JP2008254348A - Laminated sheet for coating metal sheet and laminated sheet-coated metal sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet-coated metal sheet which is excellent in embossing aptitude, has a resistance when immersed in boiling water, and has no fear of generating processing failure such as breakages and cracks on the resin layer of a bent part even when a secondary processing such as bending is performed after a long period of time passes after a laminated sheet is laminated on a metal sheet to prepare the laminated sheet-coated metal sheet, and to provide the laminated metal sheet constituting this laminated sheet-coated metal sheet. <P>SOLUTION: The laminated sheet is composed of two layers consisting of an embossing layer (layer A) and a substrate resin layer (layer B). The layer A comprises a PBT resin and/or a PTT resin with respectively specified amounts, a substantially amorphous polyester resin with a specified Tg and a thermoplastic elastomer with epoxy groups and being non-polyester. The layer B mainly comprises a PBT resin and/or a PTT resin. The total thickness of the laminated sheet is ≥100 μm and ≤450 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated sheet for covering a metal plate and a laminated sheet-covered metal plate, and in particular, constitutes a laminated sheet-covered metal plate used as an elevator interior material, a unit bus member, a general inner wall material, and a partition material, and the metal plate. The present invention relates to a laminated sheet for covering a metal plate.

  Conventionally, as a covering material having an embossed design, soft polyvinyl chloride to which an embossed design is imparted (hereinafter, polyvinyl chloride may be abbreviated as “PVC”) is a synthetic resin molded product, plywood, wood fiber plate, metal plate. Etc. 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) Because it has excellent compatibility with various additives and has been studied for improving physical properties with additives for many years, it has sufficient durability for interior building materials. Can be mentioned.

  As a method for continuously embossing the long sheet of soft PVC, a roll obtained by softening a sheet after film formation by reheating and engraving an embossed pattern (hereinafter, this roll is referred to as an “embossed plate roll”). In some cases, a method of transferring the pattern continuously is suppressed. As a method for heating the sheet, a contact type in which the sheet is heated by being brought into contact with a heated metal roll, a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater, a hot air heater, or the like can be considered. In an actual production line, only either one may be used, but generally both are often used together. Moreover, the equipment which has these series of processes is called an embossing apparatus.

  In general, the embossing apparatus incorporates a design that can easily replace and remove the embossing plate roll. The diameter of the embossing plate roll is small compared to the casting roll of the extrusion film forming equipment, etc. Since it is possible to easily and economically change the embossed pattern by preparing various embossing plate rolls, small lots This embossing method is suitable for handling.

  In addition, for soft PVC sheets having a printing design at the same time as the embossed design, after printing is performed on the surface of the colored soft PVC sheet, the transparent soft PVC sheet is laminated and integrated, and the laminated sheet is continuously connected to the embossing apparatus. It was obtained by passing through. In this case, the sheet preheating in the embossing device is used to laminate and integrate two layers of sheets by heat fusion, and production is not required because a special process for lamination is not required. It was good in terms of cost and cost.

  Although it is a soft PVC sheet having such excellent characteristics, in recent years, problems with heavy metal compounds caused by some stabilizers contained in PVC, VOC problems caused by some plasticizers and stabilizers, The use of PVC has been restricted due to problems such as endocrine disrupting action and problems of generating hydrogen chloride gas and other chlorine-containing gases during combustion.

  Therefore, it has been studied to use a polyester resin sheet having a good balance between workability and surface hardness as a base material. In Patent Document 1 and Patent Document 2, a multilayer composite using a transparent film made of an amorphous polyester resin typified by PETG6763 manufactured by Eastman Chemical Co., Ltd. and a colored opaque film made of an amorphous polyester resin. Is described. Patent Document 3 discloses a layer mainly composed of an amorphous polyester-based resin, which is excellent in embossing suitability and shows a good result in a boiling water immersion test included as a test item of a unit bath member. And a laminated resin sheet including at least a layer mainly composed of a crystalline polyester resin.

Patent Document 4 describes a copolymerized polyester sheet and film in which deterioration of processability over time is prevented by adding a specific methyl methacrylate / butadiene / styrene resin (MBS resin) to a polyester resin. ing.
Japanese Patent No. 3429265 Japanese Patent No. 3678063 WO03 / 045690 JP 2002-121367 A

  However, in the decorative film described in Patent Document 1 and Patent Document 2, both the transparent film layer and the colored opaque film layer are made of an amorphous resin, and the glass transition temperature (Tg) of the resin is about 70 ° C. to Since it exists in the range of 90 degreeC, there was no tolerance with respect to the boiling water immersion test contained as a test item of a unit bath member.

  Further, since it is composed of an amorphous polyester-based resin, there has been a problem that mechanical properties such as elongation at break gradually decrease when stored for a long period of time at or below the glass transition temperature of the resin after thermoforming.

  This decrease in mechanical properties is thought to be due to the progress of so-called enthalpy relaxation. In a resin-coated metal plate having a general thickness structure, even if enthalpy relaxation progresses, problems such as cracks and cracks occurring in the resin layer due to secondary processing such as bending are not caused. However, in order to obtain a deep embossed design, in a resin-coated metal plate using a relatively thick resin sheet and a resin-coated metal plate using a relatively thick metal plate as in elevator interior materials, Due to enthalpy relaxation, the mechanical properties of the resin layer deteriorate over time, which may cause a problem that the secondary workability of the resin-coated metal sheet is reduced.

  The resin-coated metal sheet whose workability has been lowered due to such enthalpy relaxation can be recovered by heating the coating resin to a temperature higher than the glass transition temperature of the resin immediately before being subjected to secondary processing. it can. However, since such a process increases the number of processes, it has not been accepted by processing manufacturers.

  In addition, the laminated resin sheet described in Patent Document 3 also includes a layer mainly composed of a substantially amorphous polyester resin as an embossing layer. In the resin-coated metal plate used or a resin-coated metal plate using a relatively thick metal plate, enthalpy relaxation occurs, resulting in a problem that the secondary workability of the resin-coated metal plate is reduced as described above. It was.

  In the copolyester sheet and film described in Patent Document 4, an effect of preventing a decrease in elongation at break resulting from the enthalpy relaxation is recognized. However, the polyester sheet and film are not intended for use as a resin-coated metal plate, and when the resin-coated metal plate is subjected to a bending process, the processed portion is whitened. This is presumably because void whitening occurs in the resin layer at the bent portion because the cross-linked elastic component is added to the polyester sheet and film.

  Therefore, the present invention is excellent in embossing suitability and has resistance when immersed in boiling water. After a long period of time has passed since the laminated sheet is laminated on a metal plate to form a laminated sheet-coated metal plate, the sheet is bent, etc. It is an object to provide a laminated sheet-covered metal plate that does not cause processing defects such as cracks and cracks in the resin layer of the bent portion even after the next processing, and a laminated sheet constituting the laminated sheet-coated metal plate And

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

The first aspect of the present invention is a laminated sheet comprising two layers of an embossing layer (A layer) (10) and a base resin layer (B layer) (20), wherein the A layer (10) , 100% by mass of the entire resin component in layer A (10),
(A-1 component) 17% by mass or more and 38% by mass or less of polybutylene terephthalate resin (PBT resin) and / or polytrimethylene terephthalate resin (PTT resin),
(A-2 component) A polyester-based resin having a glass transition temperature of 51% by mass or more and 78% by mass or less, which is substantially amorphous having a glass transition temperature of 60 ° C. or more and 90 ° C. or less, and
(A-3 component) a non-polyester thermoplastic elastomer having an epoxy group of 3% by mass to 15% by mass,
“A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” is 0.2 or more and 0.4 or less,
Layer B (20) is a layer mainly composed of polybutylene terephthalate resin (PBT resin) and / or polytrimethylene terephthalate resin (PTT resin), and has a total thickness of 100 μm or more and 450 μm or less. Laminated sheet (100) for use.

  Here, the “main body” in the B layer (20) is 60% by mass or more of the PBT resin and / or the PTT resin, based on the mass (100% by mass) of the entire resin component of the B layer (20). Preferably it means 70% by mass or more. Moreover, the code | symbol 100 is used as a high-order concept containing 100a-100c. Further, “substantially non-crystalline” means to include low crystallinity (the same applies hereinafter).

  In the laminated sheet for metal plate coating (100) according to the first aspect of the present invention, the A layer (10) contains a predetermined amount of a substantially amorphous polyester-based resin (A-2 component). (10) can be a layer excellent in embossing suitability. Further, the layer A (10) contains a predetermined amount of PBT resin and / or PTT resin (component A-1), thereby preventing deterioration of appearance due to return of embossing when immersed in boiling water. it can. Moreover, after A layer (10) contains the non-polyester-type thermoplastic elastomer (A-3 component) which has a predetermined amount of epoxy groups, after manufacturing a lamination sheet coating | coated metal plate (200), after a long time passed. Even if it is subjected to secondary processing such as bending, it is possible that there is no possibility of causing problems in workability.

