 mm diameter metal roll engraved with embossing to give a textured surface with a centerline average roughness (Ra) of 1 μm and a maximum height (Ry) of 6 μm on the surface. Using. The embossing imparted to the surface of the metal roll is not for imparting an embossed design feeling to the laminated sheet, but for imparting slipperiness to the film-formed sheet and improving the rollability. In addition, it is extruded so that the side which forms A layer may be the take-up roll side, and the take-up roll is temperature adjusted by circulating hot water whose temperature is adjusted to the glass transition temperature of the resin composition of layer A -15 ° C. A silicone rubber touch roll is brought into contact with the side on which the C layer is formed.
Further, 24 parts by mass of a white pigment mainly composed of a titanium oxide pigment is added to the B layer based on the total amount of the resin components of the B layer (100 parts by mass). The pigment was added by mixing a required amount of a pigment master batch having a pigment component concentration of 50% by mass using PETG or PCTG as a base resin. The extruded sheet is not subjected to special crystallization treatment or curing in a temperature-controlled room.

In Comparative Example 1, the resin composition of layer A was formed into a sheet by single-layer film formation using only a single-screw extruder of φ65 mm, and the implementation was performed except that no feed block was interposed between the extruder and the die. Extrusion film formation is performed under the same conditions as in Examples 1 to 15 and Comparative Examples 5 to 14.
Comparative Example 2 to Comparative Example 4 have a configuration in which any one of the A layer, the B layer, and the C layer does not exist, and a comparative example 2 and a comparative example using a two-layer merged feed block and a necessary connection conduit. As for Example 3, two-layer coextrusion film formation using a single screw extruder of φ65 mm, a single screw and a twin screw extruder of φ65 mm in the same direction is carried out. For Comparative Example 4, two-layer coextrusion film formation is carried out using a φ65 mm co-directional twin-screw extruder and two units. For the extruder, Examples 1 to 15 and Comparative Examples 5 to 14 are used. It is the same as that used, and the temperature conditions at the time of film formation are the same. The same take-up roll is used and the temperature conditions are set similarly. In Comparative Example 4 where the A layer does not exist, the take-up roll is heated to a glass transition temperature of −15 ° C. of the resin composition of the B layer. It was adjusted.

  About the composition of the resin used in each layer of Examples 1 to 15 and Comparative Examples 1 to 14, the thickness of the layer, etc., the A layer is shown in Table 1, the B layer is shown in Table 2, and the C layer is shown in Table 3. Each is shown. Moreover, in Table 4, the combination of each layer in the sheet | seat of Examples 1-15 and Comparative Examples 1-14 and the layer thickness of a lamination sheet are shown.

<Example 16, Example 17>
Using two co-directional twin screw extruders with φ65mm with vent suction holes, the resin flowing out from the T die was cast by a casting roll using a co-extrusion method using a two-layer merged feed block and a single-layer T die. A two-layer laminate sheet of B layer and C layer was obtained by a general method of pulling. As the resin composition and thickness of the B layer, those corresponding to b-4 in Table 2 are used, and white based on the titanium oxide pigment based on the total amount of the resin components of the B layer (100 parts by mass). 24 parts by mass of a pigment are added. Further, as the resin component and thickness of the C layer, those corresponding to c-4 in Table 3 are used. Extrusion conditions and take-up conditions are the same as in Comparative Example 4 that does not have the A layer.
On the surface of the layer B side of the laminated sheet, a printed pattern D was printed as a stone pattern by gravure printing using an acrylic / urethane ink.

Separately, using a single-screw extruder with a φ65 mm vent, the A layer is extruded and formed as a single-layer transparent sheet with a T-die, or as a transparent laminated sheet by co-extrusion using two extruders. A layer and E layer were formed into a film. These A layer, or A layer and E layer, and the above B layer and C layer are heat-sealed and laminated at the heating roll portion of the embossing apparatus shown in FIG. Seventeen laminated sheets were produced. Extrusion conditions and take-up conditions in Example 16 are the same as in Comparative Example 1 in which the A layer is formed as a single layer, and the extrude conditions and take-up conditions in Example 17 consist of the A layer and the B layer. This is the same as in Comparative Example 2 in which a two-layer coextruded sheet was formed. About Example 17 using the transparent laminated sheet of A layer and E layer, the surface by the side of E layer was laminated | stacked and integrated with the surface of B layer via the printing pattern D by heat-fusion lamination.
Regarding the resin composition and thickness of the A layer, those corresponding to a-1 in Table 1 were used in both Examples 16 and 17. As the E layer, a pigment-free layer composed of only Easter PETG · 6763 as a resin component was provided with a thickness of 20 μm. Table 5 shows combinations of layers in the sheets of Example 16 and Example 17 and the presence or absence of the E layer.

