JP2008100383A - Laminated sheet, embossed design sheet and embossed design sheet-coated metal plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet having good lamination adequacy with respect to a metal plate, well applying an embossed design having heat resistance and well transferring even a precise embossed design. <P>SOLUTION: The laminated sheet with the total thickness of 55-300 μm has an A-layer, which is a non-oriented layer with a thickness of 10 μm or above based on a blend composition of a polyester resin and an aromatic polycarbonate resin or the aromatic polycarbonate resin and has a single glass transition temperature of 100-150°C, a B-layer which contains a color pigment and is based on a substantially amorphous polyester resin, and a C-layer which is a non-oriented layer with a thickness of above 20 μm containing 70-95 mass% of a polybutylene terephthalate (PBT) resin or a polytrimethylene terephthalate (PTT) resin with a melting point of 215-235°C, successively from a surface side. <P>COPYRIGHT: (C)2008,JPO&INPIT

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 embossing suitability and metal plate laminating suitability, which can be suitably used for a coating material having an embossed design such as a building interior material, an embossed design sheet obtained by embossing the laminated sheet, and The present invention relates to an embossed design sheet-covered metal plate coated with an 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 embossing the long sheet of soft PVC, the sheet after film formation is softened by reheating and the pattern is continuously suppressed by a roll engraved with an embossed pattern (embossed plate roll). In general, a method of transferring images is generally 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. Equipment having these series of steps is called an embossing machine or the like.

  In this embossing machine, it is common to incorporate a design that makes it easy to replace and remove the embossing plate roll, and the diameter of the embossing plate roll is small compared to the casting roll of the extrusion film-forming equipment, Since it is possible to easily and economically change the embossed pattern by preparing various types of embossed plate rolls, it can be said to be an embossing method suitable for small lot compatibility.

  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 the embossing machine. In this case, the sheet is preheated with an embossing machine, and two layers of sheets are laminated and integrated by thermal fusion, etc., and production is not required because a special process for lamination is not required. It was good in terms of cost and cost.

  As described above, the flexible PVC sheet itself has excellent characteristics, and an embossing technique and a printing technique for the flexible PVC sheet have been established, and various forms of PVC sheet-coated metal sheets are manufactured. It had been. However, in recent years, the use of vinyl chloride resins has been restricted due to the VOC problem and the problem of endocrine disrupting action.

  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 as a resin-coated metal plate having an embossed design has been studied. As such a sheet, for example, Patent Document 1 discloses a decorative sheet in which a base film layer mainly composed of an amorphous polyester resin and a protective film layer mainly composed of a transparent amorphous polyester resin are laminated. 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 2 containing a large amount of the resin composition, and a layer (B layer) that imparts tension to the laminated sheet during heating with the embossing machine and simultaneously imparts non-adhesiveness to the heated metal with the embossing machine. It is disclosed that by using a laminated sheet having a layer structure, an existing embossing device for PVC can be used without causing sheet fusing, sticking to a heating roll, or winding problems.
JP 2000-233480 A International Publication No. 03/045690 Pamphlet

  However, in the composition in Patent Document 1, since the two layers are mainly composed of an amorphous polyester resin, the tension when the sheet is heated by an embossing machine is not sufficient. There is a risk of width shrinkage, wrinkling, breakage, etc., and it is difficult to stably produce a sheet having an embossed design by an embossing machine. In general, amorphous polyester resins that can be used have a glass transition temperature (Tg) lower than 100 ° C. Therefore, the boiling water immersion test included in the evaluation items for resin-coated metal plates for unit baths is conducted. When doing so, the elastic modulus of the resin layer is significantly reduced in boiling water, which may cause fluid deformation and poor appearance.

  Patent Document 2 is excellent in non-adhesiveness to a heating roll of an embossing machine and a layer mainly composed of a substantially amorphous polyester resin excellent in emboss transferability, and is heated by an embossing machine. In this case, the embossing suitability is improved by functionally differentiating into a layer mainly composed of a specific crystalline polyester resin that can maintain a sufficient tension. In addition, since it has a layer mainly composed of crystalline polyester resin, flow deformation during immersion in boiling water is effectively prevented even for resin-coated metal plates laminated with this laminated sheet, resulting in poor appearance. There is nothing.

  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.

  When embossing is applied to a layer containing a substantially amorphous polyester-based resin as a main component, the embossing plate roll is set to a relatively high temperature 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 imparted, which causes inferior precision embossing transferability. ing.

  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. When the embossed plate itself is given a precision embossed design that is extremely shallow, even when a slight embossing return occurs, the embossing transfer is unsatisfactory.

  The present invention has been made in order to solve the above-described problems of the prior art, and is suitable for embossing, particularly good embossing precision, and a laminated sheet capable of imparting an embossing design having embossing heat resistance, An object of the present invention is to provide an embossed design sheet obtained by embossing the laminated sheet, an embossed design sheet-coated metal plate, a building interior material, and the like.

  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 comprises three layers of an A layer (10), a B layer (20), and a C layer (30) shown below in order from the surface side, and a total thickness of 55 μm or more and 300 μm or less. It is a sheet (100A, 100B).
Layer A (10): a resin mainly composed of an aromatic polycarbonate resin or a resin mainly composed of a blend composition of a polyester resin and an aromatic polycarbonate resin, and the heating rate by differential scanning calorimetry of the resin A non-oriented layer having a thickness of 10 μm or more, having a single glass transition temperature (Tg) measured at 10 ° C./min, the glass transition temperature being 100 ° C. or more and 150 ° C. or less,
B layer (20): a layer comprising a resin composition mainly containing a polyester-based resin which contains a color pigment and is substantially amorphous;
Layer C (30): polybutylene terephthalate (PBT) resin having a melting point (Tm) of 215 ° C. or higher and 235 ° C. and / or polytrimethylene terephthalate having a melting point (Tm) of 215 ° C. or higher and 235 ° C. or lower ( A non-oriented layer having a thickness exceeding 20 μm, comprising a PTT) -based resin in an amount of 70% by mass to 95% by mass with respect to 100% by mass of the entire resin component.

  In this laminated sheet (100A, 100B), the A layer (10) is a layer having good embossing transferability including precision embossing, and at the same time, even a layer having good embossing heat resistance, particularly embossing persistence after immersion in boiling water. is there. The layer B (20) is a layer that imparts a colored design to the laminated sheets (100A, 100B) by adding a color pigment, and at the same time, when the embossed pattern is transferred to the laminated sheets (100A, 100B), Similar to the A layer (10), it is a layer that is deformed by pressing with an embossed plate, and the A layer (10), which has a relatively high raw material cost, is relatively thin in each layer of the laminated structure. This is a layer that enables transfer of an embossed pattern having a depth corresponding to the total thickness of (10) and B layer (20). The C layer (30) imparts sufficient sheet tension when the laminated sheet (100A, 100B) is heated by an embossing machine, resulting from melt fracture and significant elongation of the laminated sheet (100A, 100B). While preventing wrinkles and the like, this layer is non-adhesive to the heated metal roll of the embossing machine. Further, when laminating to the metal plate (60), it is a layer capable of obtaining sufficient adhesive strength even when the temperature of the metal plate (60) is the same as that when laminating a conventional soft PVC sheet. . Therefore, according to the first aspect of the present invention, by combining these layers, it is possible to provide a laminated sheet (100A, 100B) excellent in embossing suitability and handleability and in suitability for lamination to the metal plate (60). it can.

  In addition, since the B layer (20) is mainly composed of an amorphous polyester resin, for example, in a configuration in which the B layer (20) alone is laminated on a metal plate, the resin layer is not immersed in boiling water. Significant flow deformation occurs, or blister-like peeling from the metal plate (60). On the other hand, in the present invention, since the upper and lower sides are sandwiched between layers having resistance to boiling water immersion and the adhesion between the layers is strong, the laminated sheet (100A) having excellent heat resistance 100B).

  In the first invention, the polyester resin constituting the blend composition of the layer A (10) is such that the dicarboxylic acid component is mainly terephthalic acid or dimethylterephthalic acid, and the diol component is the diol component. An aromatic polyester-based resin that is a mixture of 50 mol% or more and 75 mol% or less 1,4-cyclohexanedimethanol and 25 mol% or more and 50 mol% or less ethylene glycol, based on the whole (100 mol%). It is preferable.