  In addition, since the B layer (20) is a layer mainly composed of crystalline PBT resin and / or PTT resin, the concavo-convex design is formed by an embossing plate using an embossing apparatus, and the A layer (10) of the laminated sheet (100). There is no possibility that the B layer (20) side of the laminated sheet (100) will stick to the heated metal roll when it is applied. Moreover, the tension of the heated laminated sheet (100) is insufficient, and there is little risk of causing problems such as abnormal elongation, width shrinkage, and wrinkles. Even when the laminated sheet-coated metal plate (200) is used and then immersed in boiling water, the elastic modulus of the laminated sheet (100) does not decrease, so there is no fear of fluid deformation.

  In the laminated sheet (100) for covering a metal plate of the first invention, a printed pattern C (30) may be provided between the A layer (10) and the B layer (20). Thereby, in addition to the design by an embossed pattern, it can be set as the laminated sheet (100b) which also has the design by a printed pattern.

In the laminated sheet (100) for covering a metal plate according to the first aspect of the present invention, a D layer (40) may be provided between the printed pattern C (30) and the B layer (20). In this case, the composition of the D layer (40) is based on the total resin component in the D layer (40) (100% by mass).
(D-1 component) 17% by mass or more and 38% by mass or less of polybutylene terephthalate resin and / or trimethylene terephthalate resin,
(D-2 component) A polyester resin having a glass transition temperature of 51% by mass or more and 78% by mass or less, which is substantially amorphous having a glass transition temperature of 60 ° C. or more and 90 ° C. or less, and
(D-3 component) containing 3% by mass or more and 15% by mass or less of a non-polyester thermoplastic elastomer having an epoxy group,
“D-1 component (mass%) / (D-1 component (mass%) + D-2 component (mass%))” can be 0.2 or more and 0.4 or less.

  By adopting the configuration including the D layer (40), the lower side of the printed pattern C (30) (the B layer (20) side) also includes a layer having embossing suitability. 10) The thickness of 10) is relatively reduced, and the printed pattern C (30) has good transparency, and deeper embossing can be transferred.

  In the laminated sheet for metal plate coating (100) according to the first aspect of the present invention, the B layer (20) is 70% by mass or more and 95% by mass or less based on the entire resin component in the B layer (20) (100% by mass). A polybutylene terephthalate resin (PBT resin) having a melting point of 215 ° C. or higher and 235 ° C. or lower and / or a polytrimethylene terephthalate resin (PTT resin) having a melting point of 215 ° C. or higher and 235 ° C. or lower. A layer containing 5% by mass or more and 30% by mass or less of a substantially amorphous polyester resin is preferable.

  The PBT resin and PTT resin in the melting point range can be easily obtained commercially, and cost merit can be obtained. Moreover, since melting | fusing point is 235 degrees C or less, the heating temperature at the time of laminating a laminated sheet (100) to a metal plate (60) can be made into the same grade as the case of the conventional soft PVC sheet laminated metal plate. . Further, when the amount of the PBT resin and / or PTT resin is 70% by mass or more of the resin component of the B layer (20), when the laminated sheet (100) is heated by the embossing apparatus, the heated metal roll The non-adhesiveness and the melt fracture resistance can be improved. Moreover, by setting it as 95 mass% or less, it can prevent that the crystallinity of B layer (20) becomes high too much, and can prevent that remarkable curvature generate | occur | produces in a lamination sheet (100) after film forming. Further, even when laminating to the metal plate 60 at the same laminating temperature as in the past, it is possible to make it difficult to cause poor adhesion.

  In the laminated sheet (100) for covering a metal plate according to the first aspect of the present invention, the substantially amorphous polyester resin constituting the A layer (10), the B layer (20) or the D layer (40) Terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, 25 mol% to 50 mol% of the diol component is 1.4-cyclohexanedimethanol, and the remaining 50 mol% to 75 mol% is ethylene glycol. Copolyesters that are other diol components mainly composed of can be used.

  Copolymerized polyesters having such a composition that are substantially amorphous are widely used throughout the world, and are advantageous in terms of cost and stability of raw material supply.

  2nd this invention is equipped with the uneven | corrugated shape formed by the embossing plate in the A layer (10) side surface of the lamination sheet (100) for metal plate coating | cover of 1st this invention, and a lamination sheet (100). It is a laminated sheet for metal plate coating (100d, 100e) having an embossed design. Since the laminated sheet (100) of the first aspect of the present invention is excellent in embossing suitability in an embossing apparatus as described above, various embossed designs can be imparted in a small lot.

  The third aspect of the present invention is a metal sheet covering laminated sheet (100) according to the first aspect of the present invention or a metal sheet covering laminated sheet (100d, 100e) having the embossed design according to the second aspect of the present invention, and a metal sheet ( 60), and a laminated sheet-covered metal plate (200) in which the layer B (20) side of the laminated sheets (100, 100d, 100e) is laminated on the metal plate (60) via an adhesive.

  The laminated sheet-coated metal plate (200) of the third aspect of the present invention is resistant to boiling water immersion and can be used for unit bath applications. And even if it uses for secondary processing after manufacture for a long time after manufacture of a lamination sheet covering metal plate (200), the problem of workability does not arise. In the laminated sheet-coated metal plate (200) of the present invention, even after a long period of time has elapsed since the laminated sheet-coated metal plate (200) was produced, the A layer (10) mainly composed of an amorphous polyester resin. And / or the fall of the secondary workability with time accompanying progress of enthalpy relaxation in the D layer (40) can be effectively prevented. For this reason, in order to obtain a deep embossed design, when using a laminated sheet-coated metal plate (200) using a relatively thick laminated sheet, or a relatively thick metal plate for elevator interior materials, etc. It can use especially suitably for the used lamination sheet covering metal plate (200). Moreover, since it has tolerance also to boiling water immersion, it can be used suitably also for unit bath members, such as a unit bath ceiling material and a unit bath wall material. In addition, the laminated sheet-coated metal plate (200) of the present invention can be used as a general interior material and a partition material.

  In the laminated sheet for metal plate coating (100) according to the first aspect of the present invention, the A layer (10) contains a predetermined amount of a substantially amorphous polyester-based resin (A-2 component). (10) can be a layer excellent in embossing suitability. Further, the layer A (10) contains a predetermined amount of PBT resin and / or PTT resin (component A-1), thereby preventing deterioration of appearance due to return of embossing when immersed in boiling water. it can. Moreover, after A layer (10) contains the non-polyester-type thermoplastic elastomer (A-3 component) which has a predetermined amount of epoxy groups, after manufacturing a lamination sheet coating | coated metal plate (200), after a long time passed. Even if it is subjected to secondary processing such as bending, it is possible that there is no possibility of causing problems in workability.

  In addition, since the B layer (20) is a layer mainly composed of crystalline PBT resin and / or PTT resin, the concavo-convex design is formed by an embossing plate using an embossing apparatus, and the A layer (10) of the laminated sheet (100). There is no possibility that the B layer (20) side of the laminated sheet (100) will stick to the heated metal roll when it is applied. Moreover, the tension of the heated laminated sheet (100) is insufficient, and there is little risk of causing problems such as abnormal elongation, width shrinkage, and wrinkles. Even when the laminated sheet-coated metal plate (200) is used and then immersed in boiling water, the elastic modulus of the laminated sheet (100) does not decrease, so there is no fear of fluid deformation.

  Hereinafter, embodiments embodying the present invention will be described.

  In addition, since the thickness of the laminated sheet of the present invention is in the range of 100 μm or more and 450 μm or less, it is more correct to describe as “film and sheet”. Using.

  The layer structure of the laminated sheet for covering a metal plate of the present invention is shown in FIGS. As shown in FIG. 1 (a), the laminated sheet 100a for covering a metal plate according to the present invention includes an embossing layer (A layer) 10 and a base resin layer (B layer) 20. Yes.

<Embossing layer (A layer) 10>
The resin component of the A layer 10 is based on the entire resin component in the A layer 10 (100% by mass).
(A-1 component) 17% by mass or more and 38% by mass or less of polybutylene terephthalate resin (PBT resin) and / or trimethylene terephthalate resin (PTT resin),
(A-2 component) 51% by mass or more and 78% by mass or less of a glass resin having a glass transition temperature of 60 ° C. or more and 90 ° C. or less and a substantially amorphous polyester, and (A-3 component) 3% by mass or more and 15% A non-polyester thermoplastic elastomer having an epoxy group of not more than mass%.

  And A-1 component so that "A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))" may be 0.2 or more and 0.4 or less. And A-2 component.

