JP2011005650A - Laminated sheet and metal sheet coated with laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which is good in lamination aptitude on a metal sheet, has embossment heat resistance, and has neither cracks even when being subjected to an alkaline immersion test, nor appearance change in a boiling water immersion test.SOLUTION: The laminated sheet is characterized in that at least one outermost layer (hereinafter A layer 10) essentially consists of resin composition comprising: ≥50 mass% of aromatic polyester resin (al component) whose glass transition temperature is ≥100°C; and ≤50 mass% of aromatic polycarbonate resin (a2 component), relative to the mass of the entire A layer resin component, that the glass transition temperature of the a2 component is higher than that of the a1 component, and that the thickness of the A layer is 5-100 μm, with rugged design provided on the exposed surface of the A layer.

Description

The present invention relates to a laminated sheet having an embossed design on the surface, and a laminated sheet-coated metal plate coated with the laminated sheet. In particular, since emboss transferability is good and emboss heat resistance is good, emboss return is caused by heat transfer from a heated metal plate when laminating to a relatively thick metal plate. There is little possibility, and it can use especially suitably for the use of the laminated sheet covering metal plate for elevator interior materials, such as an elevator cab wall and the door of an elevator car in which a thick metal plate is often used. In addition, it is possible to obtain a laminated sheet-covered metal sheet having a surface embossed design with good embossing that is less likely to cause embossing return when exposed to a relatively high temperature during use or in contact with hot water. In addition to being excellent in alkali resistance, it is also suitable for elevator interior materials that are subjected to secondary processing such as bending after being coated on a relatively thick metal plate from the viewpoint of excellent scratch resistance and workability. The present invention relates to a laminated sheet-coated metal plate that can be used, and a laminated sheet for producing the metal plate.
The laminated sheet-covered metal plate of the present invention can also be suitably used for unit bath wall materials, unit bath ceiling materials, architectural interior material applications, home appliance housing applications, and steel furniture applications. Furthermore, the laminated sheet of the present invention is suitably used for the purpose of improving the design by covering a wooden plate, an inorganic fiber plate, a thermoplastic resin plate, a thermosetting resin plate, etc. in addition to coating a metal plate. be able to.

Conventionally, synthetic resin molded products, plywood, wood fiber boards, metal plates, etc. have been coated with a soft vinyl chloride resin sheet (hereinafter referred to as “soft PVC sheet”) with an embossed design on the surface for the above applications. Things have 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) In thermoplastic resins, 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 with 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 described above, the soft PVC sheet itself has excellent characteristics, and the embossing technology to the soft PVC sheet and the equipment for applying it have been established, and the PVC sheet-coated metal having various surface embossing designs. A board was manufactured. However, in recent years, the use of vinyl chloride resins has been restricted due to the VOC problem and the endocrine disrupting action, and in particular, for interior building materials that have a long contact with humans, soft PVC is used. There is a need for a resin-coated metal plate that does not use a sheet.

  Therefore, as an alternative to a soft PVC sheet, use of a sheet made of a polyester resin excellent in processability and surface scratch resistance for use in a resin-coated metal plate having an embossed design has been studied. As such a sheet, Patent Document 1 proposes a composition composed of a substantially amorphous polyester-based resin that can be obtained by a calendering method. Patent Document 2 proposes a decorative sheet in which a printed pattern is interposed between a sheet made of a transparent amorphous polyester resin and a sheet made of a colored opaque amorphous polyester resin.

However, since the polyester-based resin used in these is a polyester-based resin having a glass transition temperature of about 80 ° C. and not having crystallinity, an embossed design is imparted to the surface of the sheet to provide a resin-coated metal plate. In the case of use, there was a problem that remarkably embossing occurred when heated in a subsequent process.
In the method of continuous embossing by the embossing device to the thermoplastic resin sheet, the stress generated in the resin sheet due to the pressure by the embossing roll is cooled before it is sufficiently relaxed. The unevenness due to embossing has the property of heat-recoverable distortion, and is caused by the recovery of distortion and subsequent emboss return when heated in a subsequent process.

As the heating in the subsequent process, the heat transfer from the heated metal plate when laminating to the metal plate mainly increases the temperature in the vicinity of the surface of the resin sheet to which embossing is applied. The use of a metal plate having an appropriate thickness is a particularly significant problem in the lamination of laminated sheet-coated metal plates for general elevator interiors.

Similarly, since the glass transition temperature of the resin composition is about 80 ° C. and it does not have crystallinity, boiling water is often included as an evaluation test item for resin-coated metal plates used for unit bath applications. When subjected to an immersion test, not only does the embossing return, but also the resin layer itself cannot retain elasticity, causing flow deformation, which causes a significant appearance defect.

In order to secure the embossing heat resistance against the heating received when laminating to a metal plate with a sheet made of polyester resin, the following methods and the like can be considered.
By providing a thermosetting coating layer on the surface of the sheet surface with embossing, the unevenness of the embossing is physically fixed by the cross-linked structure.
By increasing the thickness of the sheet, the temperature rise on the sheet surface due to heat transfer from the metal plate heated during lamination is kept low.
As the resin composition of the layer to which embossing is applied, a polyester-based resin having crystallinity is used, and the elastic modulus of the sheet is maintained up to the temperature reaching the crystal melting point by crystallizing simultaneously with embossing or after embossing. Use things.
Even if the temperature in the vicinity of the sheet surface to which embossing is applied is increased when laminating to a metal plate by using a polyester-based resin having a high glass transition temperature as the resin composition of the layer to which embossing is applied, the resin The storage modulus of the composition should not be significantly reduced.

  However, the method (1) requires a series of facilities for coating, drying and curing a solvent-based coating agent, which is not preferable in terms of production efficiency. In addition, providing a coating layer with a certain thickness on the embossed design with a bend may cause a decrease in design properties, and the coating layer is hard enough to prevent scratching on the surface. In a resin-coated metal plate obtained by laminating a sheet provided with a film, there is a possibility of causing a problem in secondary workability such as bending. In addition, when the embossed resin layer itself has a composition that cannot withstand boiling water immersion, such as the case where the glass transition temperature is about 80 ° C. and is made of a polyester resin that does not have crystallinity, Even when a surface coating layer is applied, this property is not significantly improved.

The method (2) can be implemented with a soft PVC resin having a low raw material price, but it is not a preferable method with a polyester resin or the like.
As a method of (3), in Patent Document 3, a layer made of a crystalline polyester resin that is not crystallized is used as an embossing layer, and a layer made of an amorphous polyester resin is formed on the lower surface side of the layer. In the structure of the laminated sheet, a method for securing the embossing heat resistance by heating the laminated sheet to impart emboss and simultaneously crystallizing the embossed layer is disclosed. In the examples, a layer made of a (homo) polyethylene terephthalate (hereinafter referred to as PET) resin is formed in an amorphous state, and the layer is embossed and simultaneously crystallized.

However, in the method of Patent Document 3, the glass transition temperature is certainly sufficiently higher than room temperature if it is a PET-based resin (approximately 69 ° C. with homo-PET resin, “Saturated polyester resin handbook”, Nikkan Kogyo Shimbun. (1989)) and the slow crystallization rate, and it is possible to easily obtain a non-crystallized sheet by quenching after extrusion film formation. It can be said that the embossing fixing method by crystallization is established. In addition, since the sheet is in a non-crystallized state, if it is heated to a temperature higher than the glass transition temperature, the elastic modulus of the sheet decreases and emboss transfer becomes possible, and good emboss transfer can be obtained without heating to the melting point of the PET resin. This is also an advantage. However, the slow crystallization rate is disadvantageous when embossing is attempted to be fixed by crystallization after embossing.
That is, when trying to crystallize the sheet after being separated from the embossing roll by heating, there is a risk that the embossing will return faster than crystallization because the crystallization speed is slow. In document 3, as it is expressed as “crystallize at the same time as embossing”, it is physically embossed in the state where it is in contact with the embossing roll, that is, there is an external force called pressing by the embossing roll. It is necessary to perform a crystallization process in an environment where no return occurs. However, as described above, the crystallization speed of PET-based resin is low, and thus the processing speed of the embossing process is limited. In addition, when crystallized PET resin is crystallized in a non-oriented state, haze increases due to the formation of huge spherulites, bending as a resin-coated metal plate, etc. There is concern about a decrease in secondary workability.

On the other hand, Patent Document 4 discloses a method for producing a metal plate coated with a sheet made of polybutylene terephthalate (hereinafter referred to as PBT) resin. In patent document 4, it is said that the sheet | seat which consists of a thermoplastic resin whose difference of the softening end temperature calculated | required by TMA and a softening start temperature is 30 degrees C or less is excellent in the transferability of the embossing by an extrusion cast embossing method. A sheet made of resin is preferred.

In Patent Document 4, it is technically necessary to use an extremely high-temperature embossing roll, in which the temperature of a casting roll that is an embossing roll (described as a cooling roll in the original text) is set to the softening start temperature of the extruded resin composition ± 10 ° C. In the case of a sheet made of only homo PBT resin, the temperature of the casting roll is set to about 215 ° C. However, in order to strictly control the temperature with such a high-temperature roll, it seems that appropriate technology and equipment costs are required.

Since the PBT resin has a very high crystallization speed, it can be considered that the processing speed of the embossing process can be greatly improved compared to the PET resin, and once embossing can be applied. It is considered that sufficient embossing heat resistance can be imparted by crystallization, but in addition to the high crystallization rate, the glass transition temperature is low (when the homo PBT resin is completely in an amorphous state) The glass transition temperature is about 22 ° C. ・ "Saturated Polyester Resin Handbook" published by Nikkan Kogyo Shimbun, 1989). After extrusion film formation, a casting roll lower than the glass transition temperature of PBT resin is used. However, since the crystallization of the sheet proceeds at room temperature, when embossing is attempted with a separate embossing device on the sheet obtained by extrusion film formation, It is heated above its crystalline melting point (225 ° C. approximately in the case of homo-PBT) is required.
However, the embossing apparatus that has been used for embossing soft PVC sheets is generally one where the upper limit of the heating temperature is about 200 ° C. The sheet is made of PBT resin. It is difficult to provide embossing with an embossing apparatus, and the embossing method is restricted.
In Patent Document 4, embossing is performed by a so-called extrusion cast embossing method in which an embossing roll is used as a casting roll instead of a normal mirror-finishing roll on a PBT resin melt-flowed from a die of an extruder. .
Another advantage of using a PBT resin as the resin composition of the resin-coated metal sheet is that the PBT resin is crystallized unoriented compared to the PET resin, which is also a crystalline polyester resin. However, since a very fine crystal phase is formed, it can be mentioned that extreme whitening and deterioration of workability do not occur. Still, when crystallized, a certain increase in haze is inevitable.

Next, as the method of (4), in Patent Document 5, the resin composition of the embossing layer is a blend composition of a substantially amorphous polyester resin and an aromatic polycarbonate resin. It has been proposed to prevent emboss return when laminating or immersing in boiling water by setting the storage elastic modulus at 100 ° C. of the composition to a specific value or more.
When such a resin composition is used, the embossed resin layer maintains a high elastic modulus even when subjected to heating up to the glass transition temperature or lower, thereby preventing embossing from returning. Is.

However, in Patent Document 5, as a polyester-based resin that is substantially amorphous,
Assuming that the glass transition temperature itself is less than 100 ° C., the effect of increasing the glass transition temperature of the blend composition must depend on increasing the blending ratio of the aromatic polycarbonate resin. . In addition, by defining the storage elastic modulus of the embossed layer at 100 ° C within a specific range, it is possible to suppress emboss return in a boiling water immersion test when assuming a resin-coated metal plate for unit bath applications. The resin composition is obtained, but the embossing heat resistance when laminating to a relatively thick metal plate such as 1.6 mm used in elevator applications includes a range that cannot be said to be sufficient. Yes. Based on the contents of Patent Document 5, in order to prevent embossing from returning when laminating to a thick metal plate as described above, the blending ratio of the aromatic polycarbonate resin is increased, and the aromatic polycarbonate resin is used. However, in the resin-coated metal plate, a resin sheet mainly composed of an aromatic polycarbonate resin is laminated on a relatively thick metal plate. However, although the problem of emboss return disappears, the alkali resistance tends to deteriorate. This is because a thick metal plate has a relatively large amount of heat when it is heated to the laminating temperature, so even if a cooling method such as water cooling is used, the temperature of the coated resin sheet immediately decreases. It is presumed that residual strain accompanying heating / cooling tends to remain, and that the aromatic polycarbonate resin, which occupies the main component of the resin composition, has relatively weak physical properties against stress cracks.

On the other hand, Patent Document 6 discloses a polyester resin for decorative steel sheet, from a copolymer polyester resin having terephthalic acid as a main dicarboxylic acid component, ethylene glycol 85 to 60 mol%, and spiroglycol 15 to 40 parts by mass as a glycol component. A composition obtained by laminating a sheet-like material comprising the composition on a metal plate is said to be excellent in processability, heat resistance, impact resistance, chemical resistance and stain resistance.

However, in the case of a single-layer sheet made of the composition, when embossing is to be applied with an embossing apparatus, it is necessary to heat to a temperature equal to or higher than the glass transition temperature (Tg) of the resin composition. The heated sheet has a sudden drop in elastic modulus, causing problems such as sticking and sticking to the heating drum of the embossing device, width shrinkage due to insufficient melt tension of the sheet, crease, and melt fracture of the sheet. There is a fear. In the embodiment of Patent Document 6, embossing is performed by applying a resin sheet to a metal plate and then pressing it with an embossing roll in the form of a metal sheet as a carrier sheet. However, in this method, although the resin coating is applied to one side, the metal plate is passed between the rolls, and the embossing roll surface may be damaged due to warpage of the end of the metal plate. And scratches on the roll immediately cause a decrease in the surface design of the resin-coated metal sheet.

In addition, if a metal plate having a considerably high thickness accuracy is not used, there is a risk that the embossing roll is pressed evenly on the resin layer from place to place. Depending on the type of embossed design, even if slight transfer unevenness occurs, a difference depending on the place of the design feeling becomes remarkable, which may impair the commercial value.
As a solution for this, it is conceivable to increase the thickness of the resin layer so that uneven transfer is difficult to occur. It is not preferable from the point.

Moreover, in patent document 6, although the embossing retention rate after leaving still in an oven of 90 degreeC for 5 days was evaluated in the Example regarding embossing heat resistance, the resin sheet was heated to lamination temperature, thickness 1 When laminating to a 6 mm metal plate, the temperature of the embossed resin layer surface rises to about 120 ° C. even when quenching with water or the like, so that only the spiroglycol copolymerized PET resin is used. When the composition consisting of is used as an embossing imparting layer, it is considered that the heat resistance in elevator applications is insufficient. Even the resin composition having the highest glass transition temperature in the examples of Patent Document 6 has a glass transition temperature of 111 ° C.

JP 2001-200166 A JP 2002-103544 A JP 2001-322219 A International Publication WO2000 / 026282 A1 Pamphlet JP 2007-237568 A JP 2004-035633 A

  The present invention has been made in order to solve the above-mentioned problems of the prior art, and is suitable for embossing within the range of embossing the soft PVC sheet using a conventional embossing device, Also, when laminated to a relatively thick metal plate for elevator applications, etc., a laminated sheet having an embossed design with good embossing heat resistance that does not cause emboss return and does not deteriorate alkali resistance, embossed design An object of the present invention is to provide a sheet-coated metal plate, a building interior material, and the like, and to provide an embossed design sheet or an embossed design sheet-coated metal plate having a transparent surface layer that does not cause an increase in haze due to crystallization. It is.

The present invention provides a laminated film in order to solve the above problems.
That is, the present invention solves the above-described problem by using an aromatic polyester resin (a1) in which at least one outermost surface layer (hereinafter referred to as A layer) has a glass transition temperature of 100 ° C. or higher with respect to the mass of the entire A layer resin component Component) 50 mass% or more and the aromatic polycarbonate resin (a2 component) 50 mass% or less is a main component, and the glass transition temperature of the a2 component is higher than the glass transition temperature of the a1 component, The problem is solved by a laminated sheet characterized in that the thickness of the A layer is 5 μm to 100 μm and the surface on which the A layer is exposed has an uneven design.

As the aromatic polyester-based resin in the A layer, crystalline and amorphous resins can be used. The aromatic polyester resin having a glass transition temperature of 100 ° C. or higher in the A layer may be composed of one kind of substantially amorphous copolymer polyester resin, or two or more kinds of substance. Alternatively, it may be composed of a mixture of amorphous copolyester resins. Alternatively, it may be composed of a mixture of a kind of substantially amorphous copolyester resin and a small amount of crystalline polyester resin. In the case of two or more kinds of resin mixtures, it is sufficient that the compatibility between the glass transition temperature and the aromatic polycarbonate resin is obtained as the composition of the entire resin mixture.

  In this laminated sheet, the A layer is a layer located on the outermost surface of the laminated sheet, and is also the outermost layer in the configuration of the laminated sheet-coated metal plate. The layer A is a layer having a good emboss transfer property, and at the same time, is a layer having a low possibility of causing emboss return when being laminated with a metal plate having a thickness which is heated to a laminating temperature. Moreover, even when laminated on a thick metal plate by blending the aromatic polycarbonate-based resin to 50% by mass or less, even a layer that can prevent a decrease in alkali resistance due to residual strain in the sheet. is there.