  Such an aromatic polyester resin has good compatibility with the aromatic polycarbonate resin. In addition, it is the most widely used aromatic polyester resin that is known to have a single glass transition temperature in a blend composition with an aromatic polycarbonate resin. Therefore, a merit in terms of cost can be obtained.

  In the first present invention, the substantially amorphous polyester resin constituting the B layer (20) has a dicarboxylic acid component mainly composed of terephthalic acid or dimethylterephthalic acid, and a diol component. An aromatic polyester which is a mixture of 25 mol% or more and 75 mol% or less 1,4-cyclohexanedimethanol and 25 mol% or more and 75 mol% or less ethylene glycol based on the whole diol component (100 mol%) It is preferable that it is a resin.

  According to this aspect, by using a commercially available material as the polyester-based resin, it is possible to obtain the merit of stability of raw material supply and cost. Moreover, this polyester resin can be melt kneaded at a low temperature as compared with the resin composition of the A layer (10). Therefore, it becomes possible to use coloring components, such as a pigment with comparatively low heat resistance, by making B layer (20) into a colored pigment addition layer. Thereby, a more various coloring design can be obtained than the case where A layer (10) is made into a color pigment content layer.

  In a layer mainly composed of a polybutylene terephthalate (PBT) resin, which is a crystalline polyester resin, or a polytrimethylene terephthalate (PTT) resin, as in the C layer (30) described later, the crystallization is performed. Therefore, when a desired color tone is desired by adding a color pigment, it is difficult to perform color matching in consideration of the effect of whitening due to haze. On the other hand, the B layer (20) is composed mainly of a non-crystalline polyester resin, and is a layer with little haze, so that color matching is easy and color development is good. Can do.

  In the first aspect of the present invention, the substantially amorphous polyester resin constituting the B layer (20) is 55% by mass or more and 80% by mass with respect to 100% by mass as a whole of the resin components constituting the B layer. It is preferably a mixture of 20% by mass or more of the aromatic polyester-based resin and 20% by mass to 45% by mass of polybutylene terephthalate (PBT) resin and / or polytrimethylene terephthalate (PTT) resin. .

  By using such a blend resin composition for the B layer (20), the resistance to the boiling water immersion test can be further improved.

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

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

  2nd this invention is an embossed design sheet (200A, 200B) which has the uneven | corrugated shape formed in the A layer (10) side surface of the lamination sheet (100A, 100B) of 1st this invention by the embossing plate. is there.

  Here, the “embossed plate” refers to a plate on which an embossed design is formed, and the shape thereof is not particularly limited, and may be a plate shape or a roll shape.

  The laminated sheet (100A, 100B) of the present invention is excellent not only in a normal 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 (200A, 200B) excellent in the designability.

  The third aspect of the present invention is an embossed design sheet (200A, 200B) of the second aspect of the present invention, and a metal plate (60) on which the surface on the C layer (30) side of the embossed design sheet is laminated via an adhesive. Is an embossed design sheet-covered metal plate (300A, 300B).

  According to the present invention, it is possible to provide an embossed design sheet-covered metal plate (300A, 300B) having excellent design properties and heat resistance by an embossed design, high surface hardness, and excellent scratch resistance and workability.

  4th this invention is a unit bath member using the embossed design sheet | seat covering metal plate (300A, 300B) of 3rd this invention.

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

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

  7th this invention is a household appliances housing | casing member using the embossed design sheet covering metal plate (300A, 300B) of 3rd this invention.

  Since the embossed design sheet-coated metal plates (300A, 300B) of the present invention have high surface hardness and excellent scratch resistance and workability, they are suitable for various uses such as the fourth to seventh aspects of the present invention. Can be used. In particular, since not only has excellent emboss transferability, but also a design based on the printed pattern (D) (40) can be imparted, by combining these designs, various members having excellent design properties and can do. Moreover, since the embossing heat resistance after boiling water immersion is favorable, it can be used suitably also as a use as which heat resistance is requested | required, for example, the unit bath member of 4th this invention. In addition, as a unit bath member, a unit bath wall material and a unit bath ceiling material can be mentioned, for example.

  The laminated sheets (100A, 100B) of the present invention can have excellent emboss transferability in an embossing machine by providing the A layer (10). 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. Moreover, the embossing heat resistance, in particular, the persistence of the embossed design after immersion in boiling water can be improved.

  Furthermore, by making the B layer (20), which can be melt-kneaded at a lower temperature than the A layer (10), into a layer containing a colored pigment, the generation of color burn of the pigment during film formation and the retention in the molding machine It is possible to reduce the occurrence of defects due to the outflow of deteriorated materials. Moreover, since the kind of color pigment which can be used also expands from the case where A layer (10) is used as a colored layer, a more various coloring design can be obtained.

  Further, by providing the C layer (30), when the laminated sheet (100A, 100B) of the present invention is heated by an embossing machine, a sufficient sheet tension can be applied to the laminated sheet (100A, 100B). It is possible to give a good embossed design without causing width shrinkage, wrinkling, and sheet breakage. Moreover, since C layer (30) shows non-adhesiveness with respect to the heating roll (410) of an embossing machine, the laminated sheet (100A, 100B) of the present invention is excellent in embossing suitability. it can. 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 flexible PVC sheet, and the laminated sheet (100A, 100B) of the present invention can be made excellent in metal plate lamination suitability.

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

Hereinafter, embodiments embodying the present invention will be described.
<Laminated sheet 100A, 100B>
1A to 1F schematically show the configurations of the laminated sheets 100A and 100B, the embossed design sheets 200A and 200B, and the embossed design sheet-covered metal plates 300A and 300B according to the present invention. 1A is 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 is a laminated sheet of FIG. This is a laminated sheet 100B having a printed pattern (D) 40 between the A layer 10 and the B layer 20 of 100A. Moreover, FIG.1 (c) is the embossed design sheet 200A which provided the embossed design on the surface of the lamination sheet 100A, and FIG.1 (d) is the embossed design sheet 200B which provided the embossed design on the surface of the laminated sheet 100B. is there. Further, FIG. 1E shows an embossed design sheet-covered metal plate 300A in which the C layer 30 side surface of the embossed design sheet 200A (the back surface of the embossed design sheet 200A) is laminated on the metal plate 60 via the adhesive 50. 1F is an embossed design sheet-covered metal plate 300B in which the C layer 30 side surface of the embossed design sheet 200B (the back surface of the embossed design sheet 200B) is laminated on the metal plate 60 via the adhesive 50. is there. Hereinafter, these structures and manufacturing methods will be described in detail.

  Since the laminated sheet of the present invention has a thickness in the range of 55 μm or more and 300 μm or less, it is more correct to describe it as “film and sheet”, but here also generally refers to the range referred to as “film”. 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 is not intentionally performed in order to impart some performance to the laminated sheets 100A and 100B. It does not mean that there is no orientation or the like generated by pulling with a casting roll during extrusion film formation.

<A layer 10>
The A layer 10 is a layer that becomes the surface of the laminated sheets 100A and 100B. When the laminated sheets 100A and 100B are passed through an embossing machine, the embossed pattern is transferred by being softened by heating and pressed by an embossing roll. Layer. Therefore, the A layer 10 has such high crystallinity as to exhibit a melting point (Tm) exceeding 190 ° C. which is the upper limit of the sheet heating temperature in the embossing machine generally used at the time of being pressed by the embossing roll. It must not be a resin composition.

  Further, the A layer 10 may not be a layer composed only of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. This is because the laminated sheet 100 is cooled from the embossing roll side and the embossing design is cooled and fixed simultaneously with the transfer of the embossing design by setting the temperature of the embossing roll below the glass transition temperature of the resin. This is because a precise embossed design can be transferred, but because of a glass transition temperature that is too low, the embossing heat resistance is inferior, and the embossing return after immersion in boiling water is particularly remarkable.