(A-1 component)
The purpose of adding the A-1 component to the A layer 10 is to impart appropriate crystallinity to the A layer 10. When the amount of the A-1 component is small and “A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” is less than 0.2, When the sheet-coated metal plate (200) is immersed in boiling water, the elastic modulus of the A layer 10 may be significantly reduced to cause flow deformation, and the appearance may be deteriorated due to the return of embossing, which is not preferable. Conversely, when the amount of component A-1 is large and “A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” exceeds 0.4, The crystallinity of the A layer 10 becomes too high, and crystallization may progress during heating with an embossing machine, making embossing difficult. In addition, from the allowable working condition range in the embossing machine, “A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” is 0.35 or less. It is further preferable that

  In the present invention, as the A-1 component, among crystalline polyester resins, PBT resins and / or PTT resins having a high crystallization rate are used. Other than that, for example, polyethylene terephthalate (PET) -based resin has a low crystallization rate, so that it is difficult to impart sufficient boiling water immersion resistance to the laminated sheet-coated metal plate (200). Further, when crystallization proceeds in the state of a laminated sheet-coated metal plate, secondary workability such as bending may be deteriorated due to the crystal characteristics of the PET resin.

  As the PBT resin, the same PBT resin as the main component of the B layer 20 described later can be used. Among them, a so-called homo PBT resin (which may include an unintended copolymerization component) using terephthalic acid as a dicarboxylic acid component, or dimethyl terephthalic acid, and a single component of 1.4-butanediol as a diol component. .) Is preferable from the viewpoint of cost and availability.

  As the PTT resin, the same PTT resin as the main component of the B layer 20 described later can be used. Among them, a so-called homo PTT resin (which may contain an unintended copolymerization component may be used) using terephthalic acid as a dicarboxylic acid component, or dimethyl terephthalic acid and a single component of 1.3-propanediol as a diol component. .) Is preferable from the viewpoint of cost and availability.

(A-2 component)
The A layer 10 is a layer to which the embossed pattern is transferred by being softened by heating and pressed by an embossing plate roll when the laminated sheet 100 is passed through an embossing apparatus. Accordingly, the A layer 10 should not have high crystallinity when pressed by the embossing plate roll. From such a point, the A layer 10 contains 51% by mass or more of a substantially amorphous polyester-based resin having a glass transition temperature of 60 ° C. or more and 90 ° C. or less as the A-2 component, and “A −1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%)) ”is 0.2 or more and 0.4 or less, more preferably 0.2 or more and 0.35 or less. ing.

  The A layer 10 is embossed after being heated to an A-2 component glass transition temperature (Tg) or higher by an embossing apparatus. When heated, the elastic modulus of the A layer 10 needs to be sufficiently reduced to allow embossing. In that case, if the sheet to be embossed is a single-layer sheet consisting only of the A layer 10 having low crystallinity, the single-layer sheet adheres to a heated metal roll, or the width of the single-layer sheet is reduced. , Creased and sheet breakage. On the other hand, in the lamination sheet 100 of this invention, these problems are solved because the B layer 20 demonstrated below exists.

  As the polyester-based resin that is substantially amorphous as component A-2, a polyester resin that does not show a clear crystal melting peak when heated by a differential scanning calorimeter (DSC), and a crystal that has crystallinity A polyester resin having a low crystallinity and not having high crystallinity in a film forming step such as an extrusion method or a calendering method and a heating step until the embossed pattern is transferred by an embossing apparatus can be used.

  Further, the polyester resin which is substantially amorphous as the A-2 component has terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 25 mol% or more and 50 mol% or less of the diol component is 1.4- It is preferable that the remaining 50 mol% or more and 75 mol% or less of the cyclohexanedimethanol is a copolyester composed of other diol components mainly composed of ethylene glycol.

  Here, the “main component” in the dicarboxylic acid component refers to 70 mol% or more, preferably 80 mol% or more, more preferably 98 mol of terephthalic acid or dimethyl terephthalic acid based on the whole dicarboxylic acid component (100 mol%). % Is included. In addition, the “main component” in the other diol component contains 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, based on the whole other diol component (100 mol%). That means.

  If the amount of 1.4-cyclohexanedimethanol of the diol component is too small, the characteristics as a crystalline resin become remarkable, and crystallization may progress during heating with an embossing machine, which may make embossing difficult. . Moreover, in the copolyester in which the amount of 1.4-cyclohexanedimethanol is more than 50 mol% and 70 mol% or less, it is known that the progress of enthalpy relaxation during storage at room temperature is relatively small. The copolyester resin in the composition range is more expensive than the substantially amorphous polyester resin that can be used in the present invention. When the amount of 1.4-cyclohexanedimethanol exceeds 70 mol%, the characteristics as a crystalline resin become remarkable, and embossing with an embossing apparatus may be difficult.

  Examples of the polyester resin that is substantially non-crystalline include a copolyester resin that is non-crystalline. Specifically, there is a so-called PET-G resin whose cost is reduced because of the stable supply of raw materials and the large amount of production. Examples of the PET-G resin include “Easter PET-G · 6763” manufactured by Eastman Chemical Co., Ltd. “Easter PET-G · 6763” has a structure in which about 30 mol% of the diol component of the polyethylene terephthalate resin is replaced with 1.4-cyclohexanedimethanol, and is non-crystalline with no crystallization behavior observed by DSC measurement. Polyester resin.

  However, the present invention is not limited to this. In addition, neopentyl glycol copolymerized PET that does not exhibit crystallinity (for example, “COSMOSTER FN-305” manufactured by Toyobo Co., Ltd.) or low crystallinity. Polyester resins having a structure in which crystallization is inhibited by a copolymer component such as polyethylene terephthalate resin copolymerized with isophthalic acid and having a low crystallinity, etc. Can be used as

  The glass transition temperature of the polyester resin that is substantially amorphous as component A-2 is preferably in the range of 60 ° C. or higher and 90 ° C. or lower, but this is generally available as a general-purpose resin at a low cost. This is because the glass transition temperature of such a substantially amorphous polyester resin is in this range. Further, when an amorphous polyester resin having a glass transition temperature lower than the above range is used as the component A-2, it is difficult to cause a decrease in workability over time due to enthalpy relaxation. Since the layer 10 contains a predetermined amount of PBT resin and / or PTT resin (component A-1), crystallization of these crystalline polyester resins proceeds during storage of the laminated sheet, and embossing after a lapse of time. It may be difficult to transfer the embossed pattern on the apparatus. Further, it is difficult to obtain an amorphous polyester resin having a glass transition temperature higher than the above range at a low price.

(A-3 component)
The purpose of adding the non-polyester thermoplastic elastomer having an epoxy group as the A-3 component is to prevent the secondary processability from deteriorating with time as the enthalpy relaxation of the A layer 10 progresses. is there. When the addition amount of the A-3 component is less than 3% by mass, the effect cannot be sufficiently obtained, and when it exceeds 15% by mass, the surface hardness of the laminated sheet-coated metal plate 200 is sufficient. In addition, there is a risk that the scratchability may deteriorate. In addition, although it is finely dispersed in the polyester resin, it is a non-polyester material that is inherently poor in compatibility, so that it tends to cause a problem of bending whitening. Further, the blending amount of the A-3 component is more preferably 5% by mass or more and 10% by mass or less.

  Further, as secondary workability, not only the occurrence of cracks and cracks, but also whitening of the bent portion is a problem. Therefore, the one that makes whitening of the bent portion more remarkable by addition is used as the A-3 component. It is not possible. For example, a non-polyester thermoplastic elastomer having no epoxy group is poorly compatible with a polyester resin, and thus becomes a particulate dispersion having a large particle size in the polyester resin. This is not preferable because remarkable whitening occurs at the bent portion.

  Moreover, even for non-polyester thermoplastic elastomers that do not have an epoxy group, it is possible to reduce the dispersed particle size in the polyester resin to some extent by using a maleic anhydride-modified polyolefin resin or the like. . However, even in this case, it is not preferable because the bent portion of the laminated sheet-covered metal plate 200 is also whitened.

  On the other hand, the non-polyester thermoplastic elastomer of component A-3 used in the present invention has an epoxy group, so that it can be dispersed to some extent in the polyester resin. Therefore, whitening can hardly occur at the bent portion of the laminated sheet-coated metal plate 200.