<Example 18, Comparative Examples 15 and 16>
Similar to Examples 1 to 15 and Comparative Examples 5 to 14, using two vented concentric twin-screw extruders with a diameter of 65 mm and one vented φ65 mm single-screw extruder, a three-layer merged feed A non-oriented structure with a three-layer structure consisting of an A layer, a B layer, and a C layer by a general method in which the resin that has flowed out of the T die is drawn by a casting roll by a coextrusion method using a block and a single layer type T die. A laminated sheet was produced.
In Example 18 and Comparative Examples 15 and 16, a pearl mica pigment is blended in the A layer. In Example 18, a pearl mica pigment master batch having a pigment component concentration of 12 parts by mass and a resin material having the same composition as the resin composition of the A layer as a base resin was mixed in a necessary amount, whereby the entire resin component of the A layer was mixed. Based on the amount (100 parts by mass), 1.5 parts by mass of pearl mica pigment is added. As the pearl mica pigment, “DE-330R White” (particle size: 10 to 60 μm, thickness: about 1/5 to 1/10) manufactured by Dia Kogyo Co., Ltd. was used.
In Comparative Example 15, a master batch having a pearl pigment concentration of 12 parts by mass was prepared using PCTG · 5445 as a base resin, and in Comparative Example 16 as Novalex 7025A as a base resin. Based on the amount of the resin component as a reference (100 parts by mass), 1.5 parts by mass of pearl mica pigment was added. The same pearl mica pigment as used in Example 18 was used. In addition, regarding the A layer of Comparative Example 15, three raw material pellets of pearl pigment master batches using PCTG · 5445, Novalex 7025A, and PCTG · 5445 as the base resin were mixed with the mass of the composition ratio, and a single amount was determined. The feed was fed directly into the extruder from the feeder.

  Extrusion film forming conditions in Example 18 are the same as those in Examples 1-15. The cylinder set temperatures of the extruders for the B layer and the C layer in Comparative Examples 15 and 16 are the same as in Examples 1 to 15, but for the A layer in Comparative Examples 15 and 16, an aromatic polycarbonate resin is used. Since it was a composition containing, it was necessary to set the cylinder set temperature of the φ65 mm single screw extruder to 260 ° C. on the feed side and 280 ° C. on the die side. Further, the connection temperature of the connecting conduit and the three-layer merged feed block is set to 270 ° C., and the set temperature in the width direction of the T die is based on 270 ° C. Similar to the other examples and comparative examples, the fine adjustment is appropriately performed according to the state of film formation.

  Further, in Example 18, Comparative Example 15 and Comparative Example 16, the resin composition and thickness of the B layer are those corresponding to b-6 in Table 2, but the color development of the pearl mica pigment of the A layer is good. Therefore, in place of the titanium oxide white pigment, 4 parts by mass of a black pigment mainly composed of a carbon black pigment was added on the basis of the total amount of the resin component of the B layer (100 parts by mass). The pigment was added by mixing a required amount of a pigment master batch having a pigment component concentration of 15% by mass using PETG as a base resin.

  In addition, the glass transition temperature (Tg) of the resin composition of the A layer shown in Table 1 and Table 6 uses a differential scanning calorimeter “DSC-7” manufactured by Perkin Elmer Co., Ltd., and 10 mg of the sample is JIS K 7121. According to the “Plastic Transition Temperature Measurement Method”, the temperature is raised from −40 ° C. to 250 ° C. at a heating rate of 10 ° C./min, held at 250 ° C. for 1 minute, and then cooled to −40 ° C. at a cooling rate of 10 ° C./min. This is a value obtained from a thermogram when the temperature was lowered and held at the same temperature for 1 minute and then heated again at 10 ° C./min. As a sample used for the measurement, as for the A layer in the coextruded laminated sheet, a material obtained by scraping the resin using a microtome is used, and for the A layer formed as a single layer, the measurement sample is used as it is. It was. Further, regarding the glass transition temperature and melting point described in the physical properties of the raw materials used below, the raw material pellets were used as they were as samples.