In the first aspect of the present invention, when the resin component constituting the layer A is measured at a storage elastic modulus (E ′) by a dynamic viscoelastic tension method at a frequency of 10 Hz, the measured value at 120 ° C. is It is preferable that it is 2 * 10 < ⁸ > Pa-6 * 10 < ⁹ > Pa.

When the storage elastic modulus of the A layer is in the above range at 120 ° C., even when it is necessary to laminate on a relatively thick metal plate such as a resin-coated plate for elevators, emboss return is caused by insufficient emboss heat resistance. There is little fear.

In the first aspect of the present invention, the amorphous aromatic polyester resin (a1 component) having a glass transition temperature of 100 ° C. or higher and having compatibility with the aromatic polycarbonate resin is terephthalic acid or a derivative thereof. A polyester resin comprising a resin composition mainly composed of an acid component, 100 mol% of the total amount of diol component, and composed mainly of 50 mol% to 70 mol% of ethylene glycol and 30 mol% to 50 mol% of spiroglycol. Something is preferable.

According to this aspect, a commercially available material can be used as the polyester-based resin, and the merit of stability of raw material supply can be obtained. In addition, the polyester resin in the composition range has a good compatibility with the aromatic polycarbonate resin, and can provide a layer A having a good transparency with little haze.

In the first invention, the substantially amorphous aromatic polyester resin (a1 component) having a glass transition temperature of 100 ° C. or higher and having compatibility with the aromatic polycarbonate resin is terephthalic. The main component of the dicarboxylic acid component is an acid or a derivative thereof, and the total amount of the diol component is 100 mol%. 1,4-cyclohexanedimethanol 60 mol% to 80 mol%, 2,2,4,4, -tetramethyl It is preferably a polyester-based resin having a resin composition mainly composed of 20 mol% to 40 mol% of -1,3-cyclobutanediol.

Also in this embodiment, a commercially available material can be used as the polyester-based resin, and the merit of stability of raw material supply can be obtained. In addition, the polyester resin in the composition range has a good compatibility with the aromatic polycarbonate resin, and can provide a layer A having a good transparency with little haze.

The second aspect of the present invention is a resin layer comprising a polyester resin having a glass transition temperature of less than 100 ° C. of 70% by mass or more (B A laminated sheet having at least two layers.

The resin used in the B layer may be a crystalline polyester resin or a substantially amorphous polyester resin. In the case of comprising a resin composition comprising 70% by mass or more of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C., a sheet comprising a single A layer having a relatively high glass transition temperature. In comparison, the adhesiveness of the laminated sheet to various thermoplastic resin sheets, wood boards, inorganic fiber boards, thermoplastic resin boards, thermosetting resin boards, metal plates, etc. can be improved.
In addition, a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. can be obtained at a lower price than those having a glass transition temperature of 100 ° C. or higher. The merit of raw material cost can be acquired compared with the case where thickness is comprised with the resin composition of A layer. The B layer is a layer that can be deformed by pressing with an embossing plate, like the A layer, at the time of transferring the embossed pattern to the laminated sheet, and the raw material unit price is relatively high in each layer of the laminated structure. An embossed pattern having a depth corresponding to the total thickness of the A layer and the B layer can be obtained while the thickness of the A layer is relatively thin.

In the second aspect of the present invention, it is preferable that the A layer and the B layer are obtained by being laminated and integrated by a coextrusion film forming method.
According to this aspect, the laminated sheet in which both the A layer and the B layer are substantially transparent is coated on the surface of a base material such as a sheet or plate having a design property on the surface by coloring or printing. Thus, an uneven design by emboss transfer can be imparted without deteriorating the design properties of these existing colored designs and printing designs. In addition, by obtaining A and B layers in a state where they are laminated and integrated by coextrusion film formation, the number of steps for lamination and integration in the subsequent process is not required, and efficient production is possible. You can get the above benefits.

According to a third aspect of the present invention, the total amount of the resin component is 100% by mass on the surface of the layer A that is not provided with an uneven design, and the polybutylene terephthalate resin having a melting point of 210 ° C. to 230 ° C. It is a laminated sheet having at least two layers having a resin layer (C layer) having a thickness of 200 μm or less and comprising a polyester resin having a glass transition temperature of less than 100 ° C. and having a colorant added thereto.

In the third aspect of the present invention, the C layer is a layer having a coloring design and a visual concealing function such as a base metal plate by adding a colorant. A combination of relatively inexpensive polyester-based resin raw materials, even when the thickness of the C layer is relatively thick in order to provide a sufficient visual hiding function by using a resin composition for the C layer as described above. Thus, it is possible to obtain a laminated sheet that does not cause an appearance abnormality due to the resin composition of the C layer after being immersed in boiling water. Of course, even when the total thickness of the resin sheet is composed of the resin composition of the A layer, a resin-coated metal plate that does not cause abnormal appearance when immersed in boiling water can be obtained. Can be obtained.

Further, the polyester resin used in the C layer may be a substantially amorphous polyester resin. The polyester-based resin used in the layer C includes a substantially amorphous polyester-based resin having a glass transition temperature of less than 100 ° C., and is based on the amorphous or low-crystalline polyester resin. Since various types of pigment master batches are commercially available, it is possible to obtain convenience in coloration and color matching to various colors.
Furthermore, the C layer is a layer that can be deformed by pressing with an embossing plate, similar to the A layer, at the time of transferring the embossed pattern to the laminated sheet. The embossed pattern having a depth corresponding to the total thickness of the A layer and the C layer can be obtained while the thickness of the layer is relatively thin.

In the third aspect of the present invention, the A layer and the C layer are obtained in a state of being laminated and integrated by a coextrusion film forming method, and are simultaneously cast by a coextrusion film forming method. It is preferable that the embossed design is given to the surface of the A layer side by using an embossed roll on which the concave and convex sculpture of the design is given as the roll.

In the third aspect of the present invention, since the glass transition temperature of the resin composition of the A layer is relatively higher than that of the C layer, it has been conventionally used for embossing a soft PVC sheet. However, according to the so-called extrusion cast embossing method using an embossing roll as a casting roll, the surface on the A layer side of the laminated sheet composed of the A layer and the C layer is good. An uneven design by embossing can be given.
According to this aspect, the uneven surface design and coloring by emboss transfer is performed by covering the surface of the base material such as a sheet or plate that does not have design properties due to coloring, printing, or the like with the laminated sheet of the A layer and the C layer. Design can be given. Further, by obtaining the A layer and the C layer in a state of being laminated and integrated by the co-extrusion film forming method, the number of steps for the lamination and integration in the subsequent process becomes unnecessary, and a merit in manufacturing cost can be obtained.

4th this invention contains 75 mass% or more of polybutylene terephthalate type-resins whose melting | fusing point is 210 degreeC-230 degreeC by making the whole quantity of C layer and a resin component into 100 mass% on the surface which does not have the uneven | corrugated design of A layer. A laminated sheet having at least three resin layers (D layers).

Here, the function of the C layer is the same as in the case of the third aspect of the present invention. However, with respect to the D layer, an embossing device or the like is used to easily give the surface of the A layer an uneven design by embossing. It is a layer that is applied to prevent the adhesion of the laminated sheet (A layer + C layer + D layer) to the heated metal roll, etc. when the laminated sheet (A layer + C layer + D layer) is heated by an embossing device. It has a function to prevent the sheet from being melted and broken. By including 75% by mass or more of the PBT resin having a high crystallization speed, the D layer can be crystallized relatively easily. The heating temperature of the laminated sheet in the embossing apparatus By setting the temperature below the melting point and higher than the glass transition temperature of the A layer, the embossing operation can be easily performed without the risk of adhesion, wrinkling, width shrinkage, melt fracture and the like of the laminated sheet.
In addition, regarding the D layer, since it is a combination of relatively inexpensive polyester resin raw materials, it is possible to obtain the merit of the raw material cost as compared with the case where the total thickness of the resin sheet is constituted by the resin composition of the A layer. it can.
In order for the D layer to exhibit suitable properties such as non-adhesiveness and melt fracture resistance in an embossing apparatus, it is necessary that the D layer is in a crystallized state. Even when laminating to a plate, the crystallized state of the D layer is maintained, but as a crystalline polyester resin used for the D layer, a PBT resin having a melting point of 230 ° C. or lower is used. The conventional soft PVC sheet can be laminated to the metal plate under the equipment and conditions used for laminating the metal plate.

The fifth aspect of the present invention includes at least four layers and a printed pattern comprising the following B layer, C layer, and D layer in order from the A layer side on the side where the uneven design by emboss transfer of the A layer is not provided. A laminated sheet having E. The printed pattern E is preferably interposed between the B layer and the C layer.

According to this aspect, it is a layer which imparts easy adhesiveness in order from the A layer side to the side where the concavo-convex design by the emboss transfer of the A layer is not applied, and is deformed by pressing together with the A layer when embossing is applied. It has a B layer that can do things, a printed pattern E, a C layer that gives a colored design and a visual hiding function, and a D layer that gives suitability to an embossing device be able to. The roles of the B layer, the C layer, and the D layer are the same as in the second to fourth inventions.
In the fifth aspect of the present invention, the A layer and the B layer are obtained by being laminated and integrated by a coextrusion film forming method, and the C layer and the D layer Is obtained in a state of being laminated and integrated by a co-extrusion film forming method. After the printed pattern E is applied to the C layer side surface of the laminated and integrated C layer and D layer, the printed pattern E is obtained. Is preferably laminated and integrated with the B layer side surface of the laminated sheet of the A layer and the B layer.
By setting it as such a structure and a manufacturing method, the embossing design with heat resistance is provided on the surface by the embossing apparatus, and the lamination sheet which has a printing design together can be obtained by an efficient method.

The substantially amorphous polyester resin in which the glass transition temperature of the B layer of the second invention and the fifth invention is less than 100 ° C. is mainly composed of terephthalic acid or a derivative thereof, It is preferably an amorphous polyester resin mainly composed of 20 mol% to 80 mol% of 1.4-cyclohexanedimethanol and 20 mol% to 80 mol% of ethylene glycol.

Since the polyester resin in this composition range is completely amorphous or relatively low in crystallinity, a laminated sheet having a B layer or a laminated sheet-covered metal plate mainly using the polyester resin is long. Even after being subjected to storage for a long period, due to the progress of crystallization over time, the performance required for the B layer such as easy adhesion and transparency is less likely to be reduced. Cost benefits can also be obtained.

  The substantially amorphous polyester-based resin in which the glass transition temperature of the C layer of the third, fourth, and fifth inventions is less than 100 ° C. is mainly composed of terephthalic acid or a derivative thereof as a main component of the dicarboxylic acid component. It is preferably an amorphous polyester resin mainly composed of 20 mol% to 40 mol% of 1.4-cyclohexanedimethanol and 60 mol% to 80 mol% of ethylene glycol as diol components.

Since various types of pigment master batches (resin pellets preliminarily kneaded with pigments) based on an amorphous or extremely low crystalline polyester resin having such a composition range are commercially available, Convenient for coloring and color matching.
In addition, as for the resin component that is the main component of the B layer, if the same material as the substantially non-crystalline polyester raw material that is one of the constituent components of the C layer is used, the purchase of raw materials, the raw material charging facilities The advantage of sharing can be obtained.

  In 4th invention and 5th invention, the uneven | corrugated design by the emboss transfer provided to the said A-layer side surface can be provided with the embossing apparatus installed separately from the extrusion film forming equipment. . This is due to the effect of providing the aforementioned D layer.

The sixth aspect of the present invention includes a laminated sheet having an embossed design on the surface of the A layer of the first to fifth aspects of the invention, and a metal plate, and the surface of the laminated sheet that is not on the A layer side is laminated to the metal plate. It is a coated metal plate.

The laminated sheet-covered metal plate of the sixth aspect of the present invention can be suitably used as an elevator interior material, a unit bath member, a building interior material, a steel furniture member, and a home appliance housing member. Examples of the elevator interior material include an elevator cab wall, an elevator cab ceiling, and an elevator cab door, and examples of the unit bath member include a unit bath wall material and a unit bath ceiling material. Examples of building interior materials include closet door materials, partition materials, and general wall materials. The laminated sheet-coated metal plate of the present invention can be suitably used as these materials.

  The laminated sheet of the present invention can provide good emboss transferability and heat resistance of the emboss, and therefore, even after being laminated on a relatively thick metal plate used for elevator applications, It is possible to efficiently obtain a metal plate coated with a laminated sheet with a good embossed design that does not return, and it has a good embossed design using this and can also have a printing design. Embossing that does not cause problems such as cracking of the resin layer even when subjected to tests such as alkali soaking, and does not cause poor appearance such as deformation due to embossing return or softening of the resin layer even in the boiling water soaking test A designable laminated sheet-coated metal plate can be obtained. Furthermore, the laminated sheet-coated metal plate has good characteristics for secondary processing such as bending, and has high surface hardness, so it has excellent scratch resistance and excellent productivity. Therefore, it is also advantageous in terms of cost.

  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.

Hereinafter, embodiments embodying the present invention will be described.
<Laminated sheet 100>
The structure of the lamination sheet 100 of this invention is typically shown to Fig.1 (a)-(f). FIG. 1A shows a laminated sheet 100A in which two layers of an A layer 10 and a B layer 20 are laminated in order from the surface, and the surface of the A layer has an uneven design by emboss transfer, and FIG. 2 layers of A layer 10 and C layer 30 are laminated | stacked in order from the surface, and the lamination sheet 100B which has the uneven | corrugated design by emboss transfer on the surface of A layer is shown, FIG.1 (c) shows A layer 10 in order from the surface. 3C shows a laminated sheet 100C in which three layers of C layer 30 and D layer 40 are laminated, and the surface of the A layer has an uneven design by emboss transfer. In FIG. 1D, four layers of A layer 10, B layer 20, C layer 30, and D layer 40 are laminated in order from the surface, and the surface of A layer 10 has an uneven design by emboss transfer, and at the same time B A laminated sheet 100D having a printed pattern E50 between the layer 20 and the C layer 30 is shown. FIG. 1 (e) shows a laminated sheet-covered metal plate 200A obtained by coating the laminated sheet 100C shown in FIG. 1 (c) on a metal plate 60 using an adhesive 70, and FIG. A laminated sheet-covered metal plate 200B obtained by laminating the laminated sheet 100D shown in (d) is shown.

The laminated sheet 100 of the present invention is more correctly described as “film or sheet” with respect to its thickness, but here, for the sake of convenience, the single term “sheet” is also used for the range generally referred to as “film”. Is used.
In addition, the expression “non-orientation” does not mean that an orientation treatment such as a stretching operation has been performed in order to impart some performance to the laminated sheet (using a tenter, a longitudinal stretching apparatus, or the like in a post-casting process) Therefore, it does not mean that an orientation treatment such as a stretching operation is intentionally performed), and that an orientation generated by pulling by a casting roll during extrusion film formation does not exist.
In addition, the expression “substantially transparent” means that the printed pattern applied to the lower side and the layer having the colored design on the lower side can be visually recognized through the substantially transparent resin layer. In addition, this means that the layer does not significantly lower the design feeling. Specifically, depending on the embossed shape to be applied, measurement is performed according to JIS K 7105 in a state where the A layer 10 single layer or the A layer 10 and the B layer 20 are laminated and the surface is embossed. The total light transmittance is 45% or more, preferably 55% or more, and more preferably 70% or more. And haze is 85% or less, Preferably it is 55% or less, More preferably, it is 30% or less.

<A layer 10>
The A layer 10 is a layer that becomes the surface of the laminated sheet 100, and is a layer to which an embossed pattern is transferred by embossing the laminated sheet by being softened by heating and pressed by an embossing roll. Therefore, when the A layer 10 is pressed by the embossing roll, a melting point (Tm) exceeding about 200 ° C., which is the upper limit of the sheet heating temperature in the embossing apparatus generally used for embossing the soft PVC sheet. It must not be composed of a resin composition having high crystallinity. Moreover, in the case of an amorphous resin, it should not be constituted by a resin composition having a glass transition temperature exceeding about 200 ° C.

  The A layer 10 may not be a layer mainly composed of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. Even when such a resin is used, the transferability itself of the embossed design can be good, but because the glass transition temperature is too low and there is no expression of the elastic modulus retention effect due to crystallinity, The embossing is inferior in embossing resistance when laminated to a relatively thick metal plate used for elevator applications. Alternatively, when immersed in boiling water, the A layer 10 itself undergoes fluid deformation in all layers, resulting in a remarkable appearance defect.

Moreover, it is preferable that the storage elastic modulus (E ') in 120 degreeC by 10 Hz by the dynamic viscoelastic tension method of A layer 10 is 1 * 10 < ⁷ > Pa-6 * 10 < ⁹ > Pa. When the storage elastic modulus is too low, emboss return may become remarkable when laminating to a thick metal plate used for the above elevator application, while it is higher at 120 ° C. Thermoplastics with storage modulus are generally difficult to obtain and do not need to be used, but it does not mean to exclude such materials in the future if a material exceeding this upper limit is discovered. . Even if it is such a material, if the effect of this invention can be show | played, it can employ | adopt as a material which comprises A layer 10. FIG.