  When a polyester-based elastomer is used, it may be possible to obtain a blend composition that exhibits good compatibility with the polyester-based resin and does not cause whitening even if it does not have an epoxy group. However, since the polyester elastomer is a polyester resin exhibiting a glass transition temperature lower than room temperature due to the copolymerization component, the glass transition temperature of the blend composition using the polyester elastomer is also lowered. Therefore, in a blend composition containing a crystalline PBT resin and / or a PTT resin like the A layer 10 of the present invention, crystallization may proceed excessively in the A layer 10 by storing at room temperature. There exists a possibility that embossing to the lamination sheet 100 after storage may become difficult resulting from it. In addition, in the composition containing a small amount of a crystalline polyester resin, with an amorphous polyester resin as a main component, as in the A layer 10 of the present invention, if crystallization proceeds excessively, a huge spherulite is formed. In some cases, the secondary workability of the laminated sheet-covered metal plate 200 after time may be lowered. Therefore, in the present invention, from the viewpoint of not changing the glass transition temperature of the blend composition, a non-polyester thermoplastic elastomer is used, and an epoxy group is obtained from the viewpoint of obtaining a certain degree of fine dispersibility in the polyester resin. The thing which has is used.

  As the non-polyester thermoplastic elastomer having an epoxy group, an epoxy-modified styrene / butadiene block copolymer or an epoxy-modified polyolefin resin can be preferably used.

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

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

(Other components of layer A 10)
A pigment may be added to the A layer 10 for the purpose of imparting a colored design property or imparting a visual hiding effect to the metal plate 60 to be coated. The pigment to be used may be one generally used for the above purpose, and the addition amount thereof may be an amount generally added for the above purpose. For example, a white-based coloring has a high concealing effect and has a fine particle size, so that a titanium oxide pigment that has little influence on the workability of the laminated sheet 100 can be used. Further, based on the titanium oxide pigment, the color can be adjusted by adding a small amount of a chromatic organic or inorganic pigment. Furthermore, a metallic pigment, a pearl pigment, or the like may be included for the purpose of improving design properties.

  When the printed pattern C30 is applied between the A layer 10 and the B layer 20, the A layer 10 needs to be a substantially transparent layer. Therefore, it is preferable that the visibility of the printed pattern C30 is improved through the A layer 10 without adding a pigment having high concealment property to the A layer 10. Further, being substantially transparent is sufficient if the printed pattern C30 can be visually recognized through the A layer 10, and may be a translucent layer in which a colored design is imparted to the A layer 10 with a pigment or dye having low concealability. It means that.

  In addition, various amounts of various additives may be added to the A layer 10 as long as the properties are not impaired. As general additives, various antioxidants such as phosphorus and phenols, process stabilizers such as lactones and phenol acrylates, heat stabilizers, UV absorbers such as triazines, benzoates, and benzophenones, Examples include hindered amine-based radical scavengers, various processing aids, metal deactivators, lubricants, antibacterial and antifungal agents, antistatic agents, flame retardants, pigment dispersibility improvers, and fillers and extenders.

  A preferable thickness of the A layer 10 is in a range of 80 μm or more and 400 μm or less. When the thickness of the A layer 10 is too thin, it becomes difficult to provide an embossed pattern having a deep depth and therefore a large maximum height (Ry). Further, if the thickness of the A layer 10 is too thick, the total thickness of the laminated sheet 100 is limited, so that the thickness allowed for the B layer 20 is limited, which may cause problems in workability in the embossing apparatus. .

<Base resin layer (B layer) 20>
The B layer 20 is a layer mainly composed of polybutylene terephthalate resin (PBT resin) and / or polytrimethylene terephthalate resin (PTT resin). Further, the B layer 20 is a PBT resin having a melting point of 215 ° C. or more and 235 ° C. or less and / or a melting point of 215 ° C. of 70% by mass or more and 95% by mass or less with the total resin component in the B layer 20 being 100% by mass. It is preferably a layer comprising a PTT resin having a temperature of 235 ° C. or lower and a polyester resin having a substantially amorphous content of 5% by mass to 30% by mass.

  The reason why the melting point of the PBT resin or PTT resin is 215 ° C. or higher is that when the embossed pattern is transferred to a conventional soft PVC sheet with an embossing machine, the temperature at which the sheet is heated by a heater without a support is 160 ° C. It is about -190 degreeC, and it is for making the B layer 20 have sufficient tension | tensile_strength even when it heats in this temperature range. The reason why the melting point is set to 235 ° C. or lower is that when a PBT resin and / or PTT resin having a higher melting point is used as the main component of the B layer 20, a sheet of conventional soft PVC is used as the metal plate 60. This is because it is difficult to firmly adhere the B layer 20 to the metal plate 60 at the same temperature as in the case of laminating.

  The reason why the main component of the B layer 20 is a PBT resin and / or a PTT resin is that these resins have a relatively high crystallization rate, and therefore a special curing is performed between the film forming process and the embossing process. It is easy to obtain the B layer 20 crystallized in the film forming process without the need for a process, that is, the B layer 20 having non-adhesiveness to the heated metal roll and the melt fracture resistance in the embossing apparatus which is the next process. Because.

  Other reasons for using PBT-based resin and / or PTT-based resin for B layer 20 are that good processability is obtained compared to PET-based resin even in a crystallized state, and for PBT-based resin, In recent years, applications such as extrusion film-forming grades have been actively developed, and it is also easy to obtain PBT resin raw materials having various melt viscosities and melting points.

  In the B layer 20, the content of the PBT resin and / or the PTT resin is preferably 70% by mass or more based on the mass of the entire resin component in the B layer 20 (100% by mass). More preferably, it is at least mass%. When the content of the PBT resin and / or the PTT resin is too small, it is difficult to obtain a preferable melt tension even if the sheet is obtained in a crystallized state.

  In addition, the content of the PBT resin and / or the PTT resin is preferably 95% by mass or less, and more preferably 90% by mass or less. When the content of the PBT resin and / or the PTT resin is too large, the crystallinity of the B layer 20 which is the bonding surface when the laminated sheet 100 is laminated on the metal plate 60 becomes too high, and conventional heating is performed. Under the conditions, it is difficult to obtain adhesion strength with the metal plate 60. Further, when the B layer 20 and the A layer 10 are obtained by the coextrusion film forming method, or when the B layer 20 and the D layer 40 described below are obtained by the coextrusion film forming method, the laminated sheet after film formation There is a risk that the warpage will be noticeable and hinder handling.

  As a PBT resin having a melting point of 215 ° C. or higher and 235 ° C. or lower, the acid component is terephthalic acid or dimethyl terephthalic acid, and the diol component is a polycondensation of each single component of 1.4-butanediol. The obtained homo-polybutylene terephthalate resin (which may contain an unintended copolymer component) may be used. Examples of the PBT resin having such a composition include “Novaduran 5020H” manufactured by Mitsubishi Engineering Plastics. When this is used, merits such as cost merits and supply stability can be obtained.

  Examples of the PTT resin having a melting point of 215 ° C. or more and 235 ° C. or less include “Cortera CP509200” manufactured by Shell, which is a homo-PTT resin.

  The substantially non-crystalline polyester resin that is a resin component other than the PBT-based resin and / or the PTT-based resin of the B layer 20 is substantially non-crystalline used as a main component of the A layer 10 described above. The same thing as a certain polyester-type resin can be used. An example is “Easter PETG 6673” manufactured by Eastman Chemical Company. The use of a polyester resin that is substantially amorphous in this way has a slow crystallization speed such as homo-PET, but when a highly crystalline resin is used, the crystallization of the PET resin over time Since the processability of the crystal phase of the PET resin is inferior to the processability of the crystal phase of the PBT resin or the like, the processability of the B layer 20 deteriorates with time, resulting in a laminated sheet and a laminated sheet. This is because the workability of the coated metal plate may be reduced.

  The thickness of the B layer 20 is preferably 15 μm or more and 200 μm or less, more preferably 20 μm or more and 100 μm or less. When the thickness of the B layer 20 is too thin, the function as the tension applying layer in the embossing machine tends to be insufficient. On the other hand, if it is too thick, the basic various functions as the laminated sheet-coated metal plate 200 are saturated and at the same time the cost is increased.

  Furthermore, the B layer 20 includes a layer that shares the function of imparting tension in an embossing apparatus, such as “B layer and C layer” described in “JP-A-2006-095892”, and an adhesive to a heating roll. You may be comprised from 2 layers of the layer which shares a prevention function. In this case, even if the lamination temperature to the metal plate 60 is further lowered, an effect of ensuring a good adhesion can be obtained.

(Other components of layer B 20)
A color pigment may be added to the B layer 20 for imparting design properties or concealing the base metal. When the printed pattern C30 is applied to the surface of the B layer 20 on the side in contact with the A layer 10 and the D layer 40 described later is not applied, a coloring pigment is mainly added to the B layer 20. The pigment used and the amount added are the same as in the case of adding to the A layer 10. Various additives are the same as those added to the A layer 10.

  Further, 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 B layer 20 is imparted. As the lubricant, those generally used for addition to a polyester resin can be used, and examples thereof include “Lycowax OP” (manufactured by Clariant Japan), which is a montanic acid-based lubricant. The addition amount of the lubricant may be a general amount of 0.2% by mass or more and 3% by mass or less based on the entire resin component of the B layer 20 (100% by mass).