  From the above viewpoint, in the present invention, the A layer 10 is a resin mainly composed of an aromatic polycarbonate resin or a resin mainly composed of a blend composition of a polyester resin and an aromatic polycarbonate resin. A resin having a single glass transition temperature (Tg) measured at a heating rate of 10 ° C./min by differential scanning calorimetry of the resin and having a temperature of 100 ° C. or more and 150 ° C. or less is used.

  Here, “mainly” means that the resin is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass based on the mass of the entire A layer 10 (100% by mass). % Or more content.

  Generally available polyester-based resins have a glass transition temperature of less than 100 ° C, but by using a blend composition with an aromatic polycarbonate-based resin or an aromatic polycarbonate-based resin, a glass transition exceeding 100 ° C. It can be set as the resin composition which has temperature.

  Even in a blend composition of a polyester resin and an aromatic polycarbonate resin, when the glass transition temperature 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. On the other hand, a blend composition having a glass transition temperature exceeding 150 ° C. is usually distributed commercially and is difficult to obtain by a combination of resin compositions in a price range that can be used for building materials. The glass transition temperature of the resin constituting the A layer 10 is more preferably in the range of 105 ° C. or higher and 135 ° C. or lower.

  Here, the single glass transition temperature means that the glass transition temperature is measured when the glass transition temperature is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter in accordance with JIS K-7212. This means that only one temperature is observed.

(Polyester resin)
As the polyester resin contained in the blend composition, terephthalic acid or dimethyl terephthalic acid is the main component of the dicarboxylic acid component, and 50 mol% or more and 75 mol% or less of the diol component is 1,4-cyclohexanedimethanol, and the rest Using an aromatic polyester whose ethylene glycol is 25 mol% or more and 50 mol% or less is excellent in compatibility with the aromatic polycarbonate resin, and has a glass transition temperature (Tg) of each individual component at an arbitrary blend ratio. It is preferable because a single glass transition temperature located between the two can be formed.

  Here, “mainly” terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component is 70 mol% or more, preferably 90 mol of terephthalic acid or dimethylphthalic acid based on the total dicarboxylic acid component (100 mol%). % Or more, more preferably 98 mol% or more.

  In the above blend composition, since the glass transition temperature is single, the effect of improving the heat resistance of embossing is remarkable, and since it is mass-produced on a commercial basis, a stable supply can be obtained. It is preferable because it has a price advantage. Examples of the polyester resin having such a composition range include “Easter PCTG 5445” manufactured by Eastman Chemical Company and “Easter PCTG 24635” manufactured by Eastman Chemical Company.

  In the copolymer composition system, when the amount of 1,4-cyclohexanedimethanol in the diol component is less than 50 mol%, the compatibility with the aromatic polycarbonate resin becomes poor, and the glass transition temperature is low. It becomes difficult to make the heat resistance of the emboss sufficient, and when it is more than 75 mol%, the influence of crystallinity becomes remarkable, and even in the blend composition, a laminated sheet for embossing When 100A and 100B are heated, crystallization proceeds, and embossing may become difficult.

  However, in the copolymer composition system, even when the amount of 1,4-cyclohexanedimethanol in the diol component is less than 50 mol%, in the polyester resin having a specific polyalkylene glycol segment as a constituent component, It is known that relatively good compatibility is exhibited in a blend composition with an aromatic polycarbonate resin (Japanese Patent Laid-Open No. 2005-225930), and this polyester resin is also used as an aromatic polycarbonate resin of the present invention. It can be preferably used for the blend composition of Examples of the polyester resin having such characteristics include “Dianite (registered trademark) DN-124” manufactured by Mitsubishi Rayon Co., Ltd.

(Aromatic polycarbonate resin)
In addition, the aromatic polycarbonate resin that is used alone in the A layer 10 or blended with the polyester resin can be produced by a known method such as a phosgene method, a transesterification method, or a pyridine method. . Hereinafter, as an example, a method for producing an aromatic polycarbonate resin by a transesterification method will be described.

  The transesterification method is a production method in which a divalent phenol and a carbonic acid diester are added as a basic catalyst, and further an acidic substance that neutralizes the base medium is added to perform melt transesterification condensation polymerization.

  Representative examples of dihydric phenols include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is most commonly used, and the aromatic polycarbonate resin of the present invention. It is also preferable as a raw material used for Alternatively, a structure in which a part or all of bisphenol A is substituted with another dihydric phenol may be used. Other dihydric phenols include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) alkanes such as 1-bis (4-hydroxyphenyl) ethane, 1 Bis (4-hydroxyphenyl) cycloalkanes such as 1,2-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide , Compounds such as bis (4-hydroxyphenyl) ether, alkylated bisphenols such as 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4 -Hydrogen halides such as hydroxyphenyl) propane Mention may be made of phenols.

  Representative examples of carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl carbonate), m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Among them, diphenyl carbonate is most commonly used, and is preferable as a raw material used for the aromatic polycarbonate resin of the present invention.

  The aromatic polycarbonate resin used in the present invention has a molecular weight measured at 20 ° C. using methylene chloride as a solvent, a viscosity average molecular weight converted from the solution viscosity, and having a range of 20000 to 40000, It is preferable to use a material in the range of 22,000 or more and 30000 or less. Here, it is known that if the viscosity average molecular weight is too small, particularly the low temperature impact strength is lowered, while if the viscosity average molecular weight is too large, the melt viscosity becomes very high and the molding processability is lowered. The polymerization requires a long time, which is not preferable from the viewpoint of production cycle and cost. In the present invention, only one type of aromatic polycarbonate resin may be used, or two or more types may be mixed and used.

(Additive)
When the printed pattern (D) 40 does not exist under the A layer 10, a color pigment may be added to the A layer 10 for designability or concealment of the base metal. A relatively high temperature is required for the melt kneading of the resin to be included, and when a layer made of the composition is used as a colored layer, there is a restriction on usable ones from the viewpoint of heat resistance of colorants such as pigments and dyes. It becomes. Therefore, in the present invention, the B layer 20 containing a color pigment, which will be described later, is mainly responsible for the development of the colored design and the visual hiding effect of the groundwork. However, for the A layer 10, it is not problematic to add pigments that can be used without any problem in terms of heat resistance. In addition, the B layer 20 is added with a coloring design and a pigment for obtaining a visual concealing effect on the base, and then the A layer 10 has various powders such as aluminum powder, silver powder, and gold powder having an appropriate particle size. Metallic powder, glass flakes, surface-modified glass flakes, ceramic powders, and the like may be added, and a design may be applied such that the transparency of the A layer 10 is dispersed and dispersed in a dot shape to express glitter. In this case as well, an additive particle itself that does not undergo thermal degradation by melt kneading at a high temperature and that does not promote resin degradation by thermal catalysis or the like is selected and used as appropriate.

  In addition, various amounts of various additives may be added to the A layer 10 as long as the properties thereof are not impaired or in order to further improve the physical properties other than the object of the present invention. Additives include phosphoric and phenolic antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, impact modifiers, processing aids, metal deactivators, and residual polymerization catalyst deactivation. Examples thereof include those generally used for a wide range of resin materials such as agents, nucleating agents, antibacterial / antifungal agents, antistatic agents, lubricants, flame retardants, fillers, and matting agents.

(Thickness)
The preferred thickness of the A layer 10 is in the range of 10 μm to 100 μm, and more preferably in the range of 20 μm to 75 μm. Even if the thickness of the A layer 10 is thin, it is possible to transfer a relatively deep embossed pattern together with the thickness of the B layer 20, but if the thickness is thinner than this, there is a problem in handling properties as a single-layer sheet. Or 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 the co-extrusion film forming method, the laminated sheets 100A and 100B are also formed. The thickness distribution of the A layer 10 in the width direction tends to become unstable. On the other hand, if the thickness is too thick, the upper limit of the total thickness of the laminated sheets 100A and 100B is determined.

<B layer 20>
The purpose of providing the B layer 20 in the laminated sheets 100A and 100B 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 the A layer. When the resin composition containing 10 aromatic polycarbonate-based resin is added to the B layer 20 that can be melt-kneaded at a lower temperature among pigments that cause thermal discoloration and thermal fading. Since there are those that can be used without problems, the color design by adding pigments can be made more diverse. Therefore, the B layer 20 must not have high crystallinity when pressed by the embossing plate roll, and must not be a resin species that requires a relatively high temperature for melt kneading.