In the present invention, the A layer 10 is preferably obtained by being laminated and integrated with other layers such as the B layer 20 and the C layer 30 by a coextrusion film forming method. In the case of the laminated structure, it is impossible to directly measure the storage elastic modulus in the single layer A 10. Therefore, when the contents of the resin composition of the layer A 10 of the laminated sheets are clearly known, a sheet composed of a single layer of the resin composition of the layer A with the same composition is prepared by extrusion film formation. A specimen for viscoelasticity measurement is used. Alternatively, in the case of the laminated sheet of the A layer 10 and the B layer 20, when the thickness of each layer is clear and the dynamic viscoelastic behavior of the B layer is known, the A layer 10 and the B layer 20 For laminated sheets, dynamic viscoelasticity measurement is performed, and viscoelastic behavior in the case of A layer 10 single layer is excluded from the measurement results obtained by excluding viscoelastic behavior derived from known B layer 20 by calculation. It is necessary to ask for. In addition, when the resin composition of the A layer 10 is unclear, only the A layer 10 is cut out from the laminated sheet with a microtome, etc., and by NMR analysis or other analysis method or thermal measurement such as DSC. The method of specifying the resin composition of A layer, making the sheet | seat which consists of the resin composition single layer of A layer with the same mixing | blending by extrusion film formation, and making it the specimen of a dynamic viscoelasticity measurement etc. Can be obtained.

In addition, the storage elastic modulus of the A layer at 170 ° C. is preferably 1 × 10 ⁷ (Pa) or less. By being 170 degrees C or less and the said numerical value or less, embossing can be implemented without difficulty within the range of the sheet heating capability of the embossing apparatus conventionally used for embossing to a soft PVC sheet. Moreover, as a glass transition temperature of the blend composition of A layer 10, it is preferable that it is 116 degreeC or more, and it is especially preferable that it is 120 degreeC or more.

From the above viewpoint, in the present invention, the glass transition temperature of the A layer 10 is 100 ° C. or higher based on the mass of the entire resin component in the A layer 10 and is compatible with the aromatic polycarbonate resin. A layer composed mainly of a resin composition comprising 50% by mass or more of an aromatic polyester resin (a1 component) that is substantially amorphous and 50% by mass or less of an aromatic polycarbonate resin (a2 component) is used.
Here, the “main component” includes 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, based on the entire A layer 10 (100% by mass). That means.
In addition, having compatibility with an aromatic polycarbonate resin means that a single glass is used for a blend composition of an aromatic polyester resin and an aromatic polycarbonate resin obtained by an ordinary melt-kneading and extrusion film forming method. When a transition temperature is observed, and the glass transition temperature is located between the glass transition temperature of the aromatic polyester resin and the glass transition temperature of the aromatic polycarbonate resin, in the vicinity of the temperature calculated by the approximate empirical formula of Fox. Point to. The unity of the glass transition temperature can be determined by measurement with a differential scanning calorimeter (DSC), or the imaginary term of temperature dispersion (loss elastic modulus E ") in dynamic viscoelasticity measurement. It can be judged from the dispersion peak.
When an aromatic polyester resin having a glass transition temperature of layer A 10 of 100 ° C. or higher is used which is poorly compatible with an aromatic polycarbonate resin, a blend composition obtained by adding an aromatic polycarbonate resin The effect of improving the glass transition temperature is not sufficiently obtained, and the effect of suppressing the embossing return upon lamination to a thick metal plate tends to be insufficient. In the case of a blend composition having poor compatibility, the internal haze of the sheet is increased, so that the color design and the print design of the colored layer provided under the A layer 10 are clearly visible. You may not be able to get

When the blending ratio of the aromatic polycarbonate resin exceeds 50% by mass in the resin composition as the main component of the A layer 10, the resin-coated metal is laminated on a relatively thick metal plate for elevator applications. When used as a plate, there is a possibility of causing a problem in alkali resistance. In order to ensure the alkali resistance, the blending ratio of the aromatic polycarbonate resin in the resin composition of the A layer 10 is particularly preferably 45% by mass or less.

(Substantially amorphous aromatic polyester resin of layer A 10)
As a substantially non-crystalline (including low-crystalline) polyester-based resin that can be used for the A layer 10, when a measurement in accordance with JIS K 7212 is performed using a differential scanning calorimeter (DSC), Not only polyester-based resins that do not show a clear crystallization peak and / or crystal melting peak when the temperature is raised, but those that have crystallinity have a low crystallization rate (using a differential scanning calorimeter (DSC), “Perkin Elmer Crystal melting observed at elevated temperature by a differential scanning calorimeter (DSC) of those having a crystallinity and having a ½ crystallization time of 200 seconds or more measured by holding at 120 ° C. by the “method” The amount of heat (ΔHm) is as low as 10 J / g or less, and the glass transition temperature is 100 ° C. or more as described above, and is compatible with the aromatic polycarbonate resin. It can be used if.

In addition, in the blend composition with the aromatic polycarbonate-based resin, at the time of contact with the casting roll at the time of creating the sheet by the extrusion film forming method, or the silicone rubber roll facing the casting roll, or at the time of heating the sheet with an embossing device, Alternatively, during heat lamination with a relatively thick metal plate, further, the resin composition of the A layer 10 does not have high crystallinity due to a temperature rise when the resin-coated metal plate is stored in a warehouse or the like. Regarding the aromatic polyester resin forming the blend composition, any glass having a glass transition temperature of 100 ° C. or more and having compatibility with the aromatic polycarbonate resin can be used.
Generally, by using a dicarboxylic acid component or a diol component having a bulky molecular structure as a copolymer component of a polyester-based resin, the crystallinity can be lowered, and thus a polyester-based material that is substantially amorphous. It is known that a resin can be obtained, and it is known that a polyester resin having a high glass transition temperature can be obtained by using a dicarboxylic acid component or a diol component having a rigid molecular structure. Among these copolyester resins, those having physical properties to be provided as the component (a1) of the present invention can be selected and used.

Among them, terephthalic acid or a derivative thereof is the main component of the dicarboxylic acid component, and the total amount of the diol component is 100 mol%. An aromatic polyester resin comprising a resin composition mainly composed of diol component can be preferably used.
The composition of the polyester resin may be composed of one kind of substantially amorphous copolymer polyester resin, or two or more kinds of substantially amorphous copolymer polyester resins. It may be composed of a mixture of In the case of two or more kinds of resin mixtures, the above spiroglycol and ethylene glycol may be in a predetermined range as a whole resin mixture.

Further, the “main component” in the dicarboxylic acid component here is at least 70 mol% or more of terephthalic acid derivatives such as terephthalic acid or dimethyl terephthalic acid, based on the whole dicarboxylic acid component (100 mol%), preferably 80 mol% or more, more preferably 98 mol% or more. The “main component” in the diol component is preferably 90 mol% or more, more preferably 93 mol% or more, and still more preferably 95 mol%, based on the total amount of the diol component (100 mol%). Saying that it contains more than mol%.
Examples of the dicarboxylic acid component other than terephthalic acid or derivatives thereof include aromatic dicarboxylic acids such as isophthalic acid and dimethylisophthalic acid, and aliphatics such as adipic acid, succinic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. Examples thereof include various dicarboxylic acids used for polymerization of polyester resins such as dicarboxylic acids, or used as copolymerization components. Further, a polyfunctional carboxylic acid component may be contained in an amount of about several mol% or less. Among these, when 2,6-naphthalenedicarboxylic acid is used as a copolymerization component, an effect of further increasing the glass transition temperature of the resin composition can be obtained, but when the ratio of the copolymerization component is increased too much, The raw material price becomes expensive, and it becomes difficult to adapt to the use of the design resin-coated metal sheet in terms of cost.

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

The resin composition constituting the A layer 10 can be a polyester resin composition having a high glass transition temperature due to the rigidity of the molecular chain by using spiroglycol as a copolymerization component. However, when spiroglycol in an amount exceeding 50 mol% is included as the diol component, the glass transition temperature (Tg) of the resin composition becomes higher, but the blend composition with the aromatic polycarbonate resin is used in the blend composition. However, the tear resistance of the resin sheet decreases, the notch sensitivity when applying tensile stress becomes sharp, and the sheet breaks only by adding a slight elongation in the part with minute scratches. As physical properties of the sheet for the resin-coated metal plate, there is a possibility that undesired characteristics may be developed.

  Conversely, when the copolymerization ratio of spiroglycol is too low, the glass transition temperature (Tg) of the copolymerized polyester resin composition may be less than 100 ° C. Moreover, it is not preferable also from the point that crystallinity becomes remarkable and compatibility with an aromatic polycarbonate-type resin falls.

  In the case of an aromatic polyester resin composition in which the dicarboxylic acid component is only terephthalic acid and the diol component is mainly composed of spiroglycol and ethylene glycol, the copolymerization ratio of spiroglycol is less than about 30 mol% of the diol component. The glass transition temperature (Tg) of the resulting copolyester resin is lower than 100 ° C. From this point, it is preferable that the lower limit of the copolymerization ratio of spiroglycol in the diol component is 30 mol% or more.

  When the glass transition temperature of the polyester resin composition to be contained in the A layer 10 is 50% by mass or more is lower than 100 ° C., an aromatic polycarbonate resin that can contain only 50% by mass or less, and a compatible system When the blend composition is formed, the glass transition temperature of the blend composition is not sufficiently high. As a result, the heat resistance of the embossing is insufficient, and the embossing is particularly difficult when laminating to a thick metal plate. There is a risk that the return will be significant. The glass transition temperature of the aromatic polyester resin constituting the A layer 10 is more preferably 105 ° C. or higher, and particularly preferably 110 ° C. or higher.

  As the copolyester resin having a preferable composition range of the aromatic polyester resin and having a glass transition temperature of 100 ° C. or higher, for example, “Altester 45” or “Altester 30” manufactured by Mitsubishi Gas Chemical Company, Inc. Can be mentioned. “Altester 45” has a glass transition temperature (Tg) of 111 ° C. measured at a heating rate of 10 ° C./min according to JIS K 7212 by differential scanning calorimetry (DSC). It is an amorphous polyester resin in which no melting behavior is observed, and forms a compatible blend composition with an aromatic polycarbonate resin at an arbitrary blend ratio. “Altester 30” is an amorphous polyester resin having a glass transition temperature of 104 ° C. and no crystallization behavior or crystal melting behavior observed in the same manner. It is an aromatic polyester resin that forms a compatible blend composition at a blend ratio.

Alternatively, as (a1 component), terephthalic acid or its derivative is the main component of the dicarboxylic acid component, and the total amount of the diol component is 100 mol%, and 60 mol% or more and 80 mol% or less of 1,4-cyclohexanedimethanol and Alternatively, a polyester resin having a resin composition mainly composed of 2,2,4,4, -tetramethyl-1,3-cyclobutanediol of 40 mol% or less and 20 mol% or more may be used.
When 50 mol% or more of the diol component is composed of 1,4-cyclohexanedimethanol, it is known to form a compatible blend composition with an aromatic polycarbonate resin, and 2,2,4 By using, 4, -tetramethyl-1,3-cyclobutanediol as the diol component, a substantially amorphous polyester resin having a high glass transition temperature can be obtained. Such a polyester-based resin composition has a production method described in the patent publication published in JP-T-2008-544022, and among them, the glass transition temperature is 100 ° C. or higher, and is substantially amorphous. Can be used. The composition of the polyester resin may be composed of one kind of substantially amorphous copolymer polyester resin, or two or more kinds of substantially amorphous copolymer polyester resins. It may be composed of a mixture of In the case of two or more kinds of resin mixtures, the above spiroglycol and ethylene glycol may be in a predetermined range as a whole resin mixture.

Examples of commercially available raw materials include “Tritan FX-100” and “Tritan FX-200” manufactured by Eastman Chemical Company. “Tritan FX-100” has a glass transition temperature (Tg) of 110 ° C. measured at a heating rate of 10 ° C./min by differential scanning calorimetry (DSC), and no crystallization behavior or crystal melting behavior is observed. It is a crystalline polyester resin and forms a compatible blend composition with an aromatic polycarbonate resin at an arbitrary blend ratio. “Tritan FX-200” is a non-crystalline polyester resin having a glass transition temperature of 118 ° C. measured in the same manner and is compatible with an aromatic polycarbonate resin at an arbitrary blend ratio. Form.

On the other hand, an aromatic polyester-based resin using an aromatic diol has been developed as a diol component having a rigid molecular structure having an effect of increasing the glass transition temperature. For example, dicarboxylic acid components include terephthalic acid and isophthalic acid. A so-called polyarylate resin comprising an acid and a diol component comprising bisphenol A also has a glass transition temperature of 100 ° C. or higher (about 200 ° C. for “U polymer U-100” manufactured by Unitika), and aromatic. It is known to form a compatible blend composition with a polycarbonate-based resin. In the present invention, although the glass transition temperature is higher than 100 ° C., the glass transition temperature of an aromatic polycarbonate-based resin is higher. Blends less than 50 mass% aromatic polycarbonate resin to low aromatic polyester resin That it by and seeks to improve the heat resistance, the use of a polyester resin which inherently has a glass transition temperature higher than the aromatic polycarbonate resin, does not fall within the scope of the present invention. In addition, such a polyester resin having a high glass transition temperature is very expensive, and in that respect, it is difficult to use it for a resin-coated metal plate for building materials, and because the heat resistance is too high, Conventionally, there is a possibility that good emboss transfer cannot be obtained in the range of the sheet heating temperature in an embossing apparatus that has been used for embossing a soft PVC sheet.
Therefore, the case where the glass transition temperature Tg1 of the (a1 component) is lower than the glass transition temperature Tg2 of the (a2 component) is within the scope of the present invention.

(Aromatic polycarbonate-based resin of layer A 10)
The aromatic polycarbonate resin used for the A10 layer of the present invention is produced by a known method such as a phosgene method, a transesterification method, or a pyridine method. It is a polymer obtained by using an aromatic dihydroxy compound. 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 with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added to perform melt transesterification condensation polymerization. Representative examples of the dihydric phenol include bisphenols, and in particular, 2.2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is most widely used, and the aromatic polycarbonate resin of the present invention. It is also preferable as a raw material used in the above. 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-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 -Halogens such as hydroxyphenyl) propane Mention may be made of the bisphenols.

  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, and dicyclohexyl carbonate. 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 molecular weight of the aromatic polycarbonate resin used in the present invention is a viscosity average molecular weight converted from the solution viscosity measured at 20 ° C. using methylene chloride as a solvent, and the lower limit is preferably 20000 or more, more preferably 22,000 or more. Moreover, an upper limit becomes like this. Preferably it is 40000 or less, More preferably, it is 30000 or less. It is known that when the viscosity average molecular weight is too small, particularly the low temperature impact strength is lowered. On the other hand, when the viscosity average molecular weight is too large, the melt viscosity becomes very high and the molding processability is lowered. Since it takes a long time, it is not preferable in terms of production cycle and cost. In the present invention, one type of aromatic polycarbonate resin may be used alone, or two or more types may be mixed and used.

(Additive for layer A 10)
When the printed pattern F is not present under the A layer 10, a colorant may be added to the A layer 10 for providing design properties or visually hiding the underlying metal. In the present invention, the A layer Is preferably a substantially transparent layer. This is because the main components of the A layer (a1 component) and (a2 component) are resin types that require melt kneading at a relatively high temperature, so that the colorant that can be used is restricted from the viewpoint of heat resistance. This is because the colorant having the resin composition of the C layer 30 described later as a base resin is much more versatile and is more convenient because it is commercially available.

  Various additives may be added to the A layer 10 in an appropriate amount in order to further improve the physical properties other than the object of the present invention within a range not impairing the properties of the present invention. Additives include phosphorous and phenolic various antioxidants, heat stabilizers, UV absorbers, light stabilizers, impact modifiers, processing aids, hydrolysis inhibitors, chain extenders, metal deactivators Residual polymerization catalyst inactivators, transesterification inhibitors, antibacterial / antifungal agents, antistatic agents, lubricants, flame retardants, fillers, matting agents, and the like. Further, a small amount of other general-purpose resins may be included.

(Thickness of layer A 10)
The thickness of the A layer 10 is preferably 5 μm to 100 μm, more preferably 10 μm to 75 μm, and particularly preferably 25 μm to 60 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 and the C layer 30 arranged as the lower layer, but if the thickness is thinner than this, There is a risk of emboss heat resistance. In addition, even when the film is formed in a state of being integrated by the coextrusion film forming method with the configuration of the A layer 10 and the B layer 20, or the A layer 10 and the C layer 30, the A layer in the width direction of the laminated sheet. The thickness distribution of 10 tends to be unstable. On the contrary, even if the thickness of the A layer 10 is increased more than this, the effect of improving the embossing heat resistance is saturated, and at the same time, the thickness of the A layer composed of a resin having a relatively high raw material price is increased. This is also not preferable.
Further, when the laminated sheet 100 is used for coating a resin-coated metal plate, the total thickness of the laminated sheet is restricted from the viewpoint of secondary workability such as bending workability, and the excessively thick A layer 10 is There is a possibility of causing a failure to express functions that other layers of the laminated sheet should take on.