  Further, in order to make the tension of the laminated sheet 100 in the embossing machine stronger, there is a linear ultrahigh molecular weight acrylic resin (for example, “Metblene P-531” manufactured by Mitsubishi Rayon Co., Ltd.) or the like. A processing aid such as polytetrafluoroethylene that has been subjected to an easy dispersion treatment that develops into a fibril shape (for example, “Metblene A-3000” manufactured by Mitsubishi Rayon Co., Ltd.) may be added. The addition amount may be a general amount of 0.2% by mass or more and 3% by mass or less based on the total resin amount of the B layer 20.

  Furthermore, in order to sufficiently impart the crystallinity necessary for obtaining non-adhesiveness and melt fracture resistance in an embossing machine to the B layer 20 by an extrusion film forming line, a crystal nucleating agent is added for crystallization. The speed may be improved. Further, the B layer 20 may contain a small amount of various additives described in the A layer 10 and other general-purpose resins.

  Regarding the B layer 20, since the PBT resin and / or the PTT resin, which is a crystalline polyester resin, is used in a crystallized state as the main component of the resin composition, the lapse of time along with the progress of enthalpy relaxation as in the A layer 10 However, there is no need to blend a non-polyester thermoplastic elastomer having an epoxy group, but it may be blended as appropriate when it is necessary to further improve the workability of the entire laminated sheet. .

<Print pattern C30>
The laminated sheet 100 of the present invention may be provided with a printed pattern C30 by printing between the A layer 10 and the B layer 20 as shown in the layer configuration in FIG. The printed pattern C30 is applied by a known method such as gravure printing, offset printing, or screen printing, and an arbitrary pattern such as a stone pattern, a wood grain pattern, a geometric pattern, or an abstract pattern is applied.

  The printed pattern C30 may be formed by printing on the surface of the B layer 20 to be laminated with the A layer 10, or may be printed on the surface of the A layer 10 to be laminated with the B layer 20. May be formed. When the D layer 40 described below is provided, it may be formed on the surface of the D layer 40 to be laminated with the A layer 10, or the A layer 10 to be laminated with the D layer 40. It may be formed on the surface. In general, forming the printed pattern C30 on the surface of the B layer 20 or the D layer 40 prints on a sheet including a layer having high crystallinity, which facilitates handling on a printing line. preferable.

<D layer 40>
The laminated sheet 100 of the present invention includes a printed pattern C30 by printing between the A layer 10 and the B layer 20 as shown in FIG. 1 (c), and further, the printed pattern C30 and the B layer 20 are provided. The D layer 40 may be provided between the two.

The D layer 40 is based on the entire resin component in the D layer 40 (100% by mass).
(D-1 component) 17 mass% or more and 38 mass% or less of PBT-type resin and / or PTT-type resin,
(D-2 component) A polyester resin having a glass transition temperature of 51% by mass or more and 78% by mass or less, which is substantially amorphous having a glass transition temperature of 60 ° C. or more and 90 ° C. or less, and
(D-3 component) The non-polyester type thermoplastic elastomer which has 3 mass% or more and 15 mass% or less of epoxy groups is contained. “D-1 component (mass%) / (D-1 component (mass%) + D-2 component (mass%))” is preferably 0.2 or more and 0.4 or less, more preferably 0.00. D-1 component and D-2 component are mix | blended so that it may become 2 or more and 0.35 or less.

  The D layer 40 is a layer that is softened by heating in the same manner as the A layer 10 and is pressed by an embossing plate roll to transfer the embossed pattern. In the form provided with the D layer 40, the thickness of the A layer 10 can be reduced. Therefore, in the configuration in which the printed pattern C30 is provided under the A layer 10, the transparency of the printed pattern C30 is not deteriorated. In addition, a deep embossed pattern can be transferred.

  In addition, since the polyester resin is a resin that is relatively susceptible to light yellowing, yellowing with time may become conspicuous if the thickness of the transparent A layer 10 is too thick. However, it is preferable that the thickness of the A layer 10 is relatively thin and the D layer 40 is provided.

  Therefore, the resin component constituting the D layer 40 can be the same as the resin component constituting the A layer 10. The color pigments and additive components that can be added to the D layer 40 are the same as those of the A layer 10.

  Further, the B layer 20 is a highly crystalline resin layer mainly composed of a PBT resin and / or a PTT resin for that purpose, whereas the D layer 40 is composed mainly of a non-crystalline polyester resin. Therefore, it is considered that the heat fusion suitability between the sheets with the A layer 10 is also better than that of the B layer 20. Therefore, after the B layer 20 and the D layer 40 are integrally formed by coextrusion film formation, the printed pattern C30 is applied to the D layer 40, and then the A layer 10 is laminated. It becomes possible to obtain strong adhesion, and the possibility of peeling between the respective layers can be reduced.

<Layer thickness of laminated sheet 100>
A preferable thickness of the entire laminated sheet 100 is 100 μm or more and 450 μm or less. When the thickness of the laminated sheet 100 is too thin, it is necessary to add a large amount of pigment to the colored layer in order to ensure visual concealment of the base, and as a result, the workability may be lowered. On the other hand, if the thickness of the laminated sheet 100 is too thick, it becomes difficult to use a molding die that has been conventionally used for forming processing such as bending of a soft PVC resin-coated metal plate. May cause problems.

  Regarding the visual concealment effect of the base metal plate required for the entire laminated sheet 100, the degree of importance varies depending on the use, but when used as a laminated sheet-coated metal plate for interior building materials, JIS K5600-4-1. It is preferable that the concealment rate measured in accordance with “Coating General Test Method / Hiding power” is 0.95 or more in the configuration of the laminated sheet 100.

  When the concealment rate is too low, the color of the base material serving as a base such as the metal plate 60 is reflected in the color of the laminated sheet 100, and when the color of the base material changes, the surface of the laminated sheet 100 is observed. It is not preferable because the color to be added appears to change. However, in applications where color change due to this reason is not particularly problematic, the concealment rate need not be 0.95 or more.

<The manufacturing method of the lamination sheet 100 for metal plate coating>
As a method for producing the laminated sheet 100 of the present invention, various known methods, a cast film forming method using an extruder equipped with a T die, an inflation method, and the like can be employed.

  After each layer is formed alone, it may be laminated and integrated in a later process to form a laminated sheet. However, in the configuration not including the printed pattern C30 shown in FIG. 1 (a), the two layers of the A layer 10 and the B layer 20 are combined. It is most efficient and preferable to form a film integrally by a coextrusion film forming method using two extruders and a feed block or a multi-manifold die.

  In the configuration having the printed pattern C30 shown in FIG. 1B, the A layer 10 is formed as a single layer, and after the printed pattern C30 is applied to the surface of the B layer 20 that is also formed as a single layer, It is preferable to integrate them. Further, in the configuration having the printed pattern C30 shown in FIG. 1C, the printed pattern C30 is applied to the surface of the D layer 40 of the laminated sheet composed of the D layer 40 and the B layer 20 integrally formed by the coextrusion method. Thereafter, it is preferable that the A layer 10 formed as a single layer is laminated and integrated. In these cases, the printed pattern C30 may be applied to the surface of the A layer 10 on the side laminated with the B layer 20 or the D layer 40.

  The type of the resin binder of the printed pattern C30 is not particularly limited, but by appropriately selecting this binder type, the lamination integration between the A layer 10 and the B layer 20 or the A layer 10 and the D layer 40 is thermally fused. It can be a laminated layer. Alternatively, at the time of applying the printed pattern C30, a heat-adhesive coating layer can be simultaneously applied and heat-sealed and laminated. The integration of the A layer 10 and other layers by heat fusion lamination is preferably carried out at the introduction portion to the heating roll of the embossing apparatus.

  However, the lamination integration of the A layer 10 and the other layers is not necessarily performed by the heat fusion lamination with the embossing machine, and the heat fusion lamination may be performed in another process. Moreover, it can also be set as lamination | stacking with a dry lamination adhesive agent etc.

<The manufacturing method of the metal sheet coating | coated laminated sheets 100d and 100e which have an embossed design>
FIG. 2 shows an example of an embossing apparatus 300 that has been generally used for providing an embossed pattern on a soft PVC sheet. The embossing apparatus 300 according to the illustrated embodiment 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 the form shown in FIG. 2, the A layer 10 formed as a single layer, and the two-layer coextruded sheet composed of the B layer 20 and the D layer 40 with the printed pattern C30 on the D layer 40 side are supplied, respectively. As described above, heat fusion lamination is performed by the heating roll 310 of the embossing apparatus.

