JP4776905B2 - Laminated sheet, embossed design sheet and embossed design sheet coated metal plate - Google Patents

Description

  The present invention is excellent in embossing suitability and can be suitably used for AV equipment, home appliance exteriors such as air conditioner covers, plywood furniture, steel furniture, and coating materials having embossed designs such as building interiors. The present invention relates to a laminated sheet, an embossed design sheet to which embossing is applied, and an embossed design sheet-covered metal plate coated with the embossed design sheet. More specifically, there is little risk of problems such as width shrinkage, wrinkles, and sheet breakage when the laminated sheet is heated with an embossing machine, and embossing is applied in the same way as with conventional soft PVC sheets. The embossed design sheet excellent in the heat resistance of the embossing provided with the embossing by this method, and the embossed design sheet-covered metal plate coated thereby.

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

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

  In this embossing machine, it is common to incorporate a design that makes it easy to replace and remove the embossing plate roll, and the diameter of the embossing plate roll is small compared to the casting roll of the extrusion film-forming equipment, Since various types of embossing plate rolls are prepared, the embossing pattern can be easily and economically changed.

  In addition, for soft PVC sheets having a printing design at the same time as the embossing design, after printing on the surface of the colored soft PVC sheet, the transparent soft PVC sheet is laminated and integrated, and this laminated sheet is continuously connected to the embossing machine. It was obtained by passing through. In this case, the sheet is preheated with an embossing machine, and two layers of sheets are laminated and integrated by thermal fusion, etc., and production is not required because a special process for lamination is not required. It was good in terms of cost and cost.

  Thus, although it is a soft PVC sheet having excellent characteristics, in recent years, due to the VOC problem, the endocrine disrupting action problem, the problem of generating hydrogen chloride gas and other chlorine-containing gases during combustion, etc., the vinyl chloride resin Use has come to be restricted.

  Therefore, in place of the soft PVC sheet, it has been studied to use a sheet made of a polyester resin excellent in workability and surface scratch resistance for a resin-coated metal plate having an embossed design. As such a sheet, Patent Document 1 proposes a decorative sheet in which a base film layer mainly composed of an amorphous polyester resin and a protective film layer mainly composed of a transparent amorphous polyester resin are laminated. ing.

Further, in Patent Document 2, an embossable layer (layer A) containing a large amount of a substantially amorphous or low crystalline resin composition or a large amount of the substantially amorphous or low crystalline resin composition. And a sheet with a two-layer structure composed of a substantially crystalline resin composition or a base material layer (B layer) containing a large amount of the substantially crystalline resin composition, It has been proposed that the current embossing device for PVC can be used without causing problems such as sheet fusing, sticking to a heating roll, or winding even when using an embossing device for PVC.
JP 2000-233480 A WO03045690

  However, since the composition in Patent Document 1 does not provide sufficient tension when the sheet is heated by an embossing machine, the width of the sheet may be reduced, wrinkled, broken, etc. It is difficult to produce sheets with.

  In Patent Document 2, when the crystallinity of the layer mainly composed of crystalline polyester is relatively high, the work stability in the embossing machine is good, but the laminated sheet after embossing is laminated to the metal plate. In doing so, there is a fear that sufficient adhesion cannot be obtained unless the metal plate is heated to a relatively high temperature. Further, when the metal plate is heated to a high temperature, there is a concern that the coating treatment applied to the back surface of the metal plate causes thermal discoloration. On the contrary, in order to solve the above-mentioned problems when laminating with a metal plate, when the crystallinity of a layer mainly composed of crystalline polyester resin is relatively lowered, there is a problem in workability with an embossing machine. There is a possibility that it may come out, and the range in which both can be balanced has been restricted.

  Therefore, the present invention does not cause sheet shrinkage, crease, breakage, etc. when embossing is applied, and the workability in the embossing machine and the adhesion to the metal plate are well balanced, and the above problems are avoided. It is an object of the present invention to provide a laminated sheet, an embossed design sheet, an embossed design sheet-coated metal plate, a building interior material, and the like that can be solved.

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

  1st this invention is a lamination sheet which consists of at least 3 layers of A layer (10), B layer (20), and C layer (30a), Comprising: Said A layer (10) is substantially amorphous. A non-oriented resin layer having a thickness of 45 μm or more mainly composed of a polyester-based resin, wherein the B layer (20) is based on the mass of the entire resin component in the B layer (20) (100% by mass), A non-oriented resin layer having a thickness of 20 to 200 μm containing 75 to 95% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C., and the C layer (30a) is Based on the mass (100% by mass) of the entire resin component in the C layer (30a), the polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C. is 55 to 70% by mass, substantially non- Crystalline It is a non-oriented resin layer having a thickness of 5 μm or more and containing 45 to 30% by mass of a certain polyester resin, and is a laminated sheet (100a) having a total thickness in the range of 70 to 300 μm.