(Altester 45)
It is an amorphous polyester resin manufactured by Mitsubishi Gas Chemical Company. The dicarboxylic acid component is terephthalic acid, and 44 mol% of the diol component contains spiroglycol, about 53 mol% ethylene glycol, and about 3 mol% diethyleneglycol. The measured glass transition temperature was 111 ° C. and no melting point was observed.

(Easter PETG · 6763)
It is an amorphous polyester resin manufactured by Eastman Chemical Company (abbreviated as “PETG · 6763” in the table). The dicarboxylic acid component is terephthalic acid, and about 31 mol% of the diol component contains 1,4-cyclohexanedimethanol, about 65 mol% ethylene glycol, and about 4 mol% diethylene glycol. The measured glass transition temperature was 78 ° C. and no melting point was observed.

(Easter PCTG · 5445)
It is a polyester resin that can be handled as a substantially non-crystalline polyester resin manufactured by Eastman Chemical Company (abbreviated as “PCTG • 5445” in the table). The dicarboxylic acid component is terephthalic acid, and 61 mol% of the diol component contains 1,4-cyclohexanedimethanol, about 38 mol% ethylene glycol, and about 1 mol% diethylene glycol. The measured glass transition temperature was 86 ° C. and no melting point was observed.

(Novalex 7025A)
This is a bisphenol A polycarbonate resin manufactured by Mitsubishi Engineering Plastics. With a viscosity average molecular weight of 25000, the measured glass transition temperature was 150 ° C., and no melting point was observed.

(Novaduran 5020H)
(Homo) polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics. The nominal IV value was 1.2 and the measured melting point was 224 ° C.

(Coltera CP509200)
(Homo) polytrimethylene terephthalate resin manufactured by Shell. The measured melting point was 225 ° C.

(DURANEX (registered trademark) 500JP)
It is an isophthalic acid copolymerized polybutylene terephthalate resin manufactured by Wintech Polymer. The measured melting point was 205 ° C.

(BK-2180)
This is an isophthalic acid copolymerized polyethylene terephthalate resin manufactured by Mitsubishi Chemical Corporation. The measured glass transition temperature was 76 ° C. and the melting point was 246 ° C.

[Embossing on laminated sheet]
About the lamination sheet obtained in Examples 1-18 and Comparative Examples 1-16, the embossing pattern was transferred using the embossing apparatus shown by FIG. In addition, regarding the films formed by separately forming the A layer, the B layer, and the C layer of Examples 16 and 17, the heat fusion lamination is simultaneously performed in the heating roll portion of the embossing apparatus as described above. Street. Here, embossing will be described in detail.

  As an outline of the embossing process, first the sheet is pre-heated by contact-type heating using a heating roll, and then the sheet is heated to any temperature by non-contact-type heating using an infrared heater. The embossed pattern is transferred to an embossed design sheet by an embossing roll adjusted to the temperature.

In this example, the heating roll was set to 140 ° C., and then heated with an infrared heater so that the sheet surface temperature immediately before contacting the embossing roll was 160 ° C. The temperature of the embossing roll is adjusted by a hot water circulator based on “Glass transition temperature of each A layer—15 ° C.”. As an example, in Example 1, since the glass transition temperature of the resin composition of the A layer is 111 ° C., the surface temperature of the embossing roll is set to about 95 ° C.
In addition, the embossing roll used two types of embossing rolls corresponding to two types of embossing designs, a precision embossing design and a normal embossing design. The precision embossed design is an embossed design onto which fine prismatic protrusions with Ry (maximum height) = 14 μm and Ra (center line average roughness) = 2.2 μm are transferred. The normal embossed design is an embossed design to which an abstract pattern (skin tone) of Ry (maximum height) = 57 μm and Ra (centerline average roughness) = 6.5 μm is transferred.