  An embossed pattern can be imparted to the metal sheet-covering laminated sheet 100 (100a to 100c) of the present invention by an embossing apparatus 300 in the same manner as a conventional soft PVC sheet. Since the layer B 20 has the characteristics of the present invention, the laminated sheet 100 of the present invention has non-adhesiveness to the heating roll 310 heated to about 100 ° C. to 140 ° C., and the heater Even at a sheet heating temperature of 160 ° C. to 190 ° C. according to 330, width shrinkage, wrinkles, breakage, etc. do not occur. Moreover, since the A layer 10 has good embossing suitability, a laminated sheet having an embossed design to which an embossed design having a good appearance is given can be obtained.

  In FIG. 1 (d) and (e), the laminated constitution of the metal sheet coating | coated laminated sheets 100d and 100e which have an embossing design was shown. The laminated sheet 100d having an embossed design is obtained by giving an embossed design to the laminated sheet 100a. Moreover, the lamination sheet 100e which has an embossing design gives the embossing design to the lamination sheet 100c.

  Moreover, you may give the coloring design by what is called wiping printing, and the design of glossiness difference to the recessed part of A layer 10 surface in which the embossed design was formed. The colored ink layer formed in the embossed recesses by wiping printing is preferably formed with colored ink using a two-component curable urethane resin, etc., but from polyester resin, vinyl chloride resin, acrylic resin, etc. You may form using the 1 liquid ink which becomes.

  As the pigment used in the color ink, a pigment used for a normal printing ink can be used. The wiping printing itself has been carried out since the days of embossed design sheets using soft PVC sheets, and can be applied by various known methods such as a doctor blade method and a roll coating method.

  In addition, a transparent adhesive resin / adhesive resin, etc. with a thickness that completely fills even the embossed convex part is coated, and a transparent biaxially stretched polyester film, etc. is coated as a surface resin layer. It is also possible to provide a laminated sheet having a structure that has a rough surface and also has an uneven design by embossing inside.

<Method for Producing Laminated Sheet-Coated Metal Plate 200>
By laminating the B layer 20 side of the above-described laminated sheet 100 for covering a metal plate or the laminated sheet 100d, 100e having an embossed design on the metal plate 60, the laminated sheet-covered metal sheet 200 is manufactured. FIG. 1F shows a layer structure of a laminated sheet-covered metal plate 200 manufactured by laminating a laminated sheet 100e having an embossed design on a metal plate 60. FIG.

  As the metal plate 60 used for the laminated sheet-coated metal plate 200, hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, tin plated steel plate, aluminum / zinc alloy plated steel plate, aluminum / magnesium / zinc alloy plated Various steel plates such as steel plates and stainless steel plates, aluminum plates, aluminum alloy plates, titanium alloy plates and the like can be used. These metal plates may be subjected to ordinary chemical conversion treatment. The thickness of the metal plate 60 varies depending on the use of the laminated sheet-covered metal plate 200, but can be selected in the range of 0.1 mm or more and 10 mm or less.

  The method of laminating the laminated sheets 100, 100d, and 100e on the metal plate 60 is not particularly limited, but laminating with the adhesive 50 is common. Examples of the adhesive 50 include commonly used thermosetting adhesives such as acrylic adhesives, epoxy adhesives, urethane adhesives, and polyester adhesives. Among these, since a sheet | seat consists of a polyester-type resin, it is preferable to use a polyester-type adhesive agent. As a laminating method, the adhesive film thickness after drying is applied to the metal surface on which the laminated sheets 100, 100d, and 100e are bonded using the commonly used coating equipment such as reverse coater and kiss coater on the metal plate 60. The thermosetting adhesive is applied so as to be about 2 μm or more and 10 μm or less.

  Next, the coated surface is dried and heated by an infrared heater and / or a hot air heating furnace, and the surface temperature of the metal plate 60 is maintained at a temperature of about 220 ° C. to 250 ° C., and immediately using a roll laminator, The laminated sheet-covered metal plate 200 can be obtained by coating and cooling so that the B layer 20 side becomes an adhesive surface.

  In addition, the laminated sheet-covered metal plate 200 of the present invention has good workability, and is a building interior material such as a door material, a unit bath wall material, a unit bath ceiling material, a partition material, a panel material, and an elevator interior material, It can be suitably used as a household appliance housing member such as a steel furniture member, AV equipment, and air conditioner cover.

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

<Preparation of laminated sheet 100>
<Examples 1-20, 23, 24, Comparative Examples 1-10, 14, 15>
The laminated sheets of Examples 1 to 20, 23, and 24 and Comparative Examples 1 to 10, 14, and 15 shown in Tables 4 and 6 are multi-manifold systems using two twin-screw kneading extruders having a diameter of 65 mm. By co-extrusion, a two-layer laminated sheet composed of an A layer and a B layer was obtained by a general method in which the resin flowing out from the T-die was taken up by a casting roll.

  Table 1 shows the composition and thickness of the A layer in each example. The composition and thickness of the B layer are shown in Table 2. As a pigment, 24 parts by mass of a white pigment mainly composed of titanium oxide was added to the A layer (the total amount of the resin components in the A layer was 100 parts by mass).

<Examples 21 and 22, Comparative Examples 11 to 13>
The laminated sheets of Examples 21 and 22 and Comparative Examples 11 to 13 shown in Table 5 were produced as follows. First, using a twin screw kneading extruder with a diameter of 65 mm, the A layer was extruded and formed as a single-layer transparent sheet with a T die, and separately from this, using two twin screw kneading extruders with a diameter of 65 mm, By a multi-manifold type co-extrusion, a two-layer laminated sheet composed of a D layer and a B layer was obtained by a general method in which the resin flowing out from the T-die was drawn with a casting roll. Table 1 shows the composition and thickness of the A layer in each example. The composition and thickness of the B layer are shown in Table 2. The composition and thickness of the D layer are shown in Table 3. As the pigment, 20 parts by mass of a white pigment mainly composed of titanium oxide was added to both the B layer and the D layer (with the total amount of resin components in each layer being 100 parts by mass).

  On the surface of the D layer side of the obtained two-layer laminate sheet composed of the D layer and the B layer, a grainy pattern is printed by gravure printing using an acrylic / urethane-based ink, and then the A layer is shown in FIG. Thus, heat fusion lamination was performed at the heating roll portion of the embossing apparatus, and the lamination was integrated.

The raw materials used in the above examples and comparative examples are as follows.
“Easter PETG • 6763” (indicated as “PETG6763” in the table) is an amorphous polyester resin manufactured by Eastman Chemical Company. The dicarboxylic acid component is terephthalic acid, and about 30 mol% of the diol component is 1.4-cyclohexanedimethanol and about 70 mol% is ethylene glycol. The glass transition temperature was 78 ° C. and no melting point was observed.

  “PCTG 5445” is an amorphous polyester resin manufactured by Eastman Chemical Company. The dicarboxylic acid component is terephthalic acid, and about 65 mol% of the diol component is 1.4-cyclohexanedimethanol and about 35 mol% is ethylene glycol. The glass transition temperature was 86 ° C. and no melting point was observed.

  “Novaduran 5020H” (indicated as “PBT5020H” in the table) is a (homo) polybutylene terephthalate resin manufactured by Mitsubishi Engineering Plastics. The measured melting point was 224 ° C.

  “Cortera CP509200” (indicated as “PTTCP509200” in the table) is a (homo) polytrimethylene terephthalate resin manufactured by Shell. The measured melting point was 225 ° C.

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

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

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

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

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

<Embossing to laminated sheet>
The embossed pattern was transferred using an embossing apparatus generally used for embossing a soft vinyl chloride sheet as shown in FIG. Moreover, regarding the sheet | seat which has the printing pattern C, as above-mentioned, the two-layer lamination sheet which consists of A layer, D layer, and B layer is heat-seal-laminated by the heating roll part of an embossing apparatus. As an outline of the process of the embossing device, first, the sheet is preheated by contact type heating using a heating roll, and then the sheet is heated to an arbitrary temperature by non-contact type heating using an infrared heater. The embossed pattern is transferred to form an embossed design sheet.

  40 degreeC, 90% RH, after forming each sheet | seat of an Example and a comparative example on the assumption that the case where it uses for emboss provision after a certain period passes after forming a laminated sheet After being allowed to stand in a constant temperature and humidity chamber maintained at 10 days, embossing was performed.

  As the embossing condition, the heating roll was set to 110 ° C., and then heating was performed with an infrared heater so that the sheet surface temperature immediately before contacting the embossing roll was 180 ° C. The embossing roll was adjusted to 110 ° C. with a hot water circulator. With respect to Examples 1 to 22 and Comparative Examples 1 to 13, a plate on which an abstract pattern with relatively concavity and convexity having Ry (maximum height) = 127 μm and Ra (centerline average roughness) = 16 μm was transferred. Using. In Examples 23 and 24 and Comparative Examples 14 and 15, a plate on which an abstract pattern having a relatively general roughness was transferred as a resin-coated metal plate with Ry = 46 μm and Ra = 7 μm was used.