  In this laminated sheet (100a), the A layer (10) is a layer having good emboss transferability, and the B layer (20) has a sufficient sheet tension when the laminated sheet (100a) is heated by an embossing machine. C layer (30a) is non-adhesive to the heated metal roll of the embossing machine, and at the same time the metal plate temperature is lower than when the B layer (20) is directly laminated to the metal plate. Even so, it is a layer capable of obtaining sufficient adhesive strength.

  The second aspect of the present invention is a laminated sheet comprising at least three layers of an A layer (10), a B layer (20) and a C layer (30b), wherein the A layer (10) is substantially amorphous. A non-oriented resin layer having a thickness of 45 μm or more mainly composed of a polyester-based resin, wherein the B layer (20) is based on the mass of the entire resin component in the B layer (20) (100% by mass), A non-oriented resin layer having a thickness of 20 to 200 μm comprising 75 to 95% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C., and the C layer (30b) is Thickness of 5 μm comprising 70-100% by mass of polybutylene terephthalate (PBT) resin having a melting point (Tm) of less than 210 ° C., based on the mass (100% by mass) of the entire resin component in the C layer (30b). A resin layer of a non-oriented above the total thickness of the laminated sheet is in the range of 70~300μm (100b).

  In this laminated sheet (100b), the same effect as in the first aspect of the present invention can be obtained.

  In the first aspect of the present invention, the substantially amorphous polyester resin of the A layer (10) and the C layer (30a) is mainly composed of terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component. About 20-80 mol. Of the diol component. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining about 80-20 mol. % Is preferably a copolyester comprising ethylene glycol.

  Obtaining the merit of stability and cost of raw material supply by using a commercially available material as the polyester resin which is substantially amorphous for the A layer (10) and the C layer (30a) Can do.

  In the second aspect of the present invention, the substantially amorphous polyester-based resin of the A layer (10) is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and is about 20 to 80 mol of the diol component. . % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining about 80-20 mol. % Is preferably a copolyester comprising ethylene glycol.

  By using a material that is easily commercially available as the substantially amorphous polyester-based resin of the A layer (10), it is possible to obtain the merits of stability of raw material supply and cost.

The storage elastic modulus at 190 ° C. in the dynamic viscoelastic tension method 10 Hz measured as a laminated sheet is preferably 1 × 10 ⁷ Pa or more in the MD direction of the sheet.
Here, the “MD direction” refers to the longitudinal direction (Machine Direction) of the sheet.

  This clarifies the rupture resistance of the heated sheet in the embossing machine. Here, “190 ° C.” defines that when the embossed pattern is transferred to a conventional soft PVC sheet by an embossing machine, the temperature at which the sheet is heated by a heater without a support is about 160 to 190 ° C. It depends. After being heated to this temperature, an embossed design sheet with good embossing heat resistance can be obtained by transferring the embossed pattern with an embossing plate roll.

  Polybutylene terephthalate (PBT) having a melting point (Tm) of 20 to 40% by mass of 210 to 230 ° C. in the A layer (10), based on the mass (100% by mass) of the entire resin component in the A layer (10). It is preferable that a system resin is blended.

  Thereby, the survivability of embossing at the time of contact with high temperature water, such as a boiling water immersion test, can be made more favorable.

  The A layer (10) is substantially transparent, and a printed pattern (D) (40) is provided between the A layer (10) and the B layer (20). You can also.

  Thereby, the lamination sheet (100c) which has a printing design in addition to an embossing design can be obtained.

  The A layer (10) is substantially transparent, and a printed pattern (D) (40) is provided between the A layer (10) and the B layer (20). Between the printed pattern (D) (40) and the B layer (20), a non-oriented resin layer (E layer) (50) mainly composed of a substantially amorphous polyester resin is disposed. It can also be set as the structure.

  Thus, since the E layer (50) is a layer that is deformed by pressing with an embossing plate roll in the same manner as the A layer (10), the thickness of the A layer (10) is reduced to improve the transparency of the printing layer. Deeper embossed transfer is possible.

  The substantially non-crystalline polyester resin of the E layer (50) is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and about 20 to 80 mol. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining about 80-20 mol. % Is preferably a copolyester comprising ethylene glycol.