<B layer 20>
The function required for the B layer 20 is that the laminated sheet is made of various thermoplastic resin sheets, wood boards, inorganic fiber boards, thermoplastic resin boards, thermosetting resin boards, metal plates, as compared with the sheets composed of a single A layer. In the case of obtaining a laminated sheet having a printed pattern E as in the fifth aspect of the present invention, the surface of the C layer 30 separately formed and provided with the printed pattern E It is to make the heat-fusible property of this. In addition, by making a layer that is substantially transparent in combination with the A layer 10, these existing colored designs and prints can be applied to the surface of a substrate such as a sheet or plate that already has design properties by coloring or printing. It is to give the surface an uneven design by emboss transfer without deteriorating the design of the design. From this point, the transparency should not change due to the progress of crystallization over time. In addition, the number of man-hours for layer integration in the subsequent process is not required, so that efficient production is possible and manufacturing cost benefits can be obtained. It is obtained in a state of being laminated and integrated by an extrusion film forming method.

Further, the B layer 20 is formed of a resin raw material that can be obtained at a lower price than a substantially amorphous aromatic polyester resin having a glass transition temperature of 100 ° C. or higher used for the A layer 10. By this, the merit of raw material cost is acquired compared with the case where the total thickness of a resin sheet is comprised with the resin composition of A layer 10. Further, like the A layer 10, it is a layer that can be deformed by pressing with an embossing plate. An embossed pattern transfer having a depth corresponding to the total thickness of the layer 10 and the B layer 20 is obtained.

(B-layer 20 polyester resin substantially amorphous)
For the above reasons, the resin component used for the B layer 20 is preferably composed of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. as a main component. Here, “mainly” means that at least 60% by mass, preferably 65% by mass or more, and more preferably 70% by mass or more, based on the mass (100% by mass) of the entire resin component of the B layer 20. .
The substantially non-crystalline (including low crystalline) polyester-based resin forming the B layer 20 includes a clear crystallization peak at the time of temperature rise, as measured by a differential scanning calorimeter (DSC), and / Or not only a polyester-based resin that does not exhibit a crystalline melting peak but also a crystalline one that has crystallinity but has a slow crystallization rate (120 using a differential scanning calorimeter (DSC) by the “Perkin Elmer method”). ½ crystallization time measured by holding at ℃ is 200 seconds or more), in contact with a casting roll and an opposing silicone rubber roll at the time of sheet formation by extrusion film forming method, or using an embossing device When heated by sheet heating when embossing is performed or when the temperature rises in a warehouse during sheet storage, the metal plate heated during lamination with the metal plate Polyester resin that does not become highly crystalline due to the heat of the crystal, and a crystalline scanning calorimeter (DSC) that has crystallinity, the heat of crystal melting (ΔHm) observed at elevated temperature is as low as 10 J / g or less. Some can be used.
When the polyester-based resin that is the main component of the B layer 20 has remarkable crystallinity, it may not be able to obtain a function as a layer that is crystallized when embossed design is applied by an embossing device and is deformed by pressing with an embossed plate. There is. In addition, the function of a layer for obtaining easy adhesion is lost when heat-sealing and laminating to various base materials.
Moreover, it is preferable that the substantially amorphous polyester-type resin which comprises the main component of the resin component of B layer 20 has a glass transition temperature of 70 degreeC or more. When the glass transition temperature is lower than that, even when the thickness of the B layer is relatively thin, when the resin-coated metal plate laminated with the laminated sheet is immersed in boiling water, the appearance accompanying the softening of the B layer 20 There is a risk of deterioration.

  The substantially amorphous polyester-based resin constituting the B layer 20 is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 20 mol% to 80 mol% of 1,4-cyclohexanedimethanol and A copolymer polyester resin mainly composed of 20 mol% to 80 mol% of ethylene glycol as a diol component can be preferably used.

Here, the “main component” of the dicarboxylic acid component is based on the total amount of the dicarboxylic acid component (100 mol%), and terephthalic acid or dimethyl terephthalic acid is at least 70 mol%, preferably 90 mol% or more. Preferably it means 98 mol% or more.
The “main component” of the diol component is preferably 80 mol% or more, more preferably 90 mol% or more of 1,4-cyclohexanedimethanol and ethylene glycol based on the total amount of the diol component (100 mol%). More preferably, it is said to contain 95 mol% or more.

When the copolymerization ratio of 1,4-cyclohexanedimethanol is less than the above range, the characteristics as a crystalline resin become remarkable, which is not preferable. 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, which is not preferable.

  As the copolyester resin in the above preferred composition range, so-called PETG resin can be preferably used from the viewpoint of cost reduction because of the stable supply of raw materials and the large production amount. Examples of the PETG resin include “Easter PETG • 6763” manufactured by Eastman Chemical Company. "Easter PETG · 6763" has terephthalic acid as the main component of the dicarboxylic acid component, about 31 mol% of the diol component is 1,4-cyclohexanedimethanol, and the main component of the remaining diol component is ethylene glycol. It is a copolyester resin containing diethylene glycol, and is an amorphous polyester resin in which no crystallization behavior is observed by measurement with a differential scanning calorimeter (DSC).

  In addition, it must be handled as a crystalline resin under specific heating and kneading conditions such as kneading with a hot roll or calendering, but it is handled in the same way as an amorphous polyester resin in ordinary extrusion filming. Eastman Chemical Company's Easter PCTG 5445 "and Eastman Chemical Company's Easter PCTG 24635 are also copolyester resins within the above composition range. These are mainly composed of terephthalic acid as the main component of the dicarboxylic acid component, about 60 mol% of the diol component is 1,4-cyclohexanedimethanol, the main component of the remaining diol component is ethylene glycol, and contains several mol% of diethylene glycol. Polymerized polyester resin.

  However, the present invention is not limited thereto, and a PET-based resin copolymerized with neopentyl glycol as a diol component does not exhibit crystallinity (for example, “COSMOSTER SI-173” manufactured by Toyobo Co., Ltd.) Copolymers such as those with low crystallinity, polyethylene terephthalate resin copolymerized with isophthalic acid as the dicarboxylic acid component, polybutylene terephthalate resin copolymerized with isophthalic acid, those that do not exhibit crystallinity, and those with low crystallinity Copolyester resins having a structure in which crystallization is inhibited by a component can also be used as the main component of the B layer 20.

(B layer 20 thickness)
The thickness of the B layer 20 is preferably 60 μm or less, and more preferably 50 μm or less. Moreover, it is preferable that it is 3 micrometers or more, and it is more preferable that it is 5 micrometers or more.
When the thickness of the B layer 20 is too thick, when the laminated sheet 100 is used for coating a resin-coated metal plate, the total thickness of the laminated sheet is restricted from the viewpoint of secondary workability such as bending workability, There is a possibility that the excessively thick B layer 20 may cause a malfunction in the functions that other layers of the laminated sheet should take on. In addition, when the thickness of the B layer 20 is excessively thin, there is a possibility that the function as a layer that undergoes deformation by pressing with the embossed plate together with the A layer may not be obtained when the embossed design is applied. There is a possibility that the function of a layer for obtaining easy adhesion at the time of heat fusion lamination may not be sufficiently exhibited.

  Further, since the B layer 20 is mainly composed of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C., a resin coating in which a laminated sheet having an excessively thick B layer 20 is coated. The metal plate has poor boiling water immersion resistance and may cause significant fluid deformation.

(Additive of B layer 20)
An appropriate amount of various additives that can be used for the A layer 10 may be added to the B layer 20.

<C layer 30>
The purpose of providing the C layer 30 in the laminated sheet 100 of the present invention is to provide a colored design by adding a colorant, and various thermoplastic resin sheets, a wooden board, an inorganic fiber board, a thermoplastic resin board as a base material, It is to ensure the visual concealment effect of a thermosetting resin plate, a metal plate or the like. Further, in the case of the configuration having the printed pattern E as in the fifth aspect of the present invention, the color development of the printed pattern E is improved by coloring the C layer 30 corresponding to the base layer of the printed pattern E. Things are also included. Furthermore, depending on the resin composition of the C layer 30, in the fourth aspect of the present invention, the thickness of the A layer 10 and the thickness of the C layer 30 are combined, and in the fifth aspect of the present invention, the A layer 10 In addition to the thickness of the B layer 20 and the thickness of the B layer 20, the thickness of the C layer 30 can be combined to form a layer that can be deformed by pressing with an embossing plate. Transfer of embossed pattern with depth corresponding to the total thickness of A layer 10 and C layer 30 or A layer 10 and B layer 20 and C layer 30, while the thickness of A layer 10 having a high unit price is relatively thin It is to make it a layer that can get.

Further, as in the case of the B layer 20, the glass transition temperature used for the A layer 10 can be obtained at a lower price than a substantially amorphous aromatic polyester resin having a glass transition temperature of 100 ° C. or higher. By forming the C layer 30 with the resin raw material, the merit of the raw material cost is obtained as compared with the case where the entire thickness of the resin sheet is configured with the resin composition of the A layer.

  Therefore, the resin component of the C layer 30 should not be made of a resin that requires a high temperature such that the pigment component is thermally deteriorated during melt kneading and film formation. Moreover, it is preferable that toning to various colors can be easily performed. In addition, since the C layer 30 is also a layer that ensures visual concealment of the base by adding a color pigment, the C layer 30 needs to be a relatively thick layer, but a laminated sheet is laminated. When the resin-coated metal plate is used for a unit bath application, it is necessary to make the layer resistant to boiling water immersion.

  Therefore, in the present invention, the C layer 30 is composed of 20% by mass to 70% by mass of a PBT resin having a melting point of 210 ° C. to 230 ° C. and a substantially amorphous polyester having a glass transition temperature of less than 100 ° C. A resin layer composed mainly of a resin composition consisting of 30% by mass to 80% by mass of a resin and having a thickness of 200 μm or less to which a colorant is added.

When the addition ratio of the PBT resin is higher than this, there is no problem with the boiling water immersion resistance of the C layer 30 due to its crystallinity, but the master batch of the colorant having the PBT resin as the base resin is However, compared to those using a substantially amorphous polyester-based resin as a base resin, the types are poor and a problem arises in that a colored design can be freely imparted. In addition, as in the third invention, although there is no problem when embossing is given to the laminated sheet composed of the A layer 10 and the C layer 30 by the extrusion casting embossing method, as in the fourth invention and the fifth invention. When an embossing apparatus is used to provide embossing with an off-line embossing device, the C layer 30 having a high PBT resin addition ratio and therefore high crystallinity is deformed by pressing with an embossing plate roll. It cannot be given the function.
On the contrary, when the addition ratio of the PBT resin is less than this, when the C layer 30 has a thickness that can sufficiently provide the visual concealing effect of the base, the metal plate coated with the laminated sheet including the C layer 30 is boiled. When subjected to water immersion, there is a risk of poor appearance due to a decrease in the elastic modulus of the C layer 30.
The addition ratio of the PBT resin to the C layer 30 is more preferably 25% by mass to 60% by mass. Moreover, when embossing is provided by the embossing apparatus by providing the D layer 40 as in the fourth and fifth inventions, the C layer 30 is also provided with a function as a layer that is deformed by pressing with the embossing plate. The addition ratio of the PBT resin is particularly preferably 45% by mass or less.

  As a substantially amorphous aromatic polyester resin having a glass transition temperature of less than 100 ° C., which is one of the main components of the resin composition of the C layer 30, the same ones that can be used for the B layer are used. Although terephthalic acid or its derivative is the main component of the dicarboxylic acid component, 20 mol% to 40 mol% of 1.4-cyclohexanedimethanol and 80 mol% or less and 60 mol% or more of ethylene glycol are diols. It is particularly preferable that it is an amorphous aromatic polyester resin mainly composed of components.

The so-called PETG resin in the composition range is preferable from the viewpoint of cost reduction because of a stable supply of raw materials and a large amount of production, and a master of a colorant using the PETG resin as a base resin. Because the batch is abundantly marketed, it is based on the convenience of increasing the degree of freedom in applying the color design of the C layer 30.
In addition, when PETG resin is used for the resin composition that is the main component of the B layer 20, the use of the same raw material as one of the constituent components of the C layer 30 makes the raw material purchase, the raw material storage, the raw material charging equipment, etc. common. The advantage that can be achieved.

As the PBT resin having a melting point of 210 ° C. to 230 ° C., which is another main component of the resin composition of the C layer 30, the same ones that can be used for the D layer 40 described later can be used. When the same raw material as that of the layer 40 is used, there is an advantage that the raw material purchase, the raw material storage, the raw material charging equipment, etc. can be shared.

(Colored pigment of C layer 30)
The C layer 30 is a layer mainly responsible for the visual hiding effect of the colored design and the base, and is added with a colorant. The colorant used for coloring the C layer 30 may be one generally used for coloring a polyester resin, and the addition amount thereof may be an amount generally added for the above purpose. For example, in the case of a light color, it is a white-colored pigment, and based on a titanium oxide pigment having a high visible light hiding effect, a color adjustment is performed with a chromatic inorganic or organic pigment or dye. be able to. Moreover, as addition amount of a coloring agent, it is preferable to set it as 2-50 mass parts on the basis (100 mass parts) of the whole quantity of the resin component which comprises the B layer 20, for example.
As described above, there are abundantly commercially available pigment-kneaded pellets whose dispersibility is improved by pre-kneading, such as a color master batch using PET-G as a base resin. Thus, the C layer 30 can be easily made into a colored layer. In addition to the pigments, the C layer 30 may 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.

Furthermore, after the C layer 30 is formed into a two-layer structure by coextrusion film formation, a layer located on the metal plate side is added with a coloring design and a concealing pigment for obtaining a visual concealing effect on the base. The layers located on the surface side include pearl mica pigments with appropriate particle sizes, various metallic powders such as aluminum powder, silver powder, and gold powder, and so-called glitter pigments such as glass flakes, surface-modified glass flakes, and ceramic powders. It may be added to give a metallic design feeling, or a design in which particles are dispersed in a dot shape to express glitter.
Among these luster pigments, pearl mica pigment has a surface coating when added to a blend composition containing an aromatic polycarbonate resin that requires melting and kneading at a high temperature, such as the resin composition of layer A 10. When the thermal catalytic action of the titanium oxide used in the present invention becomes obvious, the resin composition is deteriorated such as yellowing and streaking, resulting in poor appearance. For example, since it can be formed into a sheet by melting and kneading at a relatively low temperature, the lustrous design feeling using the pearl mica pigment can be obtained without any problem.

(Thickness of C layer 30)
The thickness of the C layer 30 is preferably 200 μm or less, and more preferably 40 μm or more to 150 μm. More preferably, it is 75 micrometers-120 micrometers. If the thickness is too thin, it will be difficult to develop the coloring design required for the C layer 30 and the visual hiding effect of the underlying metal, and conversely, these functions will be saturated even if the thickness is excessively increased. When the laminated sheet 100 is used for coating a resin-coated metal plate, the total thickness of the laminated sheet is restricted from the viewpoint of secondary workability such as bending workability, and the excessively thick C layer 30 is laminated. There is a possibility of causing a failure in the expression of functions to be handled by other layers of the sheet.

  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 case of an embossed design sheet-coated metal plate for interior building materials use, JIS K5400 7.2 “General test method for paints” -It is preferable that the concealment rate measured based on "concealment rate" is 0.97 or more by the structure of a lamination sheet.

  When the concealment rate is lower than this, the color of the base material, such as a metal plate, is reflected in the color of the surface of the laminated sheet 100, and when the color changes due to the difference in the treatment of the metal plate surface, etc. Since the color observed from the sheet surface also appears to change, it is not preferable. However, in applications where color change due to this reason does not pose a particular problem, the concealment rate need not be 0.97 or more.

<D layer 40>
Even when the D layer 40 is heated to the same temperature as that of the conventional soft PVC when the laminated sheet 100 is passed through an embossing apparatus, the D layer 40 adheres to the heated metal roll, shrinks in width, It has the role of preventing entry and melt fracture. Therefore, when the embossed design is transferred to the laminated sheet of the present invention with an embossing apparatus, the sheet should not exhibit adhesiveness to metal at a temperature up to about 150 ° C., which is heated by a heating roll. The resin composition should not have an elastic modulus that is remarkably lowered 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. On the other hand, when laminating to the metal plate 60, it is necessary to obtain a strong adhesion to the metal plate heated to the same temperature as the conventional soft PVC, so that the state heated to about 235 ° C. However, it should not maintain a high elastic modulus, and therefore should not be a crystallized crystalline polyester resin having a melting point exceeding 235 ° C.

(PBT resin of D layer 40)
For the above purpose, the D layer 40 of the present invention contains a predetermined amount of a PBT resin resin having a melting point of 215 ° C. or higher and 235 ° C. or lower.