<Production of laminated sheet-coated metal plate>
A commercially available polyester adhesive for polyvinyl chloride coated metal sheet is applied to the metal surface to which the laminated sheet is bonded so that the adhesive film thickness after drying is about 2 μm to 4 μm, and then an infrared heater and hot air The laminated sheet-covered metal plate is coated with a roll laminator and cooled by water spraying immediately while the surface temperature of the metal plate is maintained at 235 ° C. by performing solvent drying and heating on the coated surface in a heating furnace. Obtained. As the metal plate, for Examples 1 to 22 and Comparative Examples 1 to 13, a galvanized steel plate having a thickness of 0.45 mm was used. For Examples 23 and 24 and Comparative Examples 14 and 15, a galvanized steel sheet having a thickness of 1.6 mm was used.

<Evaluation of laminated sheet for metal coating and laminated sheet-coated metal plate>
The following items were evaluated for the laminated sheet for metal coating and the laminated sheet-coated metal plate obtained in the above examples and comparative examples. The results are shown in Tables 4-6.

(Lamination of laminated sheet, handleability of laminated sheet)
About Examples 1-20 and Comparative Examples 1-10, the handleability before embossing of the laminated sheet of A layer and B layer created by the coextrusion film forming method was evaluated. These laminated sheets were cut out in an MD direction of 15 cm × TD direction of 30 cm, and placed on a surface plate so that the B layer side became the lower surface, and the state of warping was observed. When the warpage is strong and completely cylindrical, or when the arch shape with a height of 10 cm or more from the surface plate surface is warped, “×” is less than 10 cm but the warpage is 5 cm or more. In the case of “△” and a warp of less than 5 cm, it was evaluated as “◯” because the handleability was good.

(Applicability of embossing after time: non-adhesive)
When embossing was applied with the embossing machine shown in FIG. 2, the sheet stuck to the heating drum (heated metal roll) and difficult to peel was “x”. As a result, it was evaluated as “Δ” if the product could not be stably produced, and “○” if it did not stick.

(Embossing suitability after aging: fusing resistance)
When embossing was applied by the embossing machine shown in FIG. 2, the sheet was evaluated as “X” when the sheet was melt-ruptured during heating of the sheet by the heater, and “◯” when it was not. When the breakage or width shrinkage was remarkable although it did not break, it was evaluated as “Δ”.

(Embossing suitability after time: Embossed plate transferability)
The sheet embossed with the embossing machine shown in FIG. 2 is visually observed, “○” indicates that the embossed pattern is clearly transferred, and “△” indicates that the transfer is slightly shallower than this. However, those having a shallow embossed pattern or having a rough surface regardless of the embossed pattern were evaluated as “x”.

(Processability evaluation: adhesion bending test)
For the laminated sheet-coated metal plate obtained by laminating the laminated sheets of Examples 1 to 22 and Comparative Examples 1 to 13 on a metal plate having a thickness of 0.45 mm, an impact adhesion bending test was performed, and the surface state of the laminated sheet in the bent portion was determined. Judgment was made visually. The impact adhesion bending test was performed as follows. Samples each of 50 mm × 150 mm were prepared from the length direction and width direction of the laminated sheet-coated metal plate, kept at 23 ° C. for 1 hour or longer, and then subjected to 180 ° (preliminary bending radius 2 mm) as a pre-bending. ) And a cylindrical weight having a diameter of 75 mm and a mass of 5 kg was dropped from the height of 50 cm onto the sample.

  Two types of tests, “initial” and “after time”, were performed. Regarding the initial workability evaluation in which the enthalpy relaxation did not proceed, the measurement was carried out within 24 hours after the laminated sheet was laminated on the metal plate. Regarding the workability evaluation after time, after leaving the laminated sheet-covered metal plate for 30 days in a constant temperature and humidity chamber maintained at 40 ° C. and 90% RH, it was taken out and left in a room at 23 ° C. for 24 hours. Measurements were performed. The surface state of the laminated sheet in the bent part after processing is visually determined. “○” indicates that there is almost no change, “△” indicates that the surface layer is slightly cracked, and slight bending whitening occurs. The case where cracks occurred in the surface layer or the case where remarkable bending whitening occurred was evaluated as “x”.

(Processability evaluation: V bending test by hydraulic bender)
For the laminated sheet-covered metal plate obtained by laminating the laminated sheets of Examples 23 and 24 and Comparative Examples 14 and 15 on a metal plate having a thickness of 1.6 mm, a V-bending test was performed by a hydraulic bender, and the surface of the laminated sheet in the bending portion was measured. The state was judged visually. The V-bending test was performed as follows for two types of “initial” and “after time”. Samples of 50 mm x 150 mm were prepared from the length direction and width direction of the laminated sheet-coated metal plate, respectively, kept at 23 ° C for 1 hour or longer, and then using a hydraulic bending tester (hydraulic bender) to have an inner radius of 2 mm And bent at 90 degrees. The evaluation criteria are the same as in the above-mentioned adhesion bending test.

(Boiling water immersion test)
Using an Erichsen test apparatus specified in JIS K6744 on a 60 mm x 60 mm laminated sheet-coated metal plate, a 6 mm overhang is provided so that the laminated sheet coating side is convex, and then immersed in boiling water for 3 hours. The surface condition of was visually determined. The case where there was no change was evaluated as “◯”, the case where the surface was slightly roughed was evaluated as “Δ”, and the case where deformation such as significant swelling occurred in the resin layer was evaluated as “X”.

(Surface hardness: pencil hardness test)
The surface hardness of the laminated sheet-coated metal plate was evaluated according to JIS K5600-5-4 “General test method for paint / Scratch hardness (pencil method)”. In a constant temperature room of 23 ° C., drawing was performed using a jig capable of drawing with a weight of 1 kg while maintaining an angle of 45 ° with respect to the resin sheet surface of the laminated sheet-coated metal plate cut out to 80 mm × 60 mm. The surface state of the laminated sheet at the portion was visually determined. “B” where the 2B pencil was not scratched at all, “◯”, 2B was scratched, but the 3B pencil was not scratched at all, “△”, and the 3B pencil was scratched “ “×” was evaluated.

(Metal plate adhesive strength)
Using a 20 mm × 100 mm laminated sheet-coated metal plate as a test piece, a peel strength measurement in accordance with JIS Z0237 “Adhesive tape / adhesive sheet test method—180 degree peeling adhesive strength to test piece” is performed with a measurement width of 20 mm, and a laminated sheet The adhesion strength between the metal plate and the metal plate was measured. Those judged to have sufficient adhesive strength (40N / 20mm or more) “◯”, those having relatively poor adhesive strength but practically no problem (20N / 20mm or more and less than 40N / 20mm) “Δ”, and those having lower adhesive strength (less than 20 N / 20 mm) were evaluated as “x”.

  Examples 1 to 20 and Comparative Examples 1 to 10 in Table 4 are laminated on a 0.45 mm steel plate and are intended for unit bath use. A thick A layer is used for deep embossing.

  Examples 21 and 22 and Comparative Examples 11 to 13 in Table 5 are laminated on a 0.45 mm steel plate and are intended for unit bath use. Since it has a printing design, the visibility is improved by thinning the A layer, but it is provided with a D layer that is a thick embossing layer for providing deep embossing.

  Examples 23 and 24 and Comparative Examples 14 and 15 in Table 6 are laminated on a 1.6 mm steel plate, and are intended for elevator use. And it is going to transfer the embossing of the same depth as the soft PVC sheet coating | cover metal plate used for this use.

<Evaluation results>
Comparative Example 1 is a case where the amount of the non-polyester thermoplastic elastomer having an epoxy group contained in the layer A is less than the range of the present invention. It was the result that cracked.

  In Comparative Example 2, the P-layer resin or PTT-based resin was not included in the A layer, and the embossed pattern transferred to the surface of the A layer by the boiling water immersion test became shallow. When embossing at a normal depth is transferred, it may not be noticeable, but when a deep embossing is transferred as in this evaluation, the design feeling is clearly reduced.

  In Comparative Example 3, the amount of PBT resin or PTT resin contained in the A layer is too much than the range of the present invention, and “A-1 component (mass%) / (A-1 component (mass%) + A -2 component (mass%)) "exceeds 0.4, and while the laminated sheet is allowed to stand in a constant temperature and humidity chamber maintained at 90% RH at 40 ° C for 10 days, Crystallization progressed, making it difficult to transfer the embossed plate with an embossing apparatus.

  Comparative Example 4 and Comparative Example 5 are cases where the amount of the non-polyester thermoplastic elastomer having an epoxy group contained in the A layer is larger than the range of the present invention, and the scratches on the surface as the laminated sheet-coated metal plate The pencil hardness, which is a measure of sex, was reduced.