[Production of embossed design sheet coated metal sheet]
Application of a commercially available heat-curable polyester adhesive for polyvinyl chloride coated metal plates to the surface on the side where the laminated sheet of the metal plates is bonded so that the adhesive film thickness after drying is in the range of 1 μm to 3 μm. did. Next, the coated surface was dried and heated with an infrared heater and a hot air heating furnace. Then, while maintaining the surface temperature of the metal plate to be 235 ° C., the C layer side surface of the laminated sheet was immediately coated as an adhesive laminated surface using a roll laminator. Immediately after that, cooling by water jet was performed to obtain an embossed design sheet-covered metal plate. As the metal plate, an electrogalvanized steel plate having a thickness of 0.45 mm was used.

[Evaluation of laminated sheet and embossed design sheet coated metal sheet]
The following items were evaluated for the laminated sheet and the embossed design sheet-covered metal plate obtained in the above Examples and Comparative Examples. The results are summarized in Table 7, Table 8, and Table 9.

(1) Handling property of laminated sheet The laminated sheets of Examples 1 to 15 and Comparative Examples 2 to 14 produced by the coextrusion film forming method were evaluated with respect to the handling property before embossing.
The laminated sheet was cut out in the MD direction 15 cm × TD direction 30 cm, placed on the surface plate so that the C layer (B layer for Comparative Example 2) side was the lower surface, and the state of warping was observed. When the warpage is strong and completely cylindrical, or when the arch shape with a height of 10 cm or more from the surface plate surface is warped, “X” is less than 10 cm, but the warpage of 5 cm or more appears. “△”, and the case of warping less than that was evaluated as “◯” because the handleability was good. Subsequent evaluations were not performed for those with a handling property of “x”.

(2) Handling property with single layer A Since Examples 16 and 17 were formed by using a relatively thin transparent layer, the handling property was evaluated. When passing the A layer sheet or the sheet consisting of the A layer and E layer through the embossing device, if the workability is remarkably poor due to wrinkles, etc. The case where it can be set on the embossing machine is indicated by “◯”, and the case of intermediate workability is indicated by “Δ”.

(3) Designability of laminated sheet by pearl pigment The color designability of laminated sheets of Example 18 and Comparative Examples 15 and 16 in which a pearl mica pigment was added to the A layer was visually observed. A case where the design feeling is inferior due to deterioration of the pigment or deterioration of the resin due to the thermal catalytic action of the pigment is “x”, and there is no problem in the design property, and a laminated sheet having a good pearly luster has been obtained. The case was set as “◯”. This evaluation was performed on the sheet before embossing.

(4) Embossing suitability (4-1) Adhesion resistance When embossing was applied with the embossing apparatus shown in FIG. 2, the laminate sheet adhered to the heating roll and became difficult to peel, and peeling was possible. Although the sheet was markedly stretched and deformed, it was “x”, indicating slight adhesion, but it was possible to continue the work, and the sheet stretched and deformed was within the range where there was no practical problem. “△” indicates that a stable operation was possible without sticking, and “◯”. Subsequent evaluation was not performed about what became "x" by adhesion resistance.

(4-2) Fusing resistance When embossing is applied with the embossing apparatus shown in FIG. 2, the sheet is melted while the sheet is heated by an infrared heater, and the sheet is noticeably stretched or wrinkled. “×” means that the sheet was slightly stretched or reduced in width, but was within the practical range, and “△” means that these problems did not occur and stable work was possible. ○ ”. No further evaluation was performed for those evaluated as “x” in this evaluation.

(4-3) Precise embossing transfer property The sheet with precise embossing is visually observed with the embossing device shown in Fig. 2, and "○" indicates that the embossed pattern is transferred cleanly. “△” indicates that the surface is shallow, and “×” indicates that the transfer is poor and has a shallow embossed pattern, or that the surface is simply rough regardless of the embossed pattern.

(4-4) Normal emboss transferability The sheet with the normal embossing depth is visually observed with the embossing machine shown in FIG. “△” indicates that the transfer is slightly shallow, and “×” indicates that the transfer is poor and has a shallow embossed pattern, or that the surface is simply rough regardless of the embossed pattern.