  The melting point of 215 ° C. or higher is required when the embossing design is transferred to a conventional soft PVC sheet by an embossing apparatus, while the temperature at which the sheet is heated by a heater without a support is about 160 ° C. to 190 ° C. This is because when a PBT resin having a melting point of less than 215 ° C. is used as the resin component of the D layer 40, it is difficult to obtain sufficient tension at a heating temperature of 160 ° C. to 190 ° C. The upper limit of the melting point is 235 ° C., which is made of a polyester resin composition having a higher melting point. In the D layer 40 in a crystallized state, a sheet of conventional soft PVC is laminated to the metal plate 60. This is because it is difficult to obtain a strong adhesive force with the metal plate 60 at a temperature up to 235 ° C., which is the upper limit of the heating temperature of the normal metal plate, as in the case of performing.

  The reason why the D layer 40 is a layer containing a predetermined amount of the PBT resin is not only in the preferable melting point range, but also in the blend composition containing the predetermined amount of the PBT resin. Since the speed is relatively high, D layer having high crystallinity in the film forming process without providing a special curing process or the like between the film forming process and the embossing design applying process in the embossing apparatus. This is because it is easy to obtain 40, that is, it is easy to obtain non-adhesiveness to the heated metal part in the embossing step and rupture resistance during heating.

  Also in the polyethylene terephthalate (PET) resin, a resin having a melting point in the above range can be obtained by substituting a part of terephthalic acid which is a dicarboxylic acid component with isophthalic acid. However, the PET resin in this case has a very low crystallization rate, and it is difficult to obtain a sufficiently crystallized D layer 40 with a normal extrusion film forming line, and it is necessary to provide a curing step or the like separately. For this reason, it is not preferable to use a PET-based resin with only the melting point range for the D layer 40.

  Another reason for using the PBT resin is that better processability can be obtained even in a crystallized state as compared with the PET resin. Accordingly, even a resin-coated metal plate coated with a laminated sheet 100 having a non-oriented and crystallized D layer 40 is bent as compared with a non-oriented crystallized PET resin. Secondary workability such as workability can be improved.

  The content ratio of the PBT resin in the D layer 40 is preferably 75% by mass or more based on the mass of the entire resin component in the D layer 40 (100% by mass). 80% by mass or more is more preferable. When the amount of PBT is less than this, the crystallization speed of the blend composition of the D layer 40 becomes slow, so that it exhibits non-adhesiveness to the heated metal part of the embossing apparatus and has sufficient heating tension. In order to crystallize to the extent that it can be obtained, a special curing process or the like is required, and even if a sheet in a crystallized state is obtained, it is difficult to obtain a preferable tension during heating. .

  Further, the upper limit of the content ratio of the PBT resin is preferably 95% by mass or less, and more preferably 90% by mass or less. When the content of the PBT resin is larger than this, the crystallinity of the D layer 40 on the adhesive lamination surface side when the laminated sheet 100 is laminated on the metal plate 60 becomes too high, and the metal plate is not used under conventional heating conditions. This is because it may be difficult to obtain the adhesion strength with 60. In addition, when the D layer 40 is obtained by two-layer coextrusion with the C layer 30 or by a three-layer coextrusion film forming method with the A layer 10 and the C layer 30, the warp of the laminated sheet after film formation becomes significant. This is because there is a possibility that the handling may be hindered.

  As the PBT resin having a melting point in the range of 215 ° C. to 235 ° C., the same PBT resin that can be used for the C layer 30 can be used, and the acid component is terephthalic acid or dimethyl terephthalic acid. The use of a homo-PBT resin obtained by polycondensing each single component of diol component with 1,4-butanediol (an unintended copolymer component may be included) is cost and stable. It is particularly preferable from the viewpoint of supply ability and a high crystallization speed. The melting point of the homo PBT resin measured by a differential scanning calorimeter (DSC) is about 225 ° C., and has the highest melting point among PBT resins obtained as commercially available raw materials.

  As the homo-PBT resin, various commercially available materials such as “Novaduran 5020H” manufactured by Mitsubishi Engineering Plastics, “Torcon 1200S” manufactured by Toray Industries, and “Duranex 600FP” manufactured by Wintech Polymer can be used. .

(Resin component other than PBT resin of D layer 40)
As a resin component other than the PBT resin added to the D layer 40, a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C. is preferably used. As such a substantially amorphous polyester-based resin, the same resin as the main component of the B layer 20 described above can be used. For example, “Easter PETG6763” manufactured by Eastman Chemical Company. And “Easter PCTG5445”. The reason why the amorphous polyester resin is preferable is that the addition amount is small. For example, when a polyester resin having high crystallinity such as a homo-PET resin is used, the crystallization rate is low, but the crystallization proceeds with time. As the process proceeds, the crystal phase of the PET resin, which is inferior to the processability of the crystal phase of the PBT resin, adversely affects the processability of the D layer 40 over time. As a result, the laminated sheet and the metal plate coated therewith This is because the workability of 300 may be reduced. However, since the compounding amount of resin components other than PBT-based resins is limited to a relatively small amount, if no special consideration is required for deterioration of workability due to crystallization, homo-PET resin or the like is used. It may be used.

(Thickness of D layer 40)
The D layer 40 preferably has a thickness of 5 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more. When the thickness is thinner than this, the function as a tension applying layer in the embossing apparatus tends to be insufficient. Further, the upper limit of the thickness is preferably 100 μm or less, and more preferably 60 μm or less. Even if it is thicker than this, the upper limit of the total thickness of the laminated sheet is limited in order to saturate the function that the D layer 40 should take on and to ensure secondary workability such as bending as a resin-coated metal plate. For this reason, there is a possibility that the function that other layers should be responsible for may not be developed.

(Additive of D layer 40)
Although pigments for coloring may be added to the D layer 40, since the C layer 30 exists as a target layer for expressing the coloring design, only the coloring of the C layer 30 provides a visual concealment effect on the foundation. It is preferable to add a pigment as a supplement when, for example, cannot be obtained.

  In addition, an appropriate amount of lubricant may be added in order to further strengthen the non-adhesiveness with the heated metal, which is one of the purposes to which the D layer 40 is imparted. As the lubricant, those commonly used for addition to a polyester resin can be used. For example, “LICOWAX (registered trademark) OP” (manufactured by Clariant Japan), which is a montanic acid-based lubricant, can be mentioned. it can. The addition amount of the lubricant may be a general amount of about 0.2% by mass or more and 3% by mass or less based on the total resin amount of the D layer 40 (100% by mass).

Further, in order to make the tension at the time of heating the laminated sheet 100 in the embossing apparatus stronger, the D layer 40 has a linear ultrahigh molecular weight acrylic resin (for example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., Ltd. ) P-531 "and the like, and processing aids such as polytetrafluoroethylene that has been subjected to an easy dispersion treatment that expands into a fibril form (for example," METABRENE (registered trademark) A-3000 manufactured by Mitsubishi Rayon Co., Ltd.). In this case, the addition amount is generally 0.2% by mass or more and 3% by mass or less based on the total resin amount of the D layer 40 (100% by mass). The right amount.

  Furthermore, an organic or inorganic crystal nucleating agent is added in order to easily give the D layer 40 the crystallinity necessary to obtain non-adhesiveness and melt fracture resistance in an embossing apparatus. Thus, the crystallization speed 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.

<Print pattern E50>
In the laminated sheet of the present invention, the A layer 10 and the B layer 20 are substantially transparent layers,
Since the C layer 30 that is a colored layer is provided on the substrate side of those layers, between the A layer 10 and the C layer 30, or an integrated sheet of the A layer 10 and the B layer 20, A print pattern E50 may be provided between the C layer 30 and the print design. The printed pattern E50 is applied by a known method such as gravure printing, offset printing, planographic screen printing, rotary screen printing, printing with an inkjet printer, flexographic printing, letterpress printing, electrostatic printing, and the like. The pattern is arbitrary, and for example, a pattern imitating a natural material such as a stone pattern or a grain pattern, a geometric pattern, an abstract pattern, or the like can be given. The printing may be partial printing or full printing, and both partial printing and full printing may be performed.

  As the resin binder type of the printing ink, those usually used for printing on a sheet-like material made of a polyester resin can be used without limitation. Examples thereof include acrylic, acrylic / urethane, polyester, polyester / urethane, alkyd resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / urethane, and the like. By appropriately selecting the binder type, even in the configuration in which the printed pattern E50 is interposed between the B layer 20 and the C layer 30, the lamination integration can be made to be heat fusion lamination. Or at the time of provision of printing pattern E50, a heat adhesion application layer can be provided simultaneously, and heat fusion lamination nature can also be given.

Even in such a case, the transparent layer has a B layer 20 made of a resin having a lower glass transition temperature than the case of a single A layer 10 layer. There is little possibility of causing a problem, or even when a laminated sheet is prepared by a procedure of performing heat fusion lamination after embossing is applied to the surface of the A layer 10, it is possible to prevent the embossed return of the A layer 10 from being caused by heating. To preferred.
The printed pattern E50 may be formed by printing on the surface of the C layer 30 to be laminated with the B layer 20, or may be printed on the surface of the B layer 20 to be laminated with the C layer 30. May be formed.

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

  In order to produce the laminated sheet 100 of the present invention, each layer is composed of a resin composition having heat-fusibility with each other. Therefore, after each layer is formed alone, it is laminated and integrated in a subsequent process. 100, but in the case of a structure consisting of two layers of the A layer 10 and the B layer 20, a coextrusion film forming method using two extruders and a feed block and a single layer T die, or 2 It is most efficient and preferable to form two layers integrally by a coextrusion film forming method using a single extruder and a multi-manifold type T die. The same applies to the case of two layers of the A layer 10 and the C layer 30. In the configuration having no D layer 40, it is difficult to reheat the laminated sheet and emboss it with an off-line embossing apparatus. Therefore, a casting roll (take-off roll) at the time of extrusion film formation is usually used. It is preferable to emboss the surface of the A layer 10 by the so-called extrusion cast embossing method as an embossing roll instead of the mirror surface roll.

On the other hand, in the case of the configuration composed of three layers of the A layer 10, the C layer 30, and the D layer 40, it is preferable to form the three layers integrally using the three extruders and the necessary co-extrusion equipment. In the case of this configuration, since it has the D layer 40 that imparts suitability to the embossing apparatus, the casting roll of the extruder is a normal mirror surface roll or a shallow pear texture for improving the sheet winding property It is preferable to perform embossing with an embossing apparatus that is off-line from the extrusion film forming equipment using a roll that has been embossed. In this configuration, the embossed design is imparted at the same temperature conditions and processing speed as that of the conventional soft PVC sheet by various embossing apparatuses generally used for imparting the embossed design to the soft PVC sheet. be able to. In general, the embossing device incorporates a design that allows easy replacement and removal of the embossing plate roll, and the diameter of the embossing plate roll is made smaller than the casting roll of the extrusion film forming equipment. In addition, by preparing various types of embossed plate rolls, it is possible to easily and economically change the embossed pattern, so that it is possible to obtain a merit in terms of compatibility with small lots. According to this procedure, the sheet heating temperature in the embossing apparatus is about 160 ° C. to 190 ° C. even when embossing such as shallow pear texture applied by the casting roll of the extrusion equipment is applied to the surface of the A layer 10. Since it will exceed the glass transition temperature of the resin composition of the A layer 10 and will continue to be pressed with an embossing roll having a new embossing design, the embossing of the satin applied at that point disappears. It will be a thing.

In the case of a structure having a printed pattern E50 between the B layer 20 and the C layer 30, the four extruders and the required layers are formed. Using a co-extrusion facility, a sheet in which the two layers of the A layer 10 and the B layer 20 are integrally formed, and a sheet in which the two layers of the C layer 30 and the D layer 40 are integrally formed by co-extrusion are produced. Then, after giving the printed pattern E50 to the surface of the C layer 30, the B layer 20 side surface and the C layer 30 side surface of these two sets of two-layer sheets are integrated by heat fusion lamination with the printed pattern E50 interposed therebetween. It is preferable to follow the procedure for embossing the surface of the A layer 10 after the formation.
Even in this configuration, the presence of the D layer 40 has suitability for the embossing apparatus, and in the heating roll portion used for sheet heating in the embossing apparatus, the A layer 10 and B Since the integrated sheet of the layer 20 and the integrated sheet of the C layer 30 having the printed pattern E50 on the surface and the integrated layer of the D layer 40 can be integrated by heat fusion lamination, the manufacturing cost is not increased without increasing the number of processes. While securing the merit, it is possible to obtain the merit of small lot compatibility for the type of embossed design.

  In FIG. 2, an example of the embossing apparatus 300 generally used in order to provide an embossed pattern to a flexible PVC sheet is shown. The illustrated embossing apparatus 300 includes a heating roll 310, a take-off roll 320, an infrared heater 330, a nip roll 340, an embossing roll 350, and a cooling roll 360. In this embossing apparatus 300, a metal roll-shaped embossing roll 350 is used as the embossing plate. However, the shape of the embossing plate is not particularly limited as long as it is a plate on which an embossed design is formed. Further, it may be a roll shape that continuously embosses, a belt shape, a long sheet shape, or the like.

  In the embossing apparatus 300 shown in FIG. 2, a sheet composed of two layers of an A layer 10 and a B layer 20 formed by a two-layer coextrusion method, and two layers of a C layer 30 and a D layer 40 subjected to a printed pattern E50. The co-extruded sheet is supplied, and after heat fusion lamination with the heating roll 310 of the embossing apparatus 300, embossing is performed.

  However, the lamination and integration of each layer is not necessarily based on the co-extrusion film forming method and the heat fusion lamination method, but the lamination by applying and curing a thermosetting adhesive such as a dry lamination adhesive or an ultraviolet curable adhesive. Alternatively, it may be based on a method such as heat fusion lamination by sandwiching a hot melt film, but since the purpose of the present invention is to obtain a highly-designed laminated sheet at a low cost, these man-hours and materials are increased. The accompanying lamination integration method is not necessarily a good method.

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

  The thickness of the entire laminated sheet 100 of the present invention is 55 μm to 300 μm, and preferably in the range of 80 μm to 250 μm. When the thickness of the laminated sheet 100 is too thin, it becomes difficult to transfer a relatively deep embossed pattern, and the thickness of the C layer 30 is restricted in the configuration having the C layer 30 that is a colored layer. As a result, it is difficult to ensure visual concealment. When the thickness of the laminated sheet 100 is too thick, when a laminated metal sheet is used to form a resin-coated metal plate, the use of a molding die that has been conventionally used for molding such as bending of a soft PVC resin-coated metal plate May cause problems in secondary workability, and may cause abnormalities such as scraping due to strong friction with the mold or cracking in the resin layer in the bent portion.

<Embossed design sheet coated metal plate 200>
FIG. 1E shows a laminated sheet-covered metal plate 200A having an embossed design in which the D layer 40 side surface of the embossed design sheet 100C shown in FIG. 1C is laminated on the metal plate 60 via an adhesive 70. FIG. 1 (f) shows a laminated sheet-covered metal plate 200B having an embossed design and a printed pattern design obtained by laminating an embossed design sheet 100D on the metal plate 60 in the same manner.

  As the metal plate 60 used for the embossed design sheet-coated metal plate 200 of the present invention, hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, tin plated steel plate, aluminum / zinc alloy plated steel plate, high aluminum Various steel plates such as zinc alloy plated steel plate, aluminum / magnesium / zinc alloy plated steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, aluminum alloy clad plate, titanium alloy plate, nickel alloy plate, magnesium alloy A board etc. can be used and you may use these, after giving a normal chemical conversion treatment. The thickness of the metal plate 60 varies depending on the application of the resin-coated metal plate and the like, but can be selected in the range of 0.1 mm to 10 mm. As a resin-coated metal plate used for elevator applications, it is common to use a sheet having a thickness of about 1.0 mm to 1.6 mm such as a hot dip galvanized steel sheet.

In order to obtain the embossed design sheet-covered metal plate 200, the method of laminating the laminated sheet to the metal plate is preferably based on the conventional method from the viewpoint that existing equipment can be used. That is,
Using commonly used coating equipment such as a reverse coater or kiss coater on the metal plate 60, the adhesive film thickness after drying becomes about 0.5 μm to 10 μm on the metal surface on which the embossed design sheet is bonded. After applying the thermosetting adhesive as described above, the surface of the metal plate 60 is kept at a temperature of about 225 ° C. or higher and 240 ° C. or lower by drying the solvent on the coated surface and baking with an infrared heater and / or a hot air heating furnace. However, immediately using a roll laminator, the embossed design sheet 100 is coated so that the surface of the embossed design sheet 100 opposite to the side of the layer A 10 becomes an adhesive surface, and then cooled by water injection or water injection by charging into the water tank. A method is mentioned. In general, the surface temperature of the metal plate when the soft PVC sheet is coated is about 220 ° C. or higher and 240 ° C. or lower. Examples of the thermosetting adhesive 70 include commonly used thermosetting adhesives such as an acrylic adhesive, an epoxy adhesive, a urethane adhesive, and a polyester adhesive.