  Therefore, in the present invention, the B layer 20 is composed of a resin composition mainly composed of a polyester resin that is substantially amorphous. Here, “substantially amorphous” means that the embossing machine does not have crystallinity that makes embossing difficult, and is limited to polyester resins that are completely amorphous. is not. Further, “mainly” means containing at least 55% by mass, preferably 70% by mass or more based on the mass of the entire resin component of the B layer 20 (100% by mass).

(Substantially amorphous polyester resin)
As the polyester resin which is substantially non-crystalline which is the main component of the B layer 20, terephthalic acid or dimethyl terephthalic acid is the main component of the dicarboxylic acid component, and 25 mol% or more and 75 mol% or less of the diol component is 1, A copolymerized polyester which is 4-cyclohexanedimethanol and the remaining 25 mol% or more and 75 mol% or less is ethylene glycol can be preferably used.

  Here, “mainly” terephthalic acid or dimethylterephthalic acid as the main component of the dicarboxylic acid component is at least 70 mol% or more, preferably 90 mol% or more, based on the total dicarboxylic acid component (100 mol%). Preferably it means 98 mol% or more.

  When the amount of 1,4-cyclohexanedimethanol is less than the above range, the characteristic as a crystalline resin becomes remarkable, and there is a risk that the function as a layer that undergoes deformation by pressing with an embossed plate may not be obtained during embossing. There is. On the contrary, when the amount of 1,4-cyclohexanedimethanol is larger than the above range, the influence of crystallinity becomes remarkable and the same problem occurs.

  Examples of the copolyester resin in the above preferred composition range include PET-G, which is designed to reduce the cost because of the stable supply of raw materials and the large amount of production. An example of PET-G is “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, "Easter PCTG 5445" manufactured by Eastman Chemical Company and "Easter PCTG 24635" manufactured by Eastman Chemical Company, which can be used for the blend composition of layer A 10, are also described above. It is a copolyester resin in the composition range.

  However, the present invention is not limited to these, and PET that is copolymerized with neopentyl glycol or spiroglycol as the diol component does not exhibit crystallinity, has low crystallinity, or is copolymerized with isophthalic acid as the dicarboxylic acid component. Copolymerized polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins copolymerized with isophthalic acid that do not show crystallinity or those that have low crystallinity have a structure in which crystallization is inhibited by copolymerization components. It can be used as the main component of the layer 20.

  Since the B layer 20 is mainly composed of a substantially amorphous polyester-based resin, the B layer 20 itself is poor in resistance to boiling water immersion, but in the present invention, the upper and lower sides thereof are immersed in boiling water. Therefore, the laminated sheets 100A and 100B can be given resistance to the boiling water immersion test.

  In order to further ensure the boiling water immersion resistance of the laminated sheets 100A and 100B, the B layer 20 is 55% by mass or more and 80% by mass, where the total mass of the resin components constituting the B layer 20 is 100% by mass. % Or less of the aromatic polyester resin and 20% by mass or more and 45% by mass or less of polybutylene terephthalate (PBT) resin and / or polytrimethylene terephthalate (PTT) resin.

(Color pigment)
The B layer 20 is a layer mainly responsible for the development of the visual hiding effect of the colored design and the base, and is added with pigments. The pigment used for coloring the B layer 20 may be one generally used for coloring a polyester resin, and the addition amount may be an amount generally added for the above purpose. As an example, in the case of a light color, it is a white-colored pigment, and based on a titanium oxide pigment having a high visible light concealing effect, a color adjustment is performed with a chromatic inorganic or organic pigment. be able to. There are abundant commercially available pigment-kneaded pellets whose dispersibility is improved by pre-kneading, such as the aforementioned color master batch based on PET-G, and these can also be used. 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 preferable thickness of the B layer 20 is in the range of 25 μm to 250 μm, and more preferably in the range of 50 μm to 150 μm. If the thickness is thinner than this, it is difficult to develop the colored design required for the B layer 20, and conversely, if the thickness is too thick, the upper limit of the total thickness of the laminated sheets 100A and 100B is determined. There is a risk that the layer 10 or the C layer 30 may fail to express the function to be handled. When embossing with a normal depth is applied, the total thickness of the A layer 10 and the B layer 20 is preferably 50 μm or more, and more preferably 70 μm or more.

  Regarding the visual hiding effect of the base metal plate by the addition of the color pigment, the degree of importance varies depending on the use. However, in the embossed design sheet-covered metal plate for interior building materials, JIS K5600 4-1 “Paint General Test Method” -It is preferable that the concealment rate measured based on "concealment rate" is 0.95 or more in the configuration of the laminated sheets 100A and 100B.

  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 laminated sheets 100A and 100B, and when the color changes due to the difference in the treatment of the metal plate surface, Since the color observed from the surface of the laminated sheets 100A and 100B 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>
When the layer C is heated to the same temperature as that of the conventional soft PVC when the laminated sheets 100A and 100B are passed through the embossing machine, the width of the C layer 30 is not reduced, wrinkled, melt fracture, etc. Have a role to play. Therefore, when the embossing pattern is transferred with an embossing machine, the resin composition has a significantly reduced elastic modulus at a heating temperature of about 160 ° C. to 190 ° C., which is a temperature at which the sheet is heated by a heater without a support. Don't be. On the other hand, when laminating to the metal plate 60, it is necessary to obtain a strong adhesion at a temperature similar to that of the conventional soft PVC, and the high modulus of elasticity is still maintained even when heated to about 235 ° C. Therefore, it should not be a crystalline polyester resin 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. ) Based on resin.

  The melting point of 215 ° C. or higher is necessary when the embossed design is transferred to a conventional soft PVC sheet by an embossing machine, 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 having a melting point of less than 215 ° C. or a PTT resin is used as the resin component of the C layer 30, it is difficult to obtain sufficient tension at a heating temperature of 160 to 190 ° C. The upper limit of the melting point is 235 ° C., when a PBT resin having a higher melting point or a PTT resin is used as the main component of the C layer 30, a sheet of conventional soft PVC is used as the metal plate. This is because it is difficult to obtain a strong adhesion with the metal plate 60 at the same temperature as when laminating to 60.

  The reason why the main component of the C layer 30 is PBT resin and / or PTT resin is not only because these resins are in the preferable melting point range, but also because the crystallization speed is relatively fast. It is easy to obtain high crystallinity in the film-forming process without requiring a special curing process between the embossing process, that is, easy to obtain non-adhesiveness and melt fracture resistance to the heated metal in the embossing process. Because.

  In the case of polyethylene terephthalate (PET) resin, a resin having a melting point in the above range can be obtained by substituting a part of terephthalic acid that is a dicarboxylic acid component with isophthalic acid. However, it is difficult to obtain a sufficiently crystallized C layer 30 with a normal extrusion film forming line, and a curing process or the like is required.

  Other reasons for using PBT resins and / or PTT resins are that good processability can be obtained even in a crystallized state compared to PET resins, and for PBT resins, in recent years extrusion film formation Another example is that the use of PBT resin materials having various melt viscosities and melting points has become easier to obtain due to active development of applications such as grades.

  The content ratio of the PBT resin or PTT resin in the resin component of the C layer 30 is the ratio of the PBT resin or PTT resin based on the mass of the entire resin component in the C layer 30 (100% by mass). (When the PBT resin and the PTT resin are used in combination, the total ratio thereof) is preferably 70% by mass or more, and more preferably 80% by mass or more. When less than this, even if a sheet is obtained in a crystallized state, it is difficult to obtain a preferable melt tension.

  The PBT resin or PTT resin is preferably 95% by mass or less, and more preferably 90% by mass or less. When the amount of PBT or PTT is larger than this, the crystallinity of the C layer 30 on the adhesive lamination surface side when laminating the laminated sheets 100A and 100B to the metal plate 60 becomes too high, and the metal is not used under conventional heating conditions. This is because it is difficult to obtain adhesion strength with the plate 60, and when the C layer 30 is obtained by two-layer coextrusion with the B layer 20 or by the three-layer coextrusion film forming method of the A layer 10 and the B layer 20 In addition, the warpage of the laminated sheets 100A and 100B after the film formation becomes significant, and there is a possibility that the handling may be hindered.