  Thereby, the merit of stability and cost of raw material supply can be obtained by using a commercially easily available material.

  3rd this invention is an embossed design sheet which has the embossed pattern which heated said laminated sheet (100a-100d) to the range of 160-190 degreeC, and was formed in the A layer (10) side surface by the embossing plate roll. is there.

  Embossing heat resistance practically sufficient can be obtained by providing embossing to the laminated sheets (100a to 100d) heated to this temperature.

  The fourth aspect of the present invention is an embossed design sheet-covered metal plate in which the surface on the C layer side of the embossed design sheet is laminated on a metal plate using an adhesive.

  Thereby, the embossed design sheet coating | cover metal plate with favorable embossing heat resistance can be obtained.

  5th this invention is a building interior material selected from the group which consists of a door material, a unit bath wall material, a unit bath ceiling material, a partition material, and a panel material using said embossed design sheet | seat covering metal plate.

  6th this invention is a steel furniture member using said embossed design sheet covering metal plate.

  A seventh aspect of the present invention is a home appliance casing member using the embossed design sheet-covered metal plate.

  The laminated sheet of the present invention has excellent emboss pattern transferability in an embossing machine, and is less likely to stick to heated metal parts (drums for sheet heating) of the embossing machine. Can be imparted with a good embossed design without causing shrinkage, wrinkles, sheet breakage, etc. when heated, and does not cause problems when laminating to a metal plate. Further, by using the laminated structure as described above, it is possible to perform emboss transfer at a higher temperature than in the case of the single layer A. Therefore, the laminated sheet of the present invention to which the embossed of the present invention is transferred is embossed heat resistant. Excellent in properties.

  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 70 to 300 μm, it is more correct to describe it as “film and sheet”, but here, regarding the range generally referred to as “film” For convenience, the single name “sheet” was used.

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

[Resin for forming A layer 10]
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 is passed through an embossing machine. Therefore, the A layer 10 should not have high crystallinity when pressed by the embossing plate roll, and is mainly composed of a polyester resin that is substantially non-crystalline. Here, “substantially noncrystalline” means to include low crystallinity.

  Here, “being mainly” means 55% by mass or more, preferably 75% by mass, of a substantially amorphous polyester resin based on the total mass of the A layer 10 (100% by mass). As mentioned above, it means containing 90 mass% or more more preferably, and it says that the additive demonstrated below and other general purpose resin may be added a little.

  The A layer 10 is embossed after being heated above its glass transition temperature (Tg) by an embossing machine. During heating, the elastic modulus of the A layer 10 needs to be sufficiently reduced to allow embossing. If the sheet to be embossed consists of a single A layer 10 with low crystallinity, it will cause sticking to the heated metal roll, width shrinkage, wrinkles, and sheet breakage. In the laminated sheet of the invention, these problems do not occur due to the presence of the B layer 20 and the C layers 30a and 30b described below.

  The polyester resin that is substantially non-crystalline (including low-crystalline ones) forming the A layer 10 is a polyester that does not show a clear crystal melting peak when heated by a differential scanning calorimeter (DSC). Resin and polyester that has crystallinity but has a low crystallization rate, and does not become highly crystalline in the film-forming process such as extrusion and calendering, and the heating process until the embossed pattern is transferred by an embossing machine Resin can be used.

  The substantially amorphous polyester-based resin of the A layer 10 is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and about 20 to 80 mol. % Is 1.4-cyclohexanedimethanol and the remaining about 80-20 mol. % Is preferably a copolymer ester consisting of ethylene glycol.

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

  If the amount of 1.4-cyclohexanedimethanol is too small, the characteristics as a crystalline resin become remarkable, and crystallization may progress during heating in an embossing machine, making embossing difficult, which is not preferable. On the contrary, if the amount of 1.4-cyclohexanedimethanol is too large, the crystallinity becomes remarkable and a very high melting point is exhibited, which is not preferable.

  An example of a polyester resin that is substantially non-crystalline is a copolyester resin that is non-crystalline. Specifically, the cost is low because of the stable supply of raw materials and the large amount of production. Examples thereof include so-called PET-G resins that have been developed. As the PET-G resin, for example, “Easter PET-G • 6763” manufactured by Eastman Chemical Co. is preferably used. “Easter PET-G · 6763” is about 30 mol. Of the diol component of polyethylene terephthalate resin. % Is a substantially non-crystalline polyester resin having a structure in which 1.4-cyclohexanedimethanol is substituted, and no crystallization behavior is observed by DSC measurement.