(5) Emboss heat resistance (5-1) High temperature air heat resistance Surface roughness meter (manufactured by Kosaka Laboratories Co., Ltd.) on the resin layer side surface of a metal plate laminated with a sheet embossed with precision emboss by the embossing apparatus shown in FIG. “Surfcoder” SE-40D) is used to mark the measurement start and end points with ink that does not fade even when exposed to high temperatures for a short time, and then in a hot air circulation oven at 105 ° C. for 3 hours. Left to stand. After taking out from the oven and cooling, the measurement points marked with the above are subjected to roughness measurement again, the center line average roughness before being put into the oven is Ra1 (μm), and after standing in the oven Ra2 ( μm) to determine the residual ratio of emboss (residual ratio: Ra2 / Ra1 × 100 (%)).
The case where the residual rate is 75% or more is “◯”, the residual rate is less than 75%, but the case where it is not visually recognized as a remarkable abnormality is “△”, the residual rate is less than 75%, The case where the design feeling of embossing is clearly lowered visually is indicated by “x”.

(5-2) Boiling water immersion resistance The surface roughness meter ("Surfcoder" SE-S manufactured by Kosaka Laboratory) was used to measure the resin layer side surface of the metal plate laminated with a sheet embossed with precision embossing using the embossing device shown in FIG. 40D), the measurement start point and end point were marked with ink that did not fade even when immersed in boiling water for a short time, and then immersed in boiling water for 3 hours. After taking out and drying, the measurement points marked with the above are subjected to roughness measurement again, the center line average roughness before being poured into boiling water is Ra3 (μm), and after immersion in boiling water is Ra4 (μm) As a result, the residual ratio of the emboss was determined (residual ratio: Ra4 / Ra3 × 100 (%)).
The case where the residual ratio is 75% or more and there is no deformation due to softening / flow of the resin layer due to boiling water immersion other than embossing return, and the residual ratio is less than 75% However, when it is not visually recognized as a remarkable abnormality, and the residual rate is 75% or more, but there is a slight deformation due to softening and flow of the resin layer due to boiling water immersion. “△”, the residual rate is less than 70%, and the design feeling of embossing is clearly lowered visually, and regardless of the residual rate, it is remarkably caused by deformation caused by softening and flow of the resin layer. The case where the designability is reduced is indicated by “x”.

(6) Workability (Bendability of resin-coated metal sheet)
An impact adhesion bending test is performed on a metal plate laminated with a sheet with precision embossing using the embossing apparatus shown in FIG. 2, and the surface state of the embossed design sheet in the bent portion is visually determined. “○”, a case where a slight crack occurred was evaluated as “Δ”, and a case where a crack occurred was evaluated as “×”. The impact adhesion bending test was performed as follows. Samples of 50 mm x 150 mm were prepared from the length direction and width direction of the embossed design sheet-coated metal plate, kept at 23 ° C for 1 hour or longer, and then bent to 180 ° (inner bending radius 2 mm) using a bending tester. A cylindrical weight having a diameter of 75 mm and a mass of 5 kg was dropped on the sample from a height of 50 cm.

(7) Surface hardness (pencil hardness test of resin-coated metal plate)
With respect to a metal plate laminated with a sheet embossed with precision embossing by the embossing apparatus shown in FIG. 2, JIS K5600-5-4: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 4: It was carried out according to “Scratch hardness (pencil method)”. Using a jig that can draw a wire under a load of 9.8 N while maintaining a 45 ° angle with respect to the embossed design sheet surface of the embossed design sheet coated metal sheet cut out to 80 mm x 60 mm in a 23 ° C constant temperature room Then, the surface state of the resin sheet of the part is visually determined, and “○” indicates that the 2B pencil was not scratched at all. Those that were not attached were displayed as “Δ”, and those that were scratched even with the 3B pencil were displayed as “×”.

[Evaluation results]
<Examples 1-15 and Comparative Examples 1-14>
Comparative Example 1 is an example in which the A layer is used as a single layer. In this case, the heating roll of the embossing apparatus was markedly sticky and difficult to peel off, and the sheet could not be embossed.

  Comparative Example 2 is an example of a laminated sheet having a C layer that is composed of two layers of an A layer and a B layer that can be used in the present invention. In this case, the B transition layer having a low glass transition temperature and low crystallinity was brought into contact with the heating roll of the embossing apparatus, thereby causing adhesion that was difficult to peel off.