  As a PBT resin having a melting point in the range of 215 ° C. or higher and 230 ° C. or lower, 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. As the PBT resin having such a composition, “Novaduran (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) can be used. Registered trademark) 5020H ", etc., and when this is used, it is possible to obtain advantages such as cost advantages and supply stability.

  Examples of the PTT resin having a melting point of 215 ° C. or more and 235 ° C. or less include “Corterra (registered trademark) CP509200” manufactured by Shell, which is a homo-polytrimethylene terephthalate resin.

(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, and “Easter PETG • 6763” manufactured by Eastman Chemical Company. Similarly, “Easter PCTG 5445” can be mentioned. The reason why the amorphous material is preferable is that, when a highly crystalline resin is used, the crystallization progresses with time although the crystallization speed of homo-PET is slow, so that the crystallinity of the PBT resin crystallizes. The inferior crystal phase of the PET-based resin adversely affects the processability of the C layer 30 over time, and as a result, the processability of the laminated sheets 100A and 100B and the metal plates 300A and 300B covering them may be reduced. It is.

(Thickness)
The C layer 30 preferably has a thickness exceeding 20 μm, more preferably 25 μm or more, and particularly preferably 30 μm or more. When the thickness is thinner than this, the function as the tension applying layer in the embossing machine 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 the upper limit of the total thickness of the laminated sheets 100A and 100B is determined. May cause failure.

  Furthermore, as described in, for example, “Japanese Patent Application Laid-Open No. 2006-095892”, the C layer 30 is a layer that shares the function of imparting tension in the embossing machine and a layer that shares the function of preventing adhesion to the heating roll. It may be composed 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. As an example, “LICOWAX (registered trademark) OP” (manufactured by Clariant Japan), which is a montanic acid-based lubricant, is used. Can be mentioned. The addition amount of the lubricant may be a general amount of about 0.2 to 3% by mass based on the total resin amount of the C layer 30 (100% by mass).

  In addition, in order to make the tension of the laminated sheets 100A and 100B in the embossing machine 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 ", etc.) and processing aids such as polytetrafluoroethylene that has been subjected to an easy dispersion process that develops into fibrils (for example," Metblene (registered trademark) A-3000 "manufactured by Mitsubishi Rayon Co., Ltd.) In this case, a general amount of about 0.2 to 3% by mass may be used.

  Further, in order to sufficiently impart the crystallinity necessary for obtaining non-adhesiveness and melt fracture resistance in an embossing machine to the C layer 30 in an extrusion film forming line, a crystal nucleating agent is added and the crystallization rate is increased. May be improved. In addition, various additives described in the A layer 10 and other general-purpose resins may be included in a small amount.

<Printed pattern (D) 40>
In the laminated sheets 100A and 100B 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 by printing. You can also The printed pattern (D) 40 is applied by a known method such as gravure printing, offset printing, or screen printing, and an arbitrary pattern such as a stone pattern, a wood pattern, a geometric pattern, or an abstract pattern is applied.

  The printed pattern (D) 40 may be formed by printing on the surface of the B layer 20 to be laminated with the A layer 10, or on the surface of the A layer 10 to be laminated with the B layer 20. It may be formed by printing.

<Method for producing laminated sheet>
As a method for producing the laminated sheets 100A and 100B of the present invention, various known methods such as a cast film forming method or an inflation method using an extruder equipped with a T die can be employed.

  In order to produce the laminated sheet 100A of the present invention, three layers “A layer 10 + B layer 20 + C layer 30” are integrally formed by a co-extrusion film forming method using three extruders and a multi-manifold die. Most efficient and preferred. Alternatively, the A layer 10 is formed separately, and two layers of “B layer 20 + C layer 30” are separately formed by a co-extrusion film forming method using two extruders and a multi-manifold die. You may heat-seal-lamination at the introduction part to the heating roll of an embossing machine.

  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. Since the layer 30 is formed in a state where crystallization has advanced, it is easy to obtain good interlayer adhesion with the B layer 20 by heating at 160 ° C. to 190 ° C. with an embossing machine. In some cases, the B layer 20 and the C layer 30 are preferably laminated in a die by a coextrusion method.

  When producing the laminated sheet 100B to which the printed pattern (D) 40 is provided, the type of the resin binder of the printing ink is not particularly limited, but by appropriately selecting this binder type, the layer between the A layer 10 and the B layer 20 is selected. Lamination integration can be heat fusion lamination. Alternatively, at the time of applying the printed pattern (D) 40, a heat-adhesive coating layer can be simultaneously applied to perform heat fusion lamination.

  However, the lamination integration of the A layer 10 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, and heat fusion lamination may be performed in another process. Moreover, it is good also as lamination | stacking with a dry-lamination adhesive agent.

  The total thickness of the laminated sheets 100A and 100B of the present invention is in the range of 55 to 300 μm, and preferably in the range of 80 to 200 μm. When the thickness of the laminated sheets 100A and 100B 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, resulting in a decrease in workability. There is a fear. In addition, it becomes difficult to transfer a relatively deep embossed pattern. On the other hand, when the thickness of the laminated sheets 100A and 100B is too thick, it becomes difficult to use a molding die that has been conventionally used for forming processing such as bending of a flexible PVC resin-coated metal plate. This may cause a problem and cause an abnormality such as a crack in the resin layer in the bent portion.

<Embossed design sheet 200A, 200B>
The laminated sheets 100A and 100B manufactured by the above method can be used as the embossed design sheets 200A and 200B by imparting a concavo-convex shape to the surface of the A layer 10 with an embossed plate. The laminated sheets 100A and 100B of the present invention can be provided with an embossed design in the same manner as a conventional soft PVC sheet by various embossing machines generally used to give an embossed pattern to the soft PVC sheet. .

  FIG. 2 shows an example of an embossing machine 400 that is generally used to give an embossed pattern to a soft PVC sheet. The illustrated embossing machine 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 this embossing machine 400, a roll-shaped embossing roll 450 is used as the embossing plate. However, the embossing plate is not particularly limited as long as it is a plate on which an embossed design is formed. It may be in the form of a roll or a roll.

  In the embossing machine 400 shown in FIG. 2, a two-layer co-extruded sheet of the A layer 10 formed as a single layer and the B layer 20 + C layer 30 with a printed pattern (D) 40 as necessary is supplied. Heat fusion lamination is performed by the heating roll 410 of the applicator 400.

  The laminated sheets 100 </ b> A and 100 </ b> B of the present invention are non-adhesive to the heating roll 410 heated to about 100 ° C. to 140 ° C. by having the C layer 30, and are sheets formed by the infrared heater 430. Even at a heating temperature of 160 ° C. to 190 ° C., the laminated sheets 100A and 100B are not reduced in width, wrinkled, broken, or the like. Moreover, the embossed design sheet 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 to a temperature slightly lower than the glass transition temperature of the resin of the A layer 10, when the laminated sheets 100A and 100B come into contact with the embossing plate roll, Since the fixing is performed, it is difficult for the embossing to return in the embossing step, and good transferability can be obtained even for precision embossing.

  You may give the coloring design by what is called wiping printing to the recessed part of A layer 10 surface formed by emboss provision. The colored ink layer formed in the embossed recesses by wiping printing is preferably formed with colored ink using a two-component curable urethane resin, etc., but from polyester resin, vinyl chloride resin, acrylic resin, etc. You may form using the 1 liquid ink which becomes. As the pigment used in the color ink, a pigment used for a normal printing ink 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 300A, 300B>
As shown schematically in FIG. 1 (e) and FIG. 1 (f), the embossed design sheet-covered metal plates 300A and 300B of the present invention have the C layer 30 side surface in the embossed design sheets 200A and 200B. The structure is laminated on the metal plate 60 via the adhesive 50.