  However, the present invention is not limited to this, and “PCTG 5445” manufactured by Eastman Chemical Co., which can be handled as an amorphous resin under normal conditions but can be used under normal conditions can also be used. . Other than this, those that do not show crystallinity with neopentyl glycol copolymerized PET, those that have low crystallinity, those that have low crystallinity with polyethylene terephthalate resin copolymerized with isophthalic acid, etc. Those having a composition that inhibits the above can also be used as an amorphous polyester resin that is the main component of the A layer 10.

  Based on the mass (100% by mass) of the entire resin component in layer A 10, 20 to 40% by mass of polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C. is blended in layer A 10. It is preferable that 20-35 mass% is mix | blended. Thereby, it is possible to make the embossing survivability better when it comes into contact with high-temperature water during a boiling water immersion test or the like, and it can be suitably used particularly when the demand for these is severe. Moreover, solvent resistance and printability can also be improved.

  As the PBT-based resin used for the above-mentioned blending, the main component of the B layer 20 described later can be used. Among them, terephthalic acid as the dicarboxylic acid component, or dimethyl terephthalic acid, and 1.4-butane as the diol component From the viewpoint of cost and availability, it is preferable to use a so-called homo PBT resin (which may contain an unintended copolymer component) using each single component of a diol.

  When there is too much quantity of PBT type resin to mix | blend, the crystallinity of A layer 10 will become remarkable and provision of embossing will become difficult for said reason. Also, if the amount of PBT resin to be blended is too small, there will be no significant difference in the boiling water soaking property from the case where it consists essentially of an amorphous polyester resin, and there will be no reason for blending.

  When the printed pattern (D) 40 does not exist under the A layer 10, a coloring pigment may be added to the A layer 10 for imparting design properties or concealing the base metal. The pigment used may be one generally used for coloring the resin for the above-mentioned purpose, and the addition amount thereof may be an amount generally added for the above-mentioned purpose. As an example, the tint can be adjusted with a chromatic inorganic or organic pigment based on a titanium oxide pigment having a high concealing effect in white coloration.

  In addition, various amounts of various additives may be added to the A layer 10 as long as the properties are not impaired or in order to further improve physical properties other than the object of the present invention. Additives include phosphoric and phenolic antioxidants, heat stabilizers, UV absorbers, light stabilizers, nucleating agents, impact modifiers, processing aids, metal deactivators, and residual polymerization catalyst deactivation. Commonly used in a wide range of resin materials such as additives, nucleating agents, antibacterial / antifungal agents, antistatic agents, lubricants, flame retardants, fillers, carbodiimides, epoxy-based and other terminal carboxylic acids What is marketed for polyester resins, such as a sealing agent or a hydrolysis inhibitor, can be mentioned.

  The preferable thickness of the A layer 10 is in the range of 45 to 250 μm, and more preferably in the range of 50 to 150 μm. If the thickness is too thin, the type of embossed pattern that can be applied is greatly restricted. On the other hand, if the thickness is too thick, the upper limit of the total thickness of the laminated sheet is determined, so that it is necessary to reduce the thickness of the B layer 20 and it becomes difficult to obtain rupture resistance when the laminated sheet is heated. It is not preferable. Further, if the A layer 10 has a thickness of about 150 μm, it is possible to use most of the embossing plate rolls conventionally used for embossing the soft PVC sheet.

[Resin etc. forming B layer 20]
The B layer 20 is provided to give a function of preventing the width reduction, wrinkling, breakage, and the like of the laminated sheet heated to the same temperature as the conventional soft PVC when the laminated sheet is passed through an embossing machine. Therefore, it can be said that the storage elastic modulus in the tensile method at 190 ° C. defined in claim 5 of the present invention is mainly given by the composition and thickness of the B layer 20.

  The B layer 20 contains 75 to 95% by mass of a PBT resin having a melting point of 210 to 230 ° C. based on the mass (100% by mass) of the entire resin component in the B layer 20. The melting point of 210 ° C. or higher is necessary because 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 about 160 ° C. to 190 ° C. This is to obtain sufficient tension at the temperature. The reason why the upper limit of the melting point is 230 ° C. is that homo PBT having the highest melting point among PBT resins obtained as commercially available raw materials is around 225 ° C.

  Focusing only on the viewpoint of maintaining the tension by crystallization, the B layer 20 may be a homo-PET resin or the like. However, since the PBT resin in the melting point range has a relatively high crystallization speed, it is 75% by mass. In the