  Comparative Example 3 is an example of a laminated sheet having a B layer that is composed of two layers of an A layer and a C layer that can be used in the present invention. In this case, the layer to which the embossed pattern was transferred after being softened by heating and being embossed was only the A layer, and since there was no thickness, good transfer of the embossment of normal depth could not be obtained. Good results were obtained for the transfer of precision embossing, and there was no problem with the heat resistance of embossing. However, it does not satisfy the design as a resin-coated metal plate because it has no colored layer. It was.

  Comparative Example 4 is an example in which the A layer of the present invention does not exist. By using an embossing roll adjusted to a temperature lower than the glass transition temperature of the resin composition of the B layer, a good embossing transfer itself was obtained. The reason why the transfer of embossing at a normal depth is somewhat bad is considered to be due to the fact that the total thickness of the laminated sheet is reduced due to the absence of the A layer. However, the heat resistance of the embossing was poor, and the design feeling was significantly lowered especially when immersed in boiling water. It is considered that the embossing heat resistance was not obtained because the glass transition temperature of the resin composition of the B layer was as low as about 86 ° C. and the embossing roll was set at a low temperature of about −15 ° C. It is done.

  Comparative Examples 5 to 7 are examples in which the glass transition temperature of the substantially amorphous copolymer polyester resin constituting the A layer is lower than the range of the present invention. In this case, no special problem has occurred in the embossing step, and good embossing transfer has been obtained. As in the case of Comparative Example 4, the metal plate laminated with the laminated sheet after embossing was placed in boiling water. When dipped, the designability was significantly lowered, and the embossing heat resistance was insufficient.

  Comparative Example 8 is an example in which the thickness of the B layer is thinner than the range of the present invention. In this case, although there was no problem with the transfer of the precision emboss, the total thickness of the laminated sheet was insufficient to transfer the emboss of the normal depth. In addition, since the thickness of the B layer, which is a layer to which a colorant is added, is thin, the surface treatment state of the metal plate is visible from the surface of the resin layer, and the design property as a resin-coated metal plate is not satisfied. There wasn't. Although concealment can be secured by further increasing the pigment concentration of the B layer, the thickness of the B layer should be further increased in consideration of film forming properties, durability of the laminated sheet-coated metal plate, workability, etc. Is considered preferable.

  Comparative Example 9 is an example in which the blending amount of the polybutylene terephthalate resin of the C layer is less than the range of the present invention. In this case, it was possible to barely peel off while showing adhesion to the heating roll of the embossing device, but when the laminated sheet was heated with an infrared heater, significant sheet elongation and wrinkling occurred and good embossed transfer was obtained. I couldn't.

  Comparative Example 10 is an example in which the thickness of the C layer is thin although the blending ratio of the resin composition of the C layer is within the preferred range of the present invention. In this case, both ends of the sheet showed remarkable adhesion to the heating roll. Although it could be peeled off, significant sheet elongation and wrinkling occurred when the laminated sheet was heated with an infrared heater. When the laminated sheet is formed by the feed block method, the adhesion of the end part to the heating roll causes a development failure in the width direction due to the thickness of the C layer being too thin, and the C layer is formed at the end part. It may not be. It seems that this problem can also be solved by optimizing the conditions of the coextrusion method. However, the elongation of the sheet by heating with an infrared heater is also caused by the thin C layer, which is a tension holding layer.

  Comparative Example 11 is an example in which a C layer having a larger amount of polybutylene terephthalate resin than the scope of the present invention was used. In this case, the warp of the laminated sheet became remarkable, which hindered smooth introduction into the embossing apparatus.

  Comparative Example 12 is an example in which a polybutylene terephthalate resin copolymerized with isophthalic acid was used as the C-layer polybutylene terephthalate resin. In this case, after showing slight adhesion to the heating roll, the laminated sheet was significantly stretched and wrinkled by heating with an infrared heater. The slight adhesion to the heating roll is caused by the fact that the crystallization rate of the isophthalic acid copolymerized polybutylene terephthalate resin is slower than that of the homopolybutylene terephthalate resin. This is probably because the heating roll was left while crystallization was insufficient. Further, since the melting point of the resin is about 205 ° C., it is considered that the melt tension is insufficient when heated to 160 ° C. by an infrared heater.