  As the metal plate 60 used for the embossed design sheet-coated metal plates 300A and 300B 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, aluminum -Various steel plates such as magnesium / zinc alloy plated steel plates and stainless steel plates, aluminum plates, aluminum-based alloy plates, titanium-based alloy plates and the like can be used, and these may be used after performing a normal chemical conversion treatment. The thickness of the base metal plate 60 varies depending on the use of the resin-coated metal plates 300A and 300B, but can be selected in the range of 0.1 mm to 10 mm.

  The method of laminating the embossed design sheets 200A and 200B on the metal plate 60 is not particularly limited, but it is possible to use the same equipment as when laminating a conventional soft PVC sheet on the metal plate 60 because existing equipment can be used. preferable.

  That is, a laminate using an adhesive 50 is preferably used. As the adhesive 50, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, or the like that is generally used is a thermosetting type. Mention may be made of adhesives. Among these, since the laminated sheets 100A and 100B are 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 plates 300A and 300B, for example, a metal for bonding the embossed design sheets 200A and 200B to the metal plate 60 using commonly used coating equipment such as a reverse coater and a kiss coater. After applying a thermosetting adhesive on the surface so that the adhesive film thickness after drying is about 1 μm or more and about 10 μm or less, the coated surface is dried and heated by an infrared heater and / or a hot air heating furnace to form a metal plate A method of covering and cooling the embossed design sheets 200A and 200B so that the C layer 30 side of the embossed design sheets 200A and 200B becomes an adhesive surface immediately using a roll laminator while the surface temperature of 60 is maintained at a temperature of about 220 ° C. or more and 250 ° C. or less. .

  The embossed design sheet-coated metal plates 300A and 300B of the present invention can be made into metal plates having various designs by combining the design with the printed pattern (D) 40 and the embossed design. Moreover, since it has favorable workability and surface hardness, it can respond | correspond widely to various uses. 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.

[Create laminated sheet]
<Examples 1-19, Comparative Examples 1-17>
As Examples 1 to 19 and Comparative Examples 4 to 17, a multi-manifold type co-extrusion was performed using two φ65 mm vented concentric twin screw extruders and one vented φ65 mm single screw extruder. Thus, a laminated sheet having a three-layer structure composed of an A layer, a B layer, and a C layer was produced by a general method in which the resin flowing out from the T-die was taken up by a casting roll.
A 65-mm single screw extruder was used for melting and kneading the A layer, and the set temperatures of the cylinder were 260 ° C. on the feed side and 280 ° C. on the base side. A φ65 mm same-direction twin screw extruder was used for melting and kneading the B layer and the C layer, respectively. The cylinder set temperatures of the B layer and C layer extruders are 230 ° C. on the feed side and 250 ° C. on the base side. The multi-manifold die was set at a temperature of 270 ° C. and finely adjusted according to the conditions of film formation. In addition, under the same conditions, as Comparative Example 1, a sheet formed of A layer alone was co-extruded and formed as Comparative Example 2 and Comparative Example 3, respectively. A layer, B layer, and A layer respectively. A laminated sheet consisting of only the C layer was produced.
In the layer A or B layer of the laminated sheet, 100 parts by mass of the resin component of each layer, 22 parts by mass of a white pigment mainly composed of titanium oxide, and “DM-635. 3 parts by weight of “white” was added.
About the composition of the resin used in each layer of Examples 1 to 19 and Comparative Examples 1 to 17, the thickness of the layer, etc., the A layer is in Table 1, the B layer is in Table 2, and the C layer is in Table 3. Each is shown. Table 4 shows the combination of layers in the sheets of Examples 1 to 19 and Comparative Examples 1 to 17 and the temperature of the embossing plate roll during sheet production.

  In addition, the glass transition temperature (Tg) of the resin of the A layer shown in Table 1 was measured using a differential scanning calorimeter “DSC-7” manufactured by PerkinElmer Co., Ltd., and 10 mg of the sample was JIS K-7121 “plastic transition temperature”. In accordance with the “Measurement Method”, the temperature was increased from −40 ° C. to 250 ° C. at a heating rate of 10 ° C./min, held at 250 ° C. for 1 minute, and then decreased to −40 ° C. at a cooling rate of 10 ° C./min. This is a value obtained from a thermogram when the temperature is raised again at 10 ° C./min after holding for 1 minute. As a sample used for the measurement, for the A layer in the laminated sheet formed by coextrusion of the three layers, the one obtained by scraping the resin using a microtome is used. The measurement sample is used as it is. Moreover, regarding raw material physical properties, each raw material pellet is used as it is as a sample.

<Examples 20 to 22, Comparative Examples 18 and 19>
A two-layer laminated sheet of “B layer + C layer” by a general method in which the resin that has flowed out of the T die by multi-manifold co-extrusion using two co-directional twin-screw extruders with φ65 mm with vents is drawn by a casting roll. Got. On the surface of layer B side of this laminated sheet, a printed pattern (D) is printed on a sheet with a grainy pattern by gravure printing using acrylic / urethane-based ink, and a φ65 mm vented single screw extruder is used. The layers A extruded and formed as a single-layer transparent sheet by a T-die are heat-sealed and laminated at the heating roll 410 portion of the embossing machine 400 shown in FIG. The laminated sheets of Examples 18 and 19 were produced. The cylinder set temperature of each extruder is the same as in Examples 1 to 19 and Comparative Examples 1 to 17, and the same applies to the type and amount of the additive pigment. Table 5 shows the combinations of layers in the sheets of Examples 20 to 22 and Comparative Examples 18 and 19, and the temperature of the embossing plate roll during sheet production.

  The raw materials used in the above examples and comparative examples are as follows. The “measured melting point” in the following raw materials is a differential scanning calorimeter “DSC-7” manufactured by PerkinElmer Co., Ltd., and 10 mg of the sample is JIS K-7121 “Plastic transition temperature measurement method / melting temperature”. The heating rate was raised from −40 ° C. to 250 ° C. at 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 is maintained for 1 minute and then heated again at 10 ° C./minute.

(Easter PETG · 6763)
It is an amorphous polyester resin manufactured by Eastman Chemical Company (abbreviated as “PETG6763” in the table). The dicarboxylic acid component is terephthalic acid, and about 30 mol% of the diol component is 1,4-cyclohexanedimethanol and about 70 mol% is ethylene 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 “PCTG5445” in the table). The dicarboxylic acid component is terephthalic acid, and about 65 mol% of the diol component is 1,4-cyclohexanedimethanol and about 35 mol% is ethylene glycol. The measured glass transition temperature was 86 ° C. and no melting point was observed.

(Dianite (registered trademark) DN-124)
It is a substantially amorphous polyester elastomer manufactured by Mitsubishi Rayon. The dicarboxylic acid component is terephthalic acid, and about 26 mol% of the diol component is 1,4-cyclohexanedimethanol, about 68 mol% is ethylene glycol, and about 6 mol% is polytetramethylene glycol having a number average molecular weight of about 1000. . The measured glass transition temperature was 19 ° C. and no melting point was observed.

(Novalex (registered trademark) 7025A)
This is a bisphenol A polycarbonate resin manufactured by Mitsubishi Engineering Plastics. Viscosity average molecular weight 25000. The measured glass transition temperature was 149.5 ° C. and no melting point was observed.

(Novaduran (registered trademark) 5020S)
(Homo) polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics. The measured melting point was 224 ° C.

(Corterra (registered trademark) 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 melting point was 246 ° C. and the glass transition temperature was 76 ° C.

[Embossing on laminated sheet]
About the laminated sheet obtained in Examples 1-19 and Comparative Examples 1-17, the embossed pattern was transferred using the embossing machine 400 shown in FIG. In addition, with respect to the laminated sheets of Examples 20 to 22 and Comparative Examples 18 and 19 in which heat fusion lamination was performed at the heating roll portion of the embossing machine during the production of the laminated sheet, embossing was imparted simultaneously with the production of the laminated sheet. Here, embossing will be described in detail.

  As an outline of the process of the embossing machine, first, the sheet is preheated by contact-type heating using a heating roll 410, and then the sheet is heated to an arbitrary temperature by non-contact type heating using an infrared heater 430. The embossed pattern is transferred by a roll 450 to form an embossed design sheet.