The embossed design sheet-covered metal plate 200 of the present invention can have various designs by combining the design with the printed pattern E40 and the embossed design. Furthermore, since it has good workability and surface hardness, it can be widely applied to various applications. Further, even when laminated on a relatively thick metal plate, it has good embossing heat resistance that does not cause emboss return, and alkali resistance does not deteriorate. In addition, appearance abnormality does not occur even when subjected to a boiling water immersion test. Specifically, elevator interior materials, unit bath wall materials, unit bath materials such as unit bath ceiling materials, closet door materials, partition materials, panel interior materials such as panel materials, steel furniture members, AV equipment, air conditioner covers It can use suitably as household appliances housing | casing members, such as.

  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.

<Examples 1-18, Comparative Examples 1-11>
[Production of laminated sheet]
The coextruded sheets of the A layer and the C layer used in Examples 1 to 18 and Comparative Examples 1 to 11 are two co-directional twin-screw kneading extruders (manufactured by JSW Co., Ltd.) having a vent device at two locations with a cylinder diameter of 65 mm. "TEX-65"), and through the necessary connecting conduits and distribution blocks, the resin flowed out of the T die by a co-extrusion method using a two-layer multi-manifold lip width 1400 mm T-die A non-oriented laminated sheet having a two-layer structure of 1,200 mm in width composed of an A layer and a C layer was prepared by a general method of pulling up the film with a casting roll (take-off roll).
When using a blend composition as the resin component of the A layer and the C layer, rather than preparing a pre-kneaded blend master batch in advance, each raw material pellet is mixed with the mass of the composition ratio and extruded from a single quantitative supply feeder. I put it directly into the machine. However, the resin composition and the thickness of the C layer are the same for Examples 1 to 18 and Comparative Examples 1 to 11, and the Easter PETG · 6763 is 70 based on the total resin component of the C layer (100% by mass). 25% by weight of a light blue pigment composed mainly of a titanium oxide-based white pigment and an organic blue-based pigment in combination (with the total amount of the resin component in the C layer) consisting of 30% by weight of Novaturan 5020H It is colored by adding (value of 100 parts by mass). The thickness of the C layer is 100 μm. As for the colorant, a commercially available pigment master batch using a PETG resin (Easter 6763) as a base resin and having a pigment component concentration of 50% by mass (resin component amount 50% by mass) is usually used so that the required pigment concentration is obtained. It is used after being diluted with PETG raw material pellets.

  The set temperature of the extruder on the A layer side is 250 ° C. on the feed side and 270 ° C. on the base side, and the set temperature of the extruder on the C layer side is 220 ° C. on the feed side and 250 ° C. on the base side. Distribution block, multi-manifold type T-die temperature setting is 270 ° C when the resin composition of the A layer side is composed of aromatic polycarbonate resin only, when the blending ratio of amorphous aromatic polyester resin is increased Fine adjustment was appropriately performed according to the type of resin, approximately 260 ° C. Similarly, the temperature setting in the width direction of the T die is finely adjusted as appropriate.

 The temperature of the casting roll was adjusted by circulating the heat transfer oil, and the roll surface temperature was set based on the glass transition temperature of −15 ° C. of the resin composition of the A layer. The surface of the casting roll is engraved with embossing to give the irregularities of the abstract pattern based on a stone pattern with a center line average roughness (Ra) of 9 μm and a maximum height (Ry) of 54 μm. A metal roll having a surface plating treatment with a diameter of 400 mm. The molten resin flowing down from the T-die is extruded so that the side forming the A layer becomes the casting roll side, and the surface temperature of about 40 ° C. is obtained by circulating water on the side forming the C layer. The silicone rubber touch roll adjusted to be in contact with each other. The sheet flow speed (film forming speed) at the time of leaving the casting roll was 30 m / min.

  The resin compositions and layer thicknesses used in the A layers of Examples 1 to 18 and Comparative Examples 1 to 11 are shown in Table 1. Moreover, in Table 1-1 and Table 1-2, the glass transition temperature of the resin composition of each A layer of an Example and a comparative example, and the tensile method storage elastic modulus (E ') in 120 degreeC are shown. Described. Regarding the measurement sample of the glass transition temperature, it is measured by using a microtome cut out from the A layer side of the coextruded sheet of the A layer and the C layer. The measurement itself is performed by a differential scanning calorimeter in the same manner as the measurement of the glass transition temperature of the raw material resin, which will be described later. For the tensile storage elastic modulus, a single-layer sheet having the same resin composition as the A layer is 30 mm in diameter. Using a single-screw extruder and a single-layer die having a width of 300 mm, a film having a thickness of 100 μm is formed as a specimen. In Tables 1-3 and 1-4, a table summarizing the layer configurations of Examples and Comparative Examples is shown.

ここで、貯蔵弾性率の項目の「１．３Ｅ＋０８」は、１．３×１０^８（１．３掛ける１０の８乗）を示す。以下の表に関しても同様。

Here, “1.3E + 08” of the storage elastic modulus item indicates 1.3 × 10 ⁸ (1.3 times 10 to the 8th power). The same applies to the following table.

<Examples 19 to 26, Reference Examples 1 to 4>
For Examples 19 to 26 and Reference Examples 1 to 4, coextruded sheets composed of A layer and C layer were obtained in the same manner as in Examples 1 to 18, and the resin composition of the A layer was shown in Table 1-1. The same thing as "a-5" of No. 5 is used, and the resin composition and thickness of the C layer shown in Table 2-1 are used. Extrusion film forming conditions, embossing conditions, and the like are the same as in Examples 1 to 18, but as the resin composition of the C layer, “c-11” and “c” using crystalline PET resin having a high melting point. Regarding "-12", the set temperature of the extruder on the C layer side is set to 250 ° C on the feed side and 270 ° C on the base side. Regarding the coloring method of the C layer, it is carried out using a commercially available pigment master batch in the same manner as in Examples 1 to 18, but as a resin component of the C layer, “c-10” containing no PETG resin, As for “c-12”, since a commercially available pigment masterbatch using PCTG resin (PCTG 5445) as a base resin was not available, required equipment such as a 25 mm diameter twin-screw kneader and pelletizer Was used to prepare a pigment master batch having a pigment component concentration of 50% by mass (resin component amount 50% by mass). And it is used by mixing and diluting with normal PCTG raw material pellets so as to obtain a required pigment concentration. Also in this case, as a coloring pigment in the C layer, 25 parts by mass of a light blue pigment mainly composed of a titanium oxide-based white pigment and an organic blue pigment combined therewith (the total amount of resin components in the C layer is 100%). It is colored so as to be added. In Tables 2-2 and 2-3, tables summarizing the layer configurations of the examples and reference examples are listed.

<Examples 27 to 42, Comparative Example 12, and Reference Examples 5 to 8>
As Examples 27 to 42, Comparative Example 12 and Reference Examples 5 to 8, two co-directional biaxials having a vent device at two locations with a cylinder diameter of 65 mm for extruding the resin composition of the A layer and the C layer Using a kneading extruder (“TEX-65” manufactured by JSW), a co-directional twin-screw kneading extruder (Toshiba Machine Co., Ltd.) having a vent device at two locations with a cylinder diameter of 37 mm for extruding the D layer resin composition. "TEM-37" manufactured by Komatsu Ltd.), using a total of three extruders, the necessary connecting conduits and a three-layer merged feed block, and a feed block using a single-layer T-die with a lip width of 1200 mm A non-oriented laminated sheet having a three-layer structure of 950 mm in width consisting of a total of three layers of A layer, C layer, and D layer was produced by a general method of pulling out the resin flowing out from the T die with a casting roll by an extrusion method. .
The extrusion conditions of the A layer and the C layer are the same as those in Examples 1 to 18, and the cylinder set temperature of the extruder for the D layer is 220 ° C. on the feed side and 250 ° C. on the base side. As in the case of Examples 1 to 18, the temperature setting of the three-layer merged feed block and the single-layer T die was appropriately finely adjusted mainly according to the change in the resin composition on the A layer side. Similarly, the temperature setting in the width direction of the T die is finely adjusted as appropriate. Regarding the C layer, which is a colored layer, 25 parts by weight of a light blue pigment mainly composed of a titanium oxide white pigment and combined with an organic blue pigment is used (the total amount of resin components in the C layer is 100 parts by weight). Value) It is colored by adding.
However, regarding “c-22” and “c-23” using a crystalline PET resin having a high melting point as the resin composition of the C layer, the set temperature of the extruder on the C layer side is 250 ° C. on the feed side, The base side is 270 ° C. Regarding the coloring method of the C layer, it is carried out in the same manner as in Examples 1 to 18, but as for the resin component of the C layer, “c-21” and “c-23” which do not contain PETG resin. Since a commercial product of a pigment masterbatch using PCTG resin (PCTG / 5445) as a base resin was not available, the pigment component concentration was 50 using a 25 mm diameter twin-screw kneader and necessary equipment such as a pelletizer. A pigment master batch of mass% (resin component amount 50 mass%) was prepared. And it is used by mixing and diluting with normal PCTG raw material pellets so as to obtain a required pigment concentration.

  The temperature of the casting roll of the extruder was adjusted by circulating the heat transfer oil, and the roll surface temperature was set based on the glass transition temperature of −15 ° C. of the resin composition of the A layer. On the surface of the casting roll, a metal roll having a diameter of 500 mm engraved with embossing to give a textured texture of a satin texture having a center line average roughness (Ra) of 1 μm and a maximum height (Ry) of 6 μm was used. The embossing imparted to the surface of the metal roll is not for imparting an embossed design feeling to the laminated sheet, but for imparting slipperiness to the film-formed sheet and improving the rollability. The molten resin flowing down from the T-die is extruded so that the side on which the A layer is formed becomes the casting roll side, and on the side on which the D layer is formed, the surface temperature is about 40 ° C. by circulating water. The silicone rubber touch roll adjusted to be in contact with each other. The sheet flow speed (film forming speed) at the time of leaving the casting roll was 25 m / min to 30 m / min.

[Embossing to laminated sheet by embossing equipment]
About the laminated sheet obtained in Examples 27-42, Comparative Example 12, and Reference Examples 5-8, the embossed pattern was transferred using the embossing apparatus shown in FIG. As an outline of the embossing process, the sheet is first pre-heated by contact-type heating using a heating roll, then the sheet is heated to any temperature by non-contact-type heating using an infrared heater, and any surface is selected. The embossed pattern is transferred to an embossed design sheet by an embossing roll adjusted to the temperature.

In this example, the heating roll was set to 140 ° C., and then heated with an infrared heater so that the sheet surface temperature immediately before contacting the embossing roll was 170 ° C. The embossing roll is temperature-controlled by a hot water circulator based on “glass transition temperature of each layer A—15 ° C.”, centerline average roughness (Ra) = 6.5 μm, maximum height (Ry) = 57 μm, This is a surface-plated metal roll having a diameter of 200 mm engraved with embosses for imparting unevenness of an abstract pattern (skin tone). And said embossing roll, A layer embossed the abstract pattern design by being pressed between two Ppuroru, C layer, and was transferred to the A layer side surface of the laminated sheet consisting of D layer. Further, the embossed sheet was guided to a cooling roll, and the emboss of the design was cooled and fixed by cooling the sheet.

Table 3 shows the composition of the resin and the layer thickness used in the A layer of Examples 27 to 42, Comparative Example 12, and Reference Examples 5 to 8. Moreover, in Table 3, the glass transition temperature of the resin composition of each A layer of an Example, a comparative example, and a reference example, and the tensile method storage elastic modulus (E ') in 120 degreeC were described. Regarding the measurement sample of the glass transition temperature, it is measured using a sample obtained by scraping the resin from the A layer side of the coextruded sheet of the A layer, the C layer, and the D layer using a microtome. The measurement itself is performed by a differential scanning calorimeter in the same manner as the measurement of the glass transition temperature of the raw material resin, which will be described later. Using a single-screw extruder and a single-layer die having a width of 300 mm, a film having a thickness of 100 μm is formed as a specimen. Moreover, although it showed in Table 4 about the composition of the resin used for C layer, and the thickness of the layer, the resin composition of C layer is fundamentally from what was used in Examples 19-26 and Reference Examples 1-4. An excerpt is used.
About the resin composition of D layer, and thickness, it is the same about Examples 27-42, Comparative Example 12, and Reference Examples 5-8, and based on the total resin component of D layer (100 mass%), Easter PETG * 6763 is composed of 15% by mass and Novaturan 5020H is composed of 85% by mass. Table 5 shows the combinations of the A layer and the C layer of Examples 27 to 42, Comparative Example 12, and Reference Examples 5 to 8.

<Examples 43 to 52, Reference Examples 9 to 16>
(Preparation of coextruded sheet of A layer + B layer)
The coextruded sheets of layer A and layer B used in Examples 43 to 52 and Reference Examples 9 to 16 were two co-directional twin-screw kneading extruders having a venting device having a cylinder diameter of 65 mm (“TEX made by JSW”). -65 "), and through the required connecting conduits and distribution blocks, the resin that has flowed out of the T die is cast by a co-extrusion method using a two-layer multi-manifold lip width of 1400 mm. A non-oriented transparent laminated sheet having a two-layer structure having a width of 1200 mm composed of the A layer and the B layer was prepared by the general method of taking up in step 1). The procedure for film formation, the temperature setting of the extruder, the adjustment of the surface temperature setting of the casting roll, and the like are performed in the same manner as in Examples 1-18. However, as the casting roll, a mirror surface metal roll having a diameter of 500 mm whose surface is not embossed is used. For the resin composition and thickness of the A layer, the same as “a-5” in Table 1 is used, and for the resin composition and thickness of the B layer, those shown in Table 6 are used.

(Production of co-extruded sheet of C layer + D layer and application of printed pattern)
Regarding the coextruded sheet of the C layer and the D layer, coextrusion film formation was performed in the same manner as in the case of the coextruded sheet of the A layer and the B layer. Extruders used and temperature settings were the same as in the case of layer A and layer B, but “d-11” and “d-12” using crystalline PET resin having a high melting point as the resin composition of layer D. ”, The set temperature of the extruder on the D layer side is 250 ° C. on the feed side and 270 ° C. on the base side. As the casting roll, a metal roll having a diameter of 500 mm engraved with embossing to give a textured texture with a center line average roughness (Ra) of 1 μm and a maximum height (Ry) of 6 μm was used. The embossing is not for the purpose of providing a matte design, but for improving the fixability of the printing ink when the printed pattern E is applied to the surface of the C layer. In addition, it is extruded so that the side on which the C layer is formed becomes the take-up roll side.
The resin composition of the C layer is composed of 75 parts by mass of Easter PETG · 6763 and 25% by mass of Novaturan 5020H, based on the total resin components of the C layer (100% by mass), and 28 parts by mass of the pigment component (C layer) The resin component is colored light blue by the addition of 100 parts by mass of the resin component, and has the same composition as “c-16” in Table 4 and a thickness of 80 μm. Also in this case, as for the colorant of the C layer, as in Examples 1 to 18, a pigment component concentration of 50% by mass (resin component amount of 50% by mass) using PETG resin (Easter 6763) as a base resin. A masterbatch is used, and a light blue pigment composed mainly of titanium oxide and combined with an organic blue pigment is used as a pigment component. The thickness of the C layer is 80 μm. Regarding the resin composition and thickness of the D layer, those shown in Table 7 are used.

 An abstract printed pattern E was printed on the surface of the C layer side of the coextruded sheet of the C layer and D layer obtained above by gravure printing using an acrylic / urethane printing ink. There was no particular problem with printability on the gravure printing press.

<A-layer + B-layer sheet and C-layer + D-layer sheet heat-sealed lamination and embossing>
As in the case of Examples 27 to 42, using the embossing apparatus shown in FIG. The emboss of the design was transferred. In this embodiment, the heating roll is set to 140 ° C., and the two kinds of sheets are overlapped by pressing with a silicone rubber touch roll at the introduction portion of the sheet to the heating roll. Thermal fusion lamination was performed. Subsequently, the laminated and integrated sheet was heated with an infrared heater so that the surface temperature immediately before coming into contact with the embossing roll 250 was 170 ° C. The embossing roll is temperature-controlled by a hot water circulator based on “glass transition temperature of each layer A—15 ° C.”, centerline average roughness (Ra) = 6.5 μm, maximum height (Ry) = 57 μm, This is a surface-plated metal roll having a diameter of 200 mm engraved with embosses for imparting unevenness of an abstract pattern (skin tone). The emboss of the abstract design was transferred by being pressed between the embossing roll and the nip roll. Further, the sheet on which the emboss was transferred was guided to a cooling roll, and the emboss of the abstract design was cooled and fixed by cooling the sheet. Table 8 shows combinations of the B layer and the C layer in Examples 43 to 52 and Reference Examples 9 to 16.