  Comparative Example 13 is an example in which a polyethylene terephthalate resin copolymerized with isophthalic acid, which has crystallinity in the C layer but has a very low crystallization rate, is used. Similar to the case of Comparative Examples 1 and 2 having a configuration without the C layer, the heating roll was extremely sticky, and it was difficult to peel off, making the subsequent operation impossible.

  Comparative Example 14 is an example in which the thickness of the A layer and the B layer was carelessly increased, and the total thickness of the laminated sheet exceeded 300 μm. In this case, there was no problem in embossing suitability and embossing heat resistance, and a resin-coated metal plate having high design properties was obtained. However, cracks occurred in the resin layer in the workability test. If the total thickness of the laminated sheet is excessive, it can be said that the workability is lowered.

  In contrast to the above comparative examples, the laminated sheets of Examples 1 to 15 of the present invention were stably obtained by the coextrusion film forming method, and the handleability of the obtained laminated sheets was good. Moreover, stable work could be performed with the embossing apparatus, and good transferability was obtained for both the precision embossed pattern and the normal embossed pattern. Moreover, the metal plate laminated with the laminated sheet had good heat resistance of embossing, and good workability and surface hardness.

<Examples 16 and 17>
Example 16 is a two-layer co-extrusion laminated sheet consisting of a B layer and a C layer, in which a layer A having a thickness of 30 μm is formed as a single layer and a printed pattern D is provided on the surface of the B layer, and a heating roll of an embossing device This is an example of heat fusion lamination at a part. In this case, there was no particular problem in heat-fusibility, and the same was true for emboss transferability, and a resin-coated metal plate having a good emboss design and printing design could be obtained. Moreover, there was no problem in embossing heat resistance and workability. However, due to the thin thickness of the A layer formed as a single layer, there was a slight problem in handling of the A layer, and workability when passing through the embossing apparatus was poor.

  On the other hand, Example 17 is an example in which the total thickness of the transparent layer is 50 μm as the co-extrusion lamination with the E layer while keeping the thickness of the A layer. In this case, the handleability of the transparent layers (A layer and E layer) was better than that of Example 16. As for the other performances, as in Example 16, it is better to secure the thickness of the transparent layer as a co-extruded laminated sheet in this way than to increase the thickness of the A layer whose raw material price is relatively expensive and ensure the handleability. It is thought that it can gain merit in terms of cost.

<Example 18, Comparative Examples 15 and 16>
Comparative Example 16 is an example in which a master batch of pearl pigment was prepared using a polycarbonate resin as a base resin. In this case, a brown sheet is formed at the time of the pellet of the master batch, and the layered sheet formed using the master batch has a brown taste in the A layer, and a good design feeling of pearly luster cannot be obtained. It was. Since the molding temperature of the aromatic polycarbonate resin is high, the titanium oxide, which is the surface coating of the pearl mica pigment, exhibits a thermal degradation catalytic action in both the steps of master batch preparation and extrusion film formation, and the resin composition of layer A It is thought that this promoted the deterioration of

  Comparative Example 15 is an example in which a master batch of pearl pigment was prepared using PCTG · 5445 as a base resin. In this case, a good pearl-like design feeling was confirmed at the time of the masterbatch pellets, but the layer A of the laminated sheet after film formation was tinged with brown color, and the design feeling of pearl luster was poor. there were. In the masterbatch production process, the base resin melt kneading temperature is lower than that of the aromatic polycarbonate resin, so it seems that there was no particular problem. It is necessary to set the temperature at which the resin can be melt-kneaded, and it is presumed that thermal degradation of the resin was promoted in the film forming process.

  On the other hand, Example 18 of the present invention uses a resin composition that can be used for the A layer of the present invention as a base resin to produce a master batch of pearl pigment, and the laminated sheet after film formation is It had a good pearl design. Moreover, the results comparable to Comparative Examples 16 and 17 were obtained with respect to emboss transferability, emboss heat resistance as a resin-coated metal plate, and workability.