  In addition, regarding the laminated sheets having the printed patterns of Examples 20 to 22 and Comparative Examples 18 and 19, in the heating roll unit 410, the laminated sheet composed of the B layer and the C layer and the A layer are heat-sealed and laminated. After that, the laminated sheet is heated to an arbitrary temperature by non-contact type heating using an infrared heater 430, and the embossed design is transferred by the embossing roll 450 to obtain an embossed design sheet.

  In this example, the heating roll 410 was set to 120 ° C., and then heated by the infrared heater 430 so that the sheet surface temperature immediately before contacting the embossing roll 450 was 190 ° C. The temperature of the embossing roll 450 is adjusted to “glass transition temperature of each A layer—20 ° C.” by a hot water circulator. 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]
Adhesive film thickness after drying on the surface of a metal plate (galvanized steel plate with a thickness of 0.45 mm) for bonding a laminated sheet to a commercially available polyester adhesive for a polyvinyl chloride coated metal plate is about 2 to 4 μm It applied so that it might become. 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 at 235 ° C., the embossed design sheet-coated metal plate was obtained by immediately coating and cooling the sheet using a roll laminator.

[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 Tables 6 and 7.

(1) Film-forming stability of laminated sheet With respect to the laminated sheets of Examples 1 to 19 and Comparative Examples 1 to 17 prepared by a three-layer coextrusion film-forming method, the appearance was visually observed to determine the film-forming stability. . “X”, especially when there is a layer with uneven unevenness at the confluence interface, or when there is a layer that cannot be evenly spread to the edge due to poor development in the width direction of one of the layers. The ones with no were marked with “○”.

(2) Color design property of laminated sheet The color design property of the laminated sheet was visually observed. When the color design is inferior due to deterioration of the pigment or deterioration of the resin due to the thermocatalytic action of the pigment, “X”, in particular, there is no problem in the color design and a white color having good pearly luster is obtained. The case was set as “◯”.

(3) Handling property of laminated sheet The laminated sheets of Examples 1 to 19 and Comparative Examples 2 to 17 produced by the coextrusion film forming method were evaluated with respect to the handling property before embossing. About Examples 20-22 and Comparative Examples 18 and 19, the handleability before printing pattern (D) provision of the 2 layer lamination sheet which consists of B layer and C layer created by the coextrusion film forming method was evaluated.
The laminated sheet was cut into 15 cm in the MD direction × 30 cm in the TD direction, 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.

(4) Handling property in A layer single layer Since Examples 20-22 and Comparative Examples 18 and 19 formed a relatively thin A layer as a single layer, the handling property was evaluated. . When passing the layer A sheet through the embossing machine, if the workability is remarkably poor due to wrinkles or the like and the efficient work is difficult, "X", and the layer A sheet can be set in the embossing machine without any trouble. The case where it was possible was marked with “◯”, and the middle workability was marked with “△”.

(5) Suitability for embossing (5-1) Adhesion resistance When embossing was applied with the embossing machine 400 shown in FIG. Although it was possible, the sheet was markedly stretched and deformed, “x”, indicating slight adhesion, but the work could be continued, and the sheet stretched and deformed was within the range where there was no practical problem. Those that were not adhered were indicated by “Δ”, and those that did not adhere were indicated by “◯”. Subsequent evaluation was not performed about what became "x" by adhesion resistance.

(5-2) Fusing resistance When embossing is applied with the embossing machine 400 shown in FIG. 2, the sheet is melted during heating of the sheet by the infrared heater 430, and the sheet is noticeably stretched or wrinkled. “×” indicates that the sheet was slightly stretched / width-shrinked, etc., but was within the practical range, and “△” indicates that these problems did not occur. . No further evaluation was performed for those evaluated as “x” in this evaluation.

(5-3) Precise embossing transfer property The sheet embossed with precise embossing by the embossing machine 400 shown in FIG. 2 is visually observed, and “○” indicates that the embossed pattern is transferred cleanly. The case where the transfer was shallow was indicated by “Δ”, and the case where the transfer was poor and the embossed pattern was shallow, or the surface was simply rough regardless of the embossed pattern was indicated by “x”.

(5-4) Emboss Transferability at Normal Depth Embossing machine 400 shown in FIG. 2 visually observes the sheet with embossing at normal depth, and “○” indicates that the embossed pattern is transferred cleanly. In comparison with this, “△” 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.

(6) Emboss heat resistance (6-1) High temperature air heat resistance The metal plate which laminated | stacked the sheet | seat which gave the precision embossing with the embossing machine 400 shown in FIG. 2 was left still in a 105 degreeC hot-air circulation type oven for 3 hours. After that, it is visually observed, “○” indicates that the shape of the emboss is almost unchanged compared to before being put into the oven, “△” indicates that the embossed return has occurred slightly compared to this, When the return is remarkable, or when the embossed pattern completely disappears and the surface is simply rough, “x” is shown.

(6-2) Resistance to boiling water immersion Before a metal plate laminated with a sheet embossed with precision embossing by the embossing machine 400 shown in FIG. 2 is immersed in boiling water for 3 hours and then visually observed and put into boiling water. Compared with, the shape of the emboss is almost unchanged “○”, when the embossed return is slightly compared to “△”, when the embossed return is noticeable, or the embossed pattern is completely Those that have disappeared and have a rough surface are indicated by “x”.

(7) Workability (bendability of resin-coated metal plate)
Perform impact adhesion bending test on resin-coated metal plate, visually determine the surface condition of the decorative sheet of the bent part, “○” if there is almost no change, “△” if there is a slight crack, What occurred was displayed as "x". The impact adhesion bending test was performed as follows. Samples of 50 mm × 150 mm were prepared from the length direction and width direction of the 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 from a height of 50 cm.

(8) Surface hardness (pencil hardness test of resin-coated metal plate)
Regarding laminated sheet-covered metal plate obtained by laminating a laminated sheet to a metal plate, JIS K5600-5-4: 1999 “General test method of paint—Part 5: Mechanical properties of coating film—Section 4: Scratch hardness (pencil method) It carried out according to. Drawing in a temperature-controlled room at 23 ° C. using a jig that can draw a load of 9.8 N while maintaining a 45 ° angle with respect to the resin sheet surface of the resin-coated metal plate cut out to 80 mm × 60 mm The surface state of the resin sheet of the portion was visually determined, and “○” indicates that the 2B pencil was not scratched at all. “2B” was scratched but the 3B pencil was not scratched at all. Items with “△” and 3B pencils with scratches were displayed as “x”.

[Evaluation results]
<Examples 1 to 19 and Comparative Examples 1 to 17>
Although the comparative example 1 is a case where A layer which can be used for this invention is used by a single layer, the sheet | seat was heated by the embossing machine, and the melt fracture of the sheet was produced.

  Comparative Example 2 is a laminated sheet composed of two layers of A layer and B layer that can be used in the present invention and has no C layer, but the B layer having a low glass transition temperature and low crystallinity is embossed. Contact with the heating drum of the applicator caused sticking that was difficult to peel off.

  Comparative Example 3 is a laminated sheet composed of two layers, A layer and C layer, that can be used in the present invention and has no B layer. However, the embossed pattern is transferred by being softened by heating and pressed by an embossing plate roll. Since the layer to be formed was only the A layer and there was no thickness, it was not possible to obtain a good transfer of embossment of normal depth.

  Comparative Example 4 is a case where a coloring pigment was added to the A layer of the present invention, but the A layer was slightly brownish and a white color having good pearl luster was not obtained. Further, a fine streak-like appearance defect parallel to the flow direction of the A layer was observed. Since the pearl luster pigment is a mica surface coated with titanium oxide, the titanium oxide exhibits a heat degradation catalytic action during melt kneading of a blend composition containing an aromatic polycarbonate resin, and the resin composition of the A layer It is judged that the deterioration of the product was promoted.

  Comparative Examples 5 to 7 and Comparative Example 10 are laminated sheets having an A layer made of a blend composition of the same type as the resin that can be used for the A layer of the present invention, and a special problem occurs in the embossing process. However, by appropriately setting the embossing plate roll temperature, good transfer can be obtained both in precision embossing and in normal embossing. However, since the glass transition temperature of the blend composition used for the A layer is lower than the range specified in the present invention, the metal plate laminated with the embossed laminated sheet is immersed in boiling water, resulting in significant embossing return. It became.