<Reference Examples 17-19, Comparative Example 13>
Two layers of multi-manifolds using two co-directional twin-screw kneading extruders (“TEX-65” manufactured by JSW) with a venting device with a cylinder diameter of 65 mm, with the necessary connecting conduits and distribution blocks interposed A two-layer non-oriented transparent structure with a width of 1200 mm consisting of A and B layers by a general method in which the resin flowing out of the T die is drawn by a casting roll by a co-extrusion method using a T die having a lip width of 1400 mm. A laminated sheet was created. The procedure for film formation, the temperature setting of the extruder, the adjustment of the surface temperature setting of the casting roll, etc. are carried out in the same manner as in Examples 1 to 18, but for Comparative Example 13, the surface temperature of the casting roll is The temperature was 60 ° C. Moreover, the casting roll uses the mirror surface metal roll of diameter 500mm which is not embossed on the surface. Regarding the resin composition and thickness of the A layer of the reference example, the same ones as “a-3”, “a-5”, and “a-25” in Table 1 are used. Novaduran 5020H, which is a homo PBT resin, is used as the resin composition of the layer. Regarding the resin composition and thickness of the B layer, the same as “b-5” in Table 3 is used.
With respect to the obtained transparent laminated sheet having a two-layer structure, total light transmittance and haze (cloudiness value) were measured in accordance with JIS K 7105. The measurement results are shown in Table 13. In addition, although the reference examples 17-19 belong to the range of this invention in each layer resin composition and thickness, since the embossed design is not provided to the A layer side surface for the purpose of measuring internal haze. This is a reference example. In Table 8-2, a table summarizing the layer configurations of the reference example and the comparative example is shown.

The raw materials used in the above Examples, Reference Examples, and Comparative Examples are as follows.
(Altester 45)
It is a non-crystalline aromatic polyester resin manufactured by Mitsubishi Gas Chemical Company. The dicarboxylic acid component is terephthalic acid, and 44 mol% of the diol component contains spiroglycol, about 53 mol% ethylene glycol, and about 3 mol% diethyleneglycol. The measured glass transition temperature was 111 ° C. and no melting point was observed.

(Altester 30)
It is a non-crystalline aromatic polyester resin manufactured by Mitsubishi Gas Chemical Company. The dicarboxylic acid component is terephthalic acid, and 30 mol% of the diol component contains spiroglycol, about 66 mol% ethylene glycol, and about 4 mol% diethyleneglycol. The measured glass transition temperature was 101 ° C. and no melting point was observed.

(Altester 20)
It is a non-crystalline aromatic polyester resin manufactured by Mitsubishi Gas Chemical Company. The dicarboxylic acid component is terephthalic acid, and the diol component contains 20 mol% spiroglycol, about 76 mol% ethylene glycol, and about 4 mol% diethyleneglycol. The measured glass transition temperature was 94 ° C. and no melting point was observed.

(Tritan FX-100)
A non-crystalline aromatic polyester resin manufactured by Eastman Chemical Company.
The dicarboxylic acid component is terephthalic acid, and about 79 mol% of the diol component. About 21, mol% of 1,4-cyclohexanedimethanol is 2,2,4,4, -tetramethyl-1,3-cyclobutanediol. The measured glass transition temperature was 110 ° C. and no melting point was observed.

(Tritan FX-200)
A non-crystalline aromatic polyester resin manufactured by Eastman Chemical Company.
The dicarboxylic acid component is terephthalic acid, and about 65 mol% of the diol component. About 35 mol% of 1,4-cyclohexanedimethanol is 2,2,4,4, -tetramethyl-1,3-cyclobutanediol. The measured glass transition temperature was 118 ° C. and no melting point was observed.

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

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

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

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

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

(Unipet RT-553): is a polyethylene terephthalate (homo PET) resin manufactured by Nippon Unipet Co., Ltd. The measured melting point was 254 ° C.

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

[Production of embossed design sheet-coated metal sheet]
<Creation of laminated sheet-coated metal sheet>
A commercially available solvent-based thermosetting polyester adhesive (manufactured by Mitsubishi Rayon Co., Ltd.) for a polyvinyl chloride coated metal plate was applied to the metal surface so that the adhesive film thickness after drying was about 2 to 3 μm. . Next, solvent drying and heating of the coated surface were performed with a hot air heating furnace and an infrared heater, and the surface temperature of the hot-dip galvanized steel sheet having a thickness of 1.2 mm and 1.6 mm was set to 230 ° C. just before the laminating roll. Then, immediately using a roll laminator, the side of the laminated sheet produced as described above that had not been embossed was coated as a laminated surface, and cooled by water jetting to produce a laminated sheet-coated metal plate. The metal plate temperature before laminating, the cooling conditions such as the cooling water amount and the cooling water temperature, and the laminating conditions such as the unwinding torque of the laminated sheet are the same for all examples and comparative examples.

[Evaluation of laminated sheet and embossed design sheet coated metal sheet]
The following items were evaluated for the laminated sheet and the embossed design sheet-covered metal plate obtained in the above Examples and Comparative Examples. The results are summarized in Table 9, Table 10, Table 11, and Table 12.
Table 13 shows the measurement results of haze (cloudiness value) of the two-layer laminated transparent sheet obtained in Reference Example and Comparative Example 32.

(1) Measurement of glass transition temperature of raw material resin and resin composition of layer A Glass transition temperature (Tg) was measured by using a differential scanning calorimeter “DSC-7” manufactured by PerkinElmer Co., Ltd. In accordance with -7121 “Plastic transition temperature measurement method”, the temperature was raised from −40 ° C. to 250 ° C. at a heating rate of 10 ° C./min, held at 250 ° C. for 1 minute, and then −40 at a cooling rate of 10 ° C./min. It is a value obtained from a thermogram when the temperature is lowered to 0 ° C., held at the same temperature for 1 minute, and then heated again at 10 ° C./minute. At the same time, the unity of glass transition temperature was also judged. Moreover, regarding the glass transition temperature and melting | fusing point described in the physical property of said raw material to use, each raw material pellet was used as a sample as it was. Moreover, when measuring the raw materials of “Unipet RT-553” and “BK-2180” which are crystalline PET resins, the temperature is raised to 275 ° C.

(2) Measurement of storage elastic modulus at 120 ° C. of resin composition of layer A Using a viscoelasticity spectrometer manufactured by Iwamoto Seisakusho, measurement was performed in the MD direction of a sheet composed of a resin composition single layer of layer A having a thickness of 100 μm. It was. The measuring method is in accordance with the usual tensile method and temperature dispersion measuring method, the temperature is increased from −100 ° C. at a rate of temperature increase of 3 ° C./min, the measurement is performed up to 250 ° C., and then the storage elasticity at 120 ° C. at a frequency of 10 hz. The rate (E ') was read. At the same time, the unity of the glass transition temperature was also determined from the dispersion peak of the imaginary term (loss modulus / E ") of the temperature dispersion.

(3) Emboss transferability Extruded cast Laminated sheets (Examples 1 to 26, Comparative Examples 1 to 11 and Reference Examples 1 to 4) subjected to embossing by embossing, or laminated layers subjected to embossing by an embossing apparatus With respect to the sheets (Examples 27 to 52, Comparative Example 12 and Reference Examples 5 to 16), the surface on the embossed side was measured with a surface roughness meter ("Surfcoder" SE-40D manufactured by Kosaka Laboratory). The center line average roughness Ra1 (μm) was determined. At the same time, using a dental impression material “GC Modeling Compound” manufactured by Niimi Kagaku Kogyo Co., Ltd., an inverted replica of the embossed irregularities on the surface of the embossed plate roll was created according to the method of use described, and the centerline average roughness of the surface Was measured as Ra0 (μm). From these measured values, the emboss transfer rate was determined by the following equation.
(Emboss transfer rate: Ra1 / Ra0 × 100 (%)).
However, there is a concern that the embossed unevenness on the surface of the embossed plate roll has a difference in roughness depending on the location, and there is a concern about whether the inverted replica can reproduce the surface unevenness completely. When used in combination, the transfer rate is 75% or more, and when there is no abnormality in the transfer by visual observation, “◯”, the residual rate is less than 75%, but it is not visually recognized as a remarkable abnormality. In the case of “△”, the residual ratio is less than 75%, and the embossed transfer is clearly shallow and the design feeling is poor, “×”. In addition, the emboss heat resistance of item (5) could not be evaluated for those for which the emboss transferability was evaluated as “x”.

(4) Embossing suitability (4-1) Adhesion resistance When embossing was applied with the embossing apparatus shown in FIG. 2, the laminated sheet adhered to the heating roll, making it difficult to peel off, making it difficult to continue the work. Although it was possible to peel the sheet, it was possible to exfoliate, but due to the effect of adhesion, the sheet was markedly stretched, deformed, and wrinkled, and it was not possible to obtain an embossed design sheet having commercial value. Although it was possible to continue the work and the sheet stretch / deformation was in the range where there was no practical problem, “△” indicates that the work was stable without sticking and “○”. Indicated. Subsequent evaluation was not performed about what became "x" by adhesion resistance. This evaluation is implemented about Examples 27-52, the comparative example 12, and the reference examples 5-16 which implemented emboss provision by the embossing apparatus. In addition, the thing evaluated as "x" regarding adhesive resistance could not carry out subsequent evaluation.

(4-2) Fusing resistance When embossing is applied by the embossing apparatus shown in FIG. 2, the sheet is blown during heating of the sheet by an infrared heater, and the sheet is noticeably stretched, contracted, wrinkled, etc. What was generated was "x", and the sheet was slightly stretched or contracted in width, but was in a range where there was no practical problem, and "△", stable work was possible without causing these problems. Items are indicated by “○”. No further evaluation was performed for those evaluated as “x” in this evaluation. This evaluation is implemented about Examples 27-52, the comparative example 12, and the reference examples 5-16 which implemented emboss provision by the embossing apparatus. In addition, what was evaluated as "x" regarding fusing resistance could not carry out subsequent evaluation.

(5) Embossing heat resistance (5-1) Embossing heat resistance during metal plate lamination (embossing residual rate)
The surface of the resin layer of the metal plate laminated with the laminated sheet was measured with a surface roughness meter ("Surfcoder" SE-40D manufactured by Kosaka Laboratory), and the center line average roughness Ra2 (μm) after lamination was obtained.
From the comparison with the centerline average roughness Ra1 (μm) of the laminated sheet after the emboss transfer measured in the term of the emboss transfer rate, the emboss residual rate at the time of lamination was determined by the following equation.
(Emboss remaining rate: Ra2 / Ra1 × 100 (%))
The case where the residual rate is 75% or more and no abnormality is visually recognized by visual observation is “◯”, and the case where the residual rate is less than 75% but is not visually recognized as a remarkable abnormality. △ ”, the residual rate is less than 75%, and the embossed transfer is clearly shallow visually, the design is poor, or the embossed transfer is partially shallow, such as streaks. Items with no value are indicated by “x”.
As the metal plate, a hot-dip galvanized steel plate having a thickness of 1.2 mm and 1.6 mm is used. In addition, about the thing which produced remarkable embossing return at the time of the lamination to a metal plate, and was evaluated as "x", the evaluation of the presence or absence of abnormality after immersion in boiling water of item (6) is not performed.

(6) Abnormality after immersion in boiling water Surface roughness meter on the resin layer side surface with embossing applied to the laminated sheet-coated metal sheet laminated with a 1.6mm thick hot-dip galvanized steel sheet (Kosaka Research) The measurement start point and end point were marked with an ink that was not discolored even when immersed in boiling water for a short time, and then immersed in boiling water for 3 hours. After taking out and drying, the surface roughness was measured again for the measurement points marked above, and the average roughness of the center line before being poured into boiling water was Ra3 (μm), and that after immersion in boiling water was Ra4 (μm ) To determine the remaining ratio of the emboss (remaining ratio: Ra4 / Ra3 × 100 (%)).
Also, visual observation of the surface of the resin-coated metal plate on the resin-coated metal plate after immersion in boiling water was performed, the emboss residual rate was 75% or more, and the resin layer was softened due to boiling water immersion other than emboss return -A case where no deformation due to flow is observed, "O", a residual rate of less than 75% but 70% or more, and visually a resin layer caused by boiling water immersion other than emboss return When the deformation due to softening / flow of the resin is not recognized as a remarkable abnormality, or the residual rate is 75% or more, the deformation due to softening / flow of the resin layer due to immersion in boiling water is slightly The case where it is recognized is “△”, the residual rate is less than 70%, and the design feeling of the emboss is clearly lowered visually, and the resin layer is softened and flowed regardless of the residual rate of the emboss. Remarkable design due to deformation caused But shows a case that has decreased in the "×".

(6) Bending workability (bending workability of resin-coated metal sheet)
The laminated sheet-covered metal plate obtained by laminating the laminated sheet on a hot-dip galvanized steel sheet having a thickness of 1.6 mm was subjected to a V-bending test by a hydraulic bender, and the surface state of the laminated sheet in the bent portion was visually determined. Samples of 50 mm x 150 mm are prepared from the length direction and width direction of the laminated sheet-covered metal plate, kept at 23 ° C for 1 hour or longer, and then covered with a laminated sheet using a hydraulic bending tester (hydraulic bender) The bent side was bent at 90 degrees with an inner radius of 2 mm so that it became the protruding side.
Visually observe the resin layer at the bent part, and if the resin layer is not whitened, occurrence of fine cracks, or abnormalities such as cracks, `` Yes '', although the resin layer is slightly whitened or fine cracks occurred The case where cracking did not occur was evaluated as “Δ”, and the case where cracking occurred and the case where cracking occurred but significant whitening or microcracking occurred was evaluated as “x”.

(7) Surface hardness (pencil hardness test of resin-coated metal plate)
Regarding a laminated sheet-coated metal sheet obtained by laminating a laminated sheet on a hot-dip galvanized steel sheet having a thickness of 1.6 mm, JIS K5600-5-4: 1999 “General Test Method for Paint—Part 5: Mechanical Properties of Coating Film—Section 4 : Scratch hardness (pencil method) ". Drawing in a temperature-controlled room at 23 ° C. using a jig that can draw a 9.8 N load 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 And the surface state of the resin sheet of the portion was visually judged, and “○” indicates that the B pencil was not scratched at all, B scratched, but the 2B pencil was not scratched at all. Items with “△” and 2B pencils with scratches were displayed as “x”.

(8) Alkali-resistant immersion test 7.5 “Chemical resistance test” of JIS K 6744 “Polyvinyl chloride-coated metal plate” regarding a laminated sheet-coated metal plate obtained by laminating a laminated sheet on a hot-dip galvanized steel sheet having a thickness of 1.6 mm In accordance with the above, after cutting the laminated sheet-coated metal plate to 50 mm × 100 mm and sealing the cut end with an acrylic silicone adhesive “Cemedine Super X” manufactured by Cemedine Co., Ltd., and then at an ambient temperature of 23 ° C. In a 10% aqueous solution of sodium hydroxide for 5 hours and taken out, the surface of the laminated sheet is visually observed, “○” indicates no change in appearance, and the resin layer is markedly cracked. “X”, and “Δ” means a case where slight fine cracks of a level that can be confirmed if observed are generated.

[Evaluation results]
<Examples 1-18 and Comparative Examples 1-11>
Comparative Example 9 is a case where only the aromatic polycarbonate-based resin (a2 component) is used as the resin composition of the A layer, and there is no problem in the emboss transfer by the extrusion cast embossing method, and good emboss transferability is obtained. In addition, even when laminated on a metal plate having a thickness of 1.6 mm, there was no problem in the heat resistance of the embossing, but a remarkable crack was generated in the alkali immersion test.
Comparative Example 1, Comparative Example 2, and Comparative Example 8 are each composed of a blend composition of an aromatic polyester resin (a1 component) having a glass transition temperature of 100 ° C. or higher and an aromatic polycarbonate resin (a2 component). The layer A is used, and the blend composition is judged to be compatible, but the blending ratio of the component (a2) exceeds the range of the present invention, and there is no problem with the heat resistance of the embossing. However, remarkable cracks are generated in the alkali immersion test. Comparative Examples 3 to 6 are cases in which an A-layer composed of an aromatic polyester resin having a glass transition temperature of less than 100 ° C. and a blend composition of (a2 component) was used. In this case, the blend composition was compatible. Although it is a system, since the glass transition temperature of the aromatic polyester resin is low, the embossing heat resistance cannot be secured unless the composition is high (over 50% by mass) of (a2 component). . As a result, only an alkaline immersion test result is obtained. In Comparative Example 3, the blending ratio of the aromatic polyester resin and the component (a2) is equal, and the alkali soaking property is improved, but it is not sufficient, and the embossing heat resistance is still insufficient. When an aromatic polyester resin having a glass transition temperature of less than 100 ° C. was used, it was impossible to achieve both embossing heat resistance and alkali resistance.
Comparative Examples 9 to 11 are aromatic polyester resins that still form a compatible blend composition with component (a2), but are those having a lower glass transition temperature. Alkaline compatibility is still a difficult result.

In contrast to the comparative examples described above, the laminated sheets of Examples 1 to 18 of the present invention have no problem in the emboss transferability by the extrusion cast embossing method, and good emboss transfer is obtained.
However, in Example 1, Example 7 and Example 11 in which the blending ratio of (a2 component) was low, there was no problem in embossing heat resistance in lamination to a metal plate having a thickness of 1.2 mm. However, the lamination to a metal plate having a thickness of 1.6 mm has insufficient embossing heat resistance. In Example 2, Example 8, and Example 12, in which the blending ratio of (a2 component) was increased from these, the embossing heat resistance with a 1.6 mm thick metal plate was improved, and the embossing return was visually Although it is no longer recognized as a quality abnormality, the emboss remaining rate is somewhat bad. Regarding the other examples, the blending ratio of (a2 component) is 50% by mass or less, but the blending ratio of (a2 component) is higher than that of the above examples, and no problem is caused in the embossing heat resistance.