  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. Rather, it can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and a laminated sheet, an embossed design sheet, an embossed design sheet-coated metal plate, and a unit bath with such changes Members, building interior materials, steel furniture members, and household appliance housing members are also to be understood as being within the scope of the present invention.

(A), (b), (c) is a schematic diagram which shows the laminated constitution of laminated sheet 100A, 100B, 100C of this invention. (D), (e), (f) is a schematic diagram which shows the layer structure of the embossed design sheet | seat 200A, 200B, 200C of this invention. (G), (h), (i) is a schematic diagram which shows the layer structure of the embossed design sheet | seat metal plate 300A, 300B, 300C of this invention. It is a schematic diagram which shows an example of the embossing apparatus 400 generally used in order to provide an embossing pattern.

Explanation of symbols

10 A layer 20 B layer 30 C layer 40 Print pattern D
50 E layer 60 Metal plate 70 Adhesive 100A, 100B, 100C Laminated sheet 200A, 200B, 200C Embossed design sheet 300A, 300B, 300C Embossed design sheet-coated metal plate 400 Embossing device 410 Heating roll 420 Take-off roll 430 Infrared heater 440 Nip roll 450 Embossing roll 460 Cooling roll

Claims (12)

A laminated sheet comprising three layers of A layer, B layer and C layer shown below in order from the surface side, and having a total thickness in the range of 55 μm to 300 μm.
Layer A: terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, 45 mol% or less of spiroglycol and 50 mol% or more of ethylene glycol as the main component of the diol component, heating rate 10 ° C / A non-oriented layer having a glass transition temperature measured in minutes of 100 ° C. or higher and a substantially amorphous copolymer polyester resin composition having a thickness of 100 μm or less.
B layer: a layer having a thickness of 40 μm or more, which is mainly composed of a polyester resin that is substantially amorphous and to which a colorant is added.
C layer: a polybutylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less and / or a polytrimethylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less, and the mass of the entire resin component in the C layer A non-oriented layer having a thickness of 5 μm or more, comprising 70% by mass or more and 95% by mass or less as 100% by mass. The A layer contains 0.5 m parts or more and 5 parts by mass or less of a pearl mica pigment in which the surface of the scaly mica is coated with titanium oxide, with the resin component of the A layer as a whole being 100 parts by mass. The laminated sheet according to claim 1. The substantially non-crystalline polyester resin of the B layer comprises terephthalic acid or dimethyl terephthalic acid as a main component of a dicarboxylic acid component, and 25 mol% or more and 75 mol% or less 1,4-cyclohexanedimethanol, 25 The laminated sheet according to claim 1 or 2, which is a copolyester resin mainly composed of mol% or more and 75 mol% or less of ethylene glycol as a main component of a diol component. The B layer has a melting point of not less than 55% by mass and not more than 80% by mass of the substantially amorphous polyester-based resin, and having a melting point of not less than 20% by mass and not more than 45% by mass, with the total resin component of the B layer being 100% by mass The laminated sheet according to any one of claims 1 to 3, comprising a polybutylene terephthalate resin having a melting point of 210 ° C to 230 ° C and / or a polytrimethylene terephthalate resin having a melting point of 210 ° C to 230 ° C. The laminated sheet according to any one of claims 1 to 4, wherein the A layer is substantially transparent and has a printed pattern D between the A layer and the B layer. Between the A layer and the printed pattern D, an E layer mainly composed of a polyester resin that is substantially transparent and substantially amorphous is interposed, and the A layer and the E layer Is a laminated sheet according to claim 5, which is laminated and integrated by a coextrusion film forming method. An embossed design sheet comprising: the laminated sheet according to any one of claims 1 to 6; and a concavo-convex shape formed by an embossed plate on the surface of the layer A of the laminated sheet. An embossed design sheet-covered metal plate comprising the embossed design sheet according to claim 7 and a metal plate, wherein the surface of the embossed design sheet on the side of the C layer is laminated to the metal plate via an adhesive. A unit bus member using the embossed design sheet-coated metal plate according to claim 8. A building interior material using the embossed design sheet-coated metal plate according to claim 8. A steel furniture member using the embossed design sheet-coated metal plate according to claim 8. A household electrical appliance housing member using the embossed design sheet-coated metal plate according to claim 8.

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