  Comparative Examples 8 and 9 were cases where the blend composition of the A layer had two peaks, and a significant embossing return was also caused by immersion in boiling water. This is probably because the heat resistance of embossing is controlled by the glass transition temperature on the low temperature side.

  In Comparative Example 11, the blend composition of the A layer satisfies the glass transition temperature defined in the present invention, but the thickness of the A layer is thin, and remarkable unevenness due to instability of the internal interface with the B layer is observed. At the same time, the expansion of the A layer in the width direction was poor. Although fine adjustments were made to the cylinder temperature, connecting pipe temperature, and multi-manifold die set temperature for each extruder, no improvement was observed. If the thickness of the A layer is too thin, it is judged that a problem occurs in the extrusion stability.

  Comparative Example 12 is a case where a C layer in which the amount of polybutylene terephthalate resin is less than the range of the present invention was used, and although it was not an unacceptable level with respect to adhesion to a heating drum in an embossing machine, When the sheet was heated with an infrared heater, significant elongation and wrinkles caused by the sheet occurred, and it was difficult to provide stable embossing.

  Comparative Example 13 is a case where a C layer having a thickness smaller than the range of the present invention was used, and since the blending amount of the polybutylene terephthalate resin was within the range of the present invention, adhesion to the heating drum did not occur. The melt tension was still insufficient, and the state similar to that of Comparative Example 12 was obtained by infrared heater heating.

  Comparative Example 14 is a case in which only the highly crystalline homo-polybutylene terephthalate resin is used for the C layer, and a remarkable warp is generated in the laminated sheet of A layer + B layer + C layer, and it is difficult to pass through the embossing machine. Met.

  Comparative Example 15 is a case where only polybutylene terephthalate resin copolymerized with isophthalic acid was used for the C layer, and the warpage of the laminated sheet was smaller than that of Comparative Example 14, but the melting point of the resin was only 205 ° C. Therefore, when heated to 190 ° C. by an infrared heater, the melt tension was insufficient.

  Comparative Example 16 is a blend of 20% by mass of substantially non-crystalline polyester resin in the C layer as compared with Comparative Example 15, but the adhesiveness to the heating drum appears, and infrared As a result, the melt tension during heating with the heater further decreased.

  Comparative Example 17 is a case where a crystalline polyester is used for the C layer, but a polyethylene terephthalate resin of isophthalic acid copolymer having a low crystallization rate is used, and no special crystallization treatment is performed after the film formation of the laminated sheet. For this reason, it was brought into contact with the heating drum in an amorphous state, and as in Comparative Example 2, sticking that was difficult to peel off occurred.

  On the other hand, the laminated sheets of Examples 1 to 19 of the present invention are stably obtained by the coextrusion film forming method, and the handleability of the obtained laminated sheets is also good, and the stability in the embossing machine is stable. As a result, it was possible to obtain good transferability for both the precision embossed pattern and the normal embossed pattern. In addition, a pigment having low heat resistance is obtained because the B layer which can be melt-kneaded at a relatively low temperature without adding a pigment to the A-layer containing an aromatic polycarbonate resin that requires a high temperature for melt-kneading is a colored layer. Even if is used, a good coloring design can be obtained. Furthermore, it can be seen that the metal plate laminated with the laminated sheet has good heat resistance of embossing, and good workability and surface height.

<Examples 20 to 22, Comparative Examples 18 and 19>
The comparative example 18 is a case where the A layer is thin, and the A layer having the same thickness as that of the comparative example 11 which causes a problem in the three-layer coextrusion film formation is formed as a single layer. In this case, the film forming property itself did not cause a problem, but the workability when passing through an embossing machine for heat fusion lamination with “B layer + C layer” was extremely poor. If the thickness is too thin, an undesirable result is obtained.

  Comparative Example 19 is a case where the same A layer as Comparative Example 4 was formed as a single layer in the three-layer coextrusion film formation by adding a color pigment to the A layer, which caused the resin deterioration of the A layer. Also, a good color design could not be obtained due to thermal degradation of the A layer resin.

  On the other hand, in Examples 20 to 22 of the present invention, in addition to the characteristics of Examples 1 to 19, a laminated sheet having a design by printing and a metal plate laminated with the laminated sheet are obtained.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. The laminated sheet, the embossed design sheet, the embossed design sheet-covered metal plate, and the building interior material that 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. Etc. are also to be understood as being included within the scope of the present invention.

1 (a) and 1 (b) are schematic views showing the layer structure of the laminated sheets 100A and 100B of the present invention, and FIGS. 1 (c) and 1 (d) show the embossed design sheets 200A and 200B of the present invention. It is a schematic diagram which shows a layer structure, FIG.1 (e), (f) is a schematic diagram which shows the layer structure of the embossed design sheet | seat metal plate 300A, 300B of this invention. It is a schematic diagram which shows an example of the embossing machine 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)
DESCRIPTION OF SYMBOLS 50 Adhesive 60 Metal plate 100A, 100B Laminated sheet 200A, 200B Embossed design sheet 300A, 300B Embossed design sheet covering metal plate 400 Embossing machine 410 Heating roll 420 Take-off roll 430 Infrared heater 440 Nip roll 450 Embossed roll 460 Cooling roll

Claims (11)

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: a resin mainly composed of an aromatic polycarbonate resin or a resin mainly composed of a blend composition of a polyester resin and an aromatic polycarbonate resin, and a heating rate of 10 ° C. / A non-oriented layer having a thickness of 10 μm or more, having a single glass transition temperature (Tg) measured in minutes, the glass transition temperature being 100 ° C. or more and 150 ° C. or less,
B layer: a layer comprising a resin composition mainly containing a polyester-based resin containing a color pigment and being substantially amorphous,
Layer C: polybutylene terephthalate (PBT) resin having a melting point (Tm) of 215 ° C. or more and 235 ° C. and / or polytrimethylene terephthalate (PTT) system having a melting point (Tm) of 215 ° C. or more and 235 ° C. or less A non-oriented layer having a thickness exceeding 20 μm, wherein the resin is contained in an amount of 70% by mass to 95% by mass with respect to 100% by mass of the entire resin component. The polyester resin constituting the blend composition of the layer A is
The dicarboxylic acid component is mainly composed of terephthalic acid or dimethyl terephthalic acid,
The diol component is a mixture of 50 mol% or more and 75 mol% or less 1,4-cyclohexanedimethanol and 25 mol% or more and 50 mol% or less ethylene glycol based on the whole diol component (100 mol%). The laminated sheet according to claim 1, which is an aromatic polyester resin. The substantially amorphous polyester-based resin constituting the B layer is
The dicarboxylic acid component is mainly composed of terephthalic acid or dimethyl terephthalic acid,
The diol component is a mixture of 25 mol% or more and 75 mol% or less 1,4-cyclohexanedimethanol and 25 mol% or more and 75 mol% or less ethylene glycol based on the whole diol component (100 mol%). The laminated sheet according to claim 1 or 2, which is an aromatic polyester resin. The substantially amorphous polyester-based resin constituting the B layer is
The total mass of the resin component constituting the B layer is 100% by mass, and 55% by mass to 80% by mass of the aromatic polyester resin and 20% by mass to 45% by mass of polybutylene terephthalate (PBT). The laminated sheet according to claim 3, which is a mixture with a resin and / or a polytrimethylene terephthalate (PTT) resin. 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. The embossed design sheet which has the uneven | corrugated shape formed in the said A layer side surface of the lamination sheet in any one of Claims 1-5 by the embossing plate. An embossed design sheet-covered metal plate comprising the embossed design sheet according to claim 6 and a metal plate on which the surface of the C layer side of the embossed design sheet is laminated via an adhesive. A unit bus member using the embossed design sheet-coated metal plate according to claim 7. A building interior material using the embossed design sheet-covered metal plate according to claim 7. A steel furniture member using the embossed design sheet-coated metal plate according to claim 7. A home appliance housing member using the embossed design sheet-covered metal plate according to claim 7.

Images