Regarding these, when the storage elastic modulus (E ′) at 120 ° C. of the resin composition of the A layer was measured, it was laminated to a 1.6 mm metal plate in the case of 2 × 10 ⁸ (Pa) or less. In the case of 4 × 10 ⁸ (Pa) or more, the embossing return in the case is remarkable.
On the other hand, in Example 6, Example 10, and Example 15, which are blend compositions of 50% by mass of (a1 component) and 50% by mass of (a2 component), the results of the alkali resistance immersion test are slightly worse. The blending ratio of (a2 component) is particularly preferably 45% by mass or less.
Thus, since the compounding ratio of the component (a1) and the component (a2) in the resin composition of the A layer is restricted from both embossing heat resistance and alkali soaking resistance, (a1) As the component, it is possible to widen the range of the blending ratio by using a component having a higher glass transition temperature, and Examples 7 to 10 using a component having a glass transition temperature of 101 ° C. as (a1 component). In comparison with Example 1, the embossing heat resistance and the alkali immersion resistance are both achieved in Examples 1 to 6 using the same 111 ° C. in a wider range of the blending ratio.

<Examples 19 to 26 and Reference Examples 1 to 4>
Regarding the resin composition and thickness of the A layer, those within the scope of the present invention were used, so there was no problem in the embossing heat resistance when laminating to a 1.6 mm metal plate. Also, no abnormality occurred in the alkali immersion test. Moreover, although the thing which has a larger value than the thickness of A layer is used as the plate depth of embossing roll (the maximum height of the unevenness | corrugation of an embossing roll, Ry value), C layer located under A layer is also an embossing roll. Since it functions as a layer that is deformed by pressing by, there is no problem in the emboss transferability in the extrusion cast embossing method.

The C layer, which is a colored layer, must be a relatively thick layer in order to ensure the required visual hiding properties, but in Reference Example 1, the C layer has a glass transition temperature of less than 100 ° C. This is a case where it is composed only of PETG resin, which is a substantially amorphous polyester resin. When immersed in boiling water, the C layer was softened, the appearance deteriorated due to flow, and the design feeling was lowered. Also in Reference Example 2 in which the resin composition of the C layer was a blend composition of 90% by mass of the non-crystalline polyester resin and 10% by mass of the PBT resin, the improvement effect conspicuous in the appearance defect due to boiling water immersion was not obtained. . On the other hand, in Example 16 in which the blending amount of the PBT resin was further increased, the appearance after immersion in boiling water was considerably improved, and Examples 17 to 17 containing PBT resin in an amount of 25% by mass or more. In Example 23, there is no difference in appearance before and after immersion in boiling water, and particularly good boiling water resistance is obtained. In Example 18, the thickness of the C layer was increased to an excessively large 200 μm, but there was still no problem with respect to boiling water resistance.
On the other hand, in Reference Example 3 and Reference Example 4 in which a crystalline copolymerized PET resin having a crystallization rate slower than that of the PBT resin was blended, the appearance of the C layer consisting of only the PETG resin and the appearance after immersion in boiling water are large. I couldn't find a difference. When immersed in boiling water, it is considered that the softening and fluid deformation of the C layer occur faster than the copolymerized PET resin crystallizes.
In elevator interior applications, boiling water immersion resistance is rarely required, but in applications such as unit bath wall materials, it is often required to pass the test, and the laminated sheet is covered. For the purpose of making the metal plate more versatile, it is preferable to set the resin composition of the C layer within the range of the examples of the present invention.

<Examples 27 to 42, Comparative Example 12, and Reference Examples 5 to 8>
With respect to the resin composition of the A layer, all are within the scope of the present invention, and studies have been made on changing the thickness of A and changing the resin composition of the C layer. Moreover, it is examination in the structure in which D layer exists in order to give emboss with the embossing apparatus in a line different from an extrusion film forming installation.
The colored layer C layer is present between the A layer and the D layer, which are resin layers having excellent heat resistance. However, the C layer is substantially amorphous with a glass transition temperature of less than 100 ° C. In Reference Example 5 composed only of PETG resin, which is a water-soluble polyester resin, a remarkable appearance defect caused by softening and flow of the C layer during boiling water immersion occurs. Also in Reference Example 6 in which the resin composition of the C layer was a blend composition of 90% by mass of the non-crystalline polyester resin and 10% by mass of the PBT resin, the improvement effect conspicuous in the appearance defect due to immersion in boiling water was not obtained. . On the other hand, in Example 35 in which the blending amount of the PBT resin was further increased, the appearance after immersion in boiling water was considerably improved, and Examples 27 to 27 containing PBT resin in an amount of 25% by mass or more. 34 and Examples 36 to 42, particularly good boiling water immersion resistance was obtained, and even in the case where the configuration of the laminated sheet and the embossing method were different, Examples 19 to The result is the same as that of No. 26. The same is true of the poor boiling water immersion resistance in Reference Examples 7 and 8 using a blend composition of a PETG resin and a crystalline copolymerized PET resin as the resin composition of the C layer.

However, in Example 38, the embossing transferability by the embossing apparatus was slightly deteriorated, and in Example 39, the embossing transferability was remarkably lowered. The compositions of these C layers were the same as those of Example 20 and Example 21, and no problem was found when embossing was transferred by the extrusion cast embossing method. Since the blending ratio of the PBT resin in the resin composition of the C layer is relatively high, the PBT resin of the C layer is crystallized upon contact with the heating roll of the embossing apparatus, whereby the C layer is embossed roll It is considered that it will not be deformed even if it is pressed by. Therefore, in the case of using an embossing apparatus, when emboss irregularities having a plate depth equal to or greater than the thickness of the A layer are provided, the blending ratio of the PBT resin of the C layer is 40% by mass or less, more preferably 30% by mass or less. However, this is not necessarily the case when the thickness of the A layer is the same as or sufficiently thick with respect to the plate depth of the embossing roll.

Even in Comparative Example 12 in which the thickness of the A layer, which is a layer that retains the heat resistance of the embossing, is extremely thin, the resin composition of the C layer is pressed by the embossing plate roll even when using an embossing apparatus. Due to the composition deforming without problems, there was no problem in the emboss transferability itself, but the emboss heat resistance during lamination was poor. In Example 17, in which the thickness of the A layer was thicker than Comparative Example 12, the embossing heat resistance at the time of lamination was improved, and no abnormality was visually observed, but the emboss residual rate was somewhat bad. It has become. The thickness of the A layer is the same level as in Example 17, but a higher glass transition temperature (component a1) is used, and in Example 34, the blending ratio of component (a2) is also higher. The situation was the same as in Example 17. On the other hand, in Examples 28 to 33 in which the thickness of the A layer was further increased, there was no problem in the embossing heat resistance. However, it is presumed that the thickness of the A layer necessary to ensure the heat resistance of the emboss can also be changed depending on the plate depth of the emboss to be transferred.

Examples 41 and 42 are combinations in which the thicknesses of both the A layer and the C layer are carelessly increased, resulting in a problem in bending workability as a resin-coated metal plate. In Examples 27 to 42, an emboss having a plate depth of center line average roughness (Ra) = 6.5 μm and maximum height (Ry) = 57 μm is transferred. Then, it is considered that the total thickness of the laminated sheets as in Examples 41 and 42 is unnecessary, and good emboss transferability is obtained even in Example 27 in which the total thickness of the laminated sheets is less than half. In Examples 41 and 42, no particular problem has occurred with respect to the evaluation items other than the bending workability, but also from the viewpoint of cost, the total thickness of the laminated sheet is 300 μm or less, preferably 250 μm or less. It is preferable to do.

<Examples 43 to 52 and Reference Examples 9 to 16>
For the configuration having the printed pattern E, the resin composition and thickness of the A layer are the same as “a-5” in Table 1, and the resin composition of the C layer is the same as “c-16” in Table 4 and the thickness. Only 80 μm is used. In addition, the D layer exists for embossing by an embossing device in a separate line from the extrusion film forming equipment, and the heat of the coextruded sheet (C layer + D layer) provided with the printed pattern E and the A layer. This is a study in a configuration in which a B layer is present in order to improve the melt lamination property.
In these examples and reference examples, no problem occurred in the heat-sealing lamination itself in the embossing apparatus.

  Reference Example 9 and Reference Example 10 are cases where the thickness of the B layer made of only PETG resin (glass transition temperature 78 ° C.) is relatively thick, and there is no problem in the emboss transfer by the embossing apparatus, and the resin composition of the A layer Since the thickness is within the range of the present invention, there was no problem with the embossing heat resistance during lamination. However, a remarkable appearance defect due to softening and flow of the B layer is caused by immersion in boiling water. Reference Example 11 is a case where a PCTG resin (glass transition temperature 86 ° C.) having a glass transition temperature higher than that of PETG resin is used. . On the other hand, in Example 43 in which the thickness of the B layer was reduced, the appearance change after immersion in boiling water was such that there was no practical problem, and Examples 44 to 46 in which the thickness was further reduced. Then, the boiling water immersion property is further improved. Even in Example 45 where the thickness of the B layer was the smallest, no problem occurred in the heat fusion lamination of the coextruded sheet of the A layer + B layer and the coextruded sheet of the C layer + D layer in the embossing apparatus.

Reference Example 12 is an example in which the amount of PBT resin in the D layer is small. In this case, it was possible to barely peel it off while showing adhesion to the heating roll of the embossing device, but when the laminated sheet was heated with an infrared heater, significant sheet elongation and wrinkling occurred, resulting in stable embossing work. It was difficult to continue.
Reference Example 13 is an example in which the thickness of the D layer is thin, although the blending ratio of the resin composition of the D layer is within a preferable range. In this case, both ends of the sheet showed remarkable adhesion to the heating roll. Although it was able to be peeled off, significant sheet elongation and wrinkling occurred when the laminated sheet was heated with an infrared heater, and it was still difficult to provide stable embossing. When the laminated sheet is formed into a film by coextrusion, the adhesion of the end part to the heating roll causes a development failure in the width direction due to the thickness of the D layer being too thin, and the D layer is formed at the end part. It may not be. Although it seems that this problem can be solved also by optimizing the conditions of the coextrusion method, the elongation of the sheet by heating with an infrared heater is due to the fact that the D layer as the tension holding layer is excessively thin.

Reference Example 14 is an example in which a PBT resin of isophthalic acid copolymer is used as the PBT resin of the D layer. In this case, after showing slight adhesion to the heating roll, the laminated sheet was significantly stretched and wrinkled by heating with an infrared heater. The slight adhesion to the heating roll is caused by the fact that the crystallization rate of the isophthalic acid copolymerized polybutylene terephthalate resin is slower than that of the homo PBT resin. This is probably because the heating roll was left while crystallization was insufficient. Further, since the melting point of the resin is about 205 ° C., it is considered that the melt tension was insufficient when heated to 170 ° C. by an infrared heater.
Reference Example 15 is an example using an isophthalic acid copolymerized PET resin, which is a crystalline polyester resin for the D layer, but has a very low crystallization rate compared to the PBT resin. In this case, the sticking to the heating roll became more remarkable than in Reference Example 14, and peeling was difficult and the subsequent work was impossible. In the case of the PET resin copolymerized with isophthalic acid, it seems that crystallization hardly progressed on the heating roll.
Reference Example 16 is a case where a homo-PET resin having a crystallization speed higher than that of isophthalic acid copolymerized PET resin was used for the D layer, but the situation was not significantly different from Reference Example 15.

On the other hand, in Examples 47 to 52 in which a PBT resin having a melting point of 210 ° C. or higher was used as the main component of the D layer, there was no hindrance to the operation in the embossing apparatus, and good productivity was achieved. Thus, embossing with a good transfer rate can be carried out. However, in Example 49 in which the thickness of the D layer is slightly thin, the sheet is slightly stretched when heated by the heater, the blending ratio of the PBT resin in the D layer is the lower limit of the range of the present invention, and the thickness of the D layer is not so thick. A similar tendency was observed in Example 50. Further, in Example 52 using only the homo-PBT resin as the resin composition of the D layer, the warpage of the co-extruded sheet of the C layer and the D layer became remarkable, and the subsequent handling was somewhat hindered. The work was not difficult.
From the above, it can be seen that by having the A layer of the present invention, it is possible to ensure good embossing heat resistance even when embossing is performed with an embossing device, but in order to impart suitability to the embossing device, D It is preferable to keep the resin composition of the layer within the range of the examples of the present invention.

<Reference Examples 17 to 19 and Comparative Example 13>
Even if the PBT resin is crystallized in a non-oriented state, it forms a very fine spherulite structure, so that much better transparency can be obtained compared to a PET resin crystallized in the same state. Although it is possible, it is still inevitable that haze increases to some extent by crystallization. Comparative Example 13 has a layer containing no pigment component made of the crystallized PBT resin. On the other hand, the laminated sheets of Reference Examples 17 to 19 are formed of a resin composition that is substantially amorphous in both the A layer and the B layer, thereby becoming a very low haze transparent sheet. When coated on various colored substrates, or when coated on a printed pattern, it can be said that there is little damage to the original color development and design, which is an embossed design on the surface. It is considered that the same applies to the transparent sheet to which is given.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. Rather, it can be changed as appropriate without departing from the scope or spirit of the invention that can be read from the claims and the entire specification, and a laminated sheet, an embossed design sheet, an embossed design sheet-covered metal plate, and a unit bath with such changes Members, building interior materials, steel furniture members, and household appliance housing members are also to be understood as being within the scope of the present invention.

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

10 A layer 20 B layer 30 C layer 40 D layer 50 Print pattern E
60 Metal plate 70 Adhesive layer 100A, 100B, 100C, 100D Laminated sheet having embossed design 200A, 200B, Metal plate coated with laminated sheet having embossed design 300 Embossing apparatus 310 Heating roll 320 Take-off roll 330 Infrared heater 340 Embossed Roll 350 Nip roll 360 Cooling roll

Claims (13)

At least one outermost surface layer (hereinafter referred to as A layer) has an aromatic polyester resin (a1 component) having a glass transition temperature of 100 ° C. or higher and 50% by weight or more based on the total mass of the A layer resin component. The main component is a resin composition comprising 50% by mass or less of a polycarbonate-based resin (a2 component), the glass transition temperature of the a2 component is higher than the glass transition temperature of the a1 component, and the thickness of the A layer is 5 μm to 100 μm A laminated sheet comprising an uneven design on the exposed surface of the A layer. From the resin composition in which the dicarboxylic acid component of the a1 component is mainly terephthalic acid or a derivative thereof, and the diol component is mainly 50 mol% to 70 mol% ethylene glycol and 30 mol% to 50 mol% spiroglycol. The laminated sheet according to claim 1, wherein the laminated sheet is an aromatic polyester resin.   The dicarboxylic acid component of the a1 component is mainly terephthalic acid or a derivative thereof, and the diol component is 60 mol% to 80 mol% of 1,4-cyclohexanedimethanol, 2,2,4,4, -tetramethyl. The laminated sheet according to claim 1 or 2, which is an aromatic polyester resin having a resin composition mainly composed of 20 mol% to 40 mol% of -1,3-cyclobutanediol. When the resin component constituting the A layer has a frequency of 10 Hz and a storage elastic modulus (E ′) by a dynamic viscoelastic tension method is measured, the measured value at 120 ° C. is 2 × 10 ⁸ (Pa) or more. It is 6 * 10 < ⁹ > (Pa) or less, The lamination sheet in any one of Claims 1-3. The laminated sheet according to any one of claims 1 to 4, wherein the layer B described below is provided on a surface not provided with the uneven design of the A layer.
B layer: A resin layer comprising 70% by mass or more of a substantially amorphous polyester resin having a glass transition temperature of less than 100 ° C., based on the mass of the entire resin component in the B layer. The laminated sheet according to any one of claims 1 to 5, which has the C layer described below on a surface not provided with the uneven design of the A layer.
C layer: Polyester based on 100% by mass of the resin component of C layer, 20% by mass to 70% by mass of polybutylene terephthalate resin having a melting point of 210 ° C. to 230 ° C., and a glass transition temperature of less than 100 ° C. Resin layer consisting of 30% to 80% by weight of resin and added with a colorant The laminated sheet according to claim 6, comprising a C layer and a D layer described below on a surface not provided with the uneven design of the A layer.
D layer: A resin layer comprising 75% by mass or more of a polybutylene terephthalate resin having a melting point of 210 ° C. to 230 ° C. with the total amount of the resin components of the D layer being 100% by mass.   The laminated sheet according to claim 7, comprising the B layer, the C layer, and the D layer described below on a surface not provided with the uneven design of the A layer. A laminated sheet, wherein the uneven design of the A layer is provided by an embossing apparatus installed separately from the extrusion film forming equipment.   A coated metal plate, which is covered with the laminated sheet according to any one of claims 1 to 9. An elevator interior material using the coated metal plate according to claim 9. A unit bus member using the product-coated metal plate according to claim 9.   A building interior material using the coated metal plate according to claim 9.

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