  Comparative Examples 6 and 7 are cases where a non-polyester thermoplastic elastomer having no epoxy group was added to the A layer, but the bending workability of the resin-coated metal plate was poor from the beginning. It is considered that void whitening occurred in the bent portion due to the elastomer component being dispersed in a relatively large size in the polyester resin of the A layer.

  Comparative Example 8 and Comparative Example 9 are cases where a polyester-based elastomer was added to the A layer, but in Comparative Example 8 where the amount added was relatively small, the effect of improving the workability of the laminated sheet-coated metal plate after aging was It was not obtained. Further, in Comparative Example 9 in which the addition amount was larger than this, it was difficult to transfer the embossed plate with the embossing apparatus. The amount of PBT resin added is within the scope of the present invention, and “A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” is also within the scope of the present invention. However, because the glass transition temperature of the blend composition of the A layer was lowered by the addition of the polyester-based elastomer, the laminated sheet was allowed to stand in a constant temperature and humidity chamber maintained at 40 ° C. and 90% RH for 10 days. It is considered that the crystallization of the A layer progressed in the meantime.

  Comparative Example 10 is a case where the layer B used is one in which the addition amount of the PBT resin or the PTT resin is smaller than the range of the present invention. When the laminated sheet is heated by the embossing apparatus, Elongation in the flow direction and wrinkles occurred, and stable embossing was difficult.

  Comparative Example 11 is a case in which a non-polyester thermoplastic elastomer having an epoxy group was not used as the composition of the D layer, and the resin layer was obtained by bending the laminated sheet-covered metal plate after the lapse of time. It was the result that cracked.

  In Comparative Example 12, as the composition of the D layer, the amount of the PBT resin contained in the D layer is too much than the range of the present invention, and “D-1 component (mass%) / (D-1 component (mass%) + D -2 component (mass%)) "exceeds 0.4, and while the laminated sheet is allowed to stand for 10 days in a constant temperature and humidity chamber maintained at 40 ° C. and 90% RH, Crystallization progressed, and the only layer that could be embossed was the A layer having a thickness of 50 μm, which made it difficult to transfer the embossed plate with an embossing apparatus.

  Comparative Example 13 is a case where a non-polyester thermoplastic elastomer having no epoxy group is added to the D layer. As a result, whitening is observed in the bent portion through the transparent A layer and the printed pattern C. It was.

  In Comparative Example 14, the same non-polyester thermoplastic elastomer having no epoxy group as in Comparative Example 6 was added to the A layer and laminated to a steel plate having a thickness of 1.6 mm. In the V-bending test, remarkable whitening was observed in the bent portion.

  In Comparative Example 15, the same polyester elastomer as in Comparative Example 9 was added to the A layer, but it was difficult to transfer the embossed plate with an embossing apparatus. Regarding Comparative Example 15, this laminated sheet with poor emboss transfer was laminated on a metal plate having a thickness of 1.6 mm, and the workability was evaluated. However, the effect of improving the workability of the laminated sheet-covered metal plate after aging was obtained. There wasn't.

  On the other hand, in Examples 1-24 of this invention, all have the favorable emboss provision suitability with an embossing apparatus. In particular, there was no problem in transferability even when embossing was performed after the laminated sheet was formed and left for a while. Further, the heat resistance of the transferred emboss was not a problem in practice. Further, even when the laminated sheet-covered metal plate was left to stand for a while and then subjected to a bending process, there was no decrease in workability due to the influence of enthalpy relaxation. Furthermore, a laminated sheet-coated metal plate having a high surface hardness and good scratch resistance was obtained. Furthermore, in Examples 21 and 22, a laminated sheet-covered metal plate having a printing design in addition to these characteristics was obtained. Moreover, about Example 20, it is a case where only PBT-type resin is used for B layer, and the curvature of the laminated sheet produced by co-extrusion film formation of A layer and B layer is remarkable, and it passes to an embossing apparatus. The workability of the work was slightly bad.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. Rather, it can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and a laminated sheet for covering a metal plate, a laminated sheet-covered metal plate, and an elevator interior material with such a change Etc. are also to be understood as being included within the scope of the present invention.

The laminated sheet for metal plate coating ((a) to (c)), the laminated sheet for metal plate coating ((d) and (e)) having an embossed design, and the laminated sheet coated metal plate ((f)) of the present invention. It is a schematic diagram which shows a layer structure. It is the schematic diagram of the embossing apparatus generally used in order to provide an embossed pattern to the sheet | seat of soft PVC conventionally.

Explanation of symbols

10 Embossing layer (A layer)
20 Base resin layer (B layer)
30 Print Pattern C
40 D layer 50 Adhesive layer 60 Metal plate 100a-100c Laminated sheet for metal plate coating 100d, 100e Laminated sheet for metal plate coating having an embossed design 200 Laminated sheet coated metal plate

Claims (13)

A laminated sheet comprising two layers of an embossing layer (A layer) and a base resin layer (B layer),
The A layer is 100% by mass of the entire resin component in the A layer,
(A-1 component) 17% by mass or more and 38% by mass or less of polybutylene terephthalate resin and / or polytrimethylene terephthalate resin,
(A-2 component) A polyester-based resin having a glass transition temperature of 51% by mass or more and 78% by mass or less, which is substantially amorphous having a glass transition temperature of 60 ° C. or more and 90 ° C. or less, and
(A-3 component) a non-polyester thermoplastic elastomer having an epoxy group of 3% by mass to 15% by mass,
“A-1 component (mass%) / (A-1 component (mass%) + A-2 component (mass%))” is 0.2 or more and 0.4 or less,
The layer B is a layer mainly composed of a polybutylene terephthalate resin and / or a polytrimethylene terephthalate resin, and has a total thickness of 100 μm or more and 450 μm or less. The substantially non-crystalline polyester resin of the component A-2 is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 25 mol% or more and 50 mol% or less of the diol component is 1.4- The laminated sheet for covering a metal plate according to claim 1, wherein the laminated sheet is a copolyester comprising cyclohexanedimethanol and the remaining 50 mol% or more and 75 mol% or less comprising other diol components mainly composed of ethylene glycol. The metal sheet covering laminated sheet according to claim 1 or 2, wherein a printed pattern C is provided between the A layer and the B layer. A D layer is provided between the printed pattern C and the B layer,
The said D layer makes the whole resin component in the said D layer 100 mass%,
(D-1 component) 17% by mass or more and 38% by mass or less of polybutylene terephthalate resin and / or polytrimethylene terephthalate resin,
(D-2 component) A polyester resin having a glass transition temperature of 51% by mass or more and 78% by mass or less, which is substantially amorphous having a glass transition temperature of 60 ° C. or more and 90 ° C. or less, and
(D-3 component) containing 3% by mass or more and 15% by mass or less of a non-polyester thermoplastic elastomer having an epoxy group,
The metal plate according to claim 3, wherein “D-1 component (mass%) / (D-1 component (mass%) + D-2 component (mass%))” is 0.2 or more and 0.4 or less. Laminated sheet for coating. The substantially non-crystalline polyester resin of component D-2 has terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 25 mol% or more and 50 mol% or less of the diol component is 1.4- The laminated sheet for covering a metal plate according to claim 4, which is a copolymerized polyester comprising cyclohexanedimethanol and the remaining 50 mol% or more and 75 mol% or less comprising other diol components mainly composed of ethylene glycol. The B layer is 100% by mass of the entire resin component in the B layer,
A polybutylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less, and / or a polytrimethylene terephthalate resin having a melting point of 215 ° C. or more and 235 ° C. or less,
The laminated sheet for metal plate coating in any one of Claims 1-5 which is a layer containing the polyester-type resin which is 5 to 30 mass% substantially amorphous. The substantially non-crystalline polyester resin constituting the B layer is mainly composed of terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component, and 25 mol% or more and 50 mol% or less of the diol component is 1.4- The laminated sheet for covering a metal plate according to claim 6, which is a copolymerized polyester comprising cyclohexane dimethanol and the remaining 50 mol% or more and 75 mol% or less comprising other diol components mainly composed of ethylene glycol. The laminated sheet for covering a metal plate according to any one of claims 1 to 7, and the laminated sheet for covering a metal plate, comprising a concavo-convex shape formed by an embossed plate on the surface of the A layer side of the laminated sheet. . A laminated sheet for covering a metal plate according to any one of claims 1 to 8, and a laminated sheet-covered metal comprising the metal plate, wherein the layer B side of the laminated sheet is laminated on a metal plate via an adhesive Board. An elevator interior material using the laminated sheet-coated metal plate according to claim 9. A unit bus member using the laminated sheet-coated metal plate according to claim 9. A general interior wall material using the laminated sheet-coated metal plate according to claim 9. A partition material using the laminated sheet-coated metal plate according to claim 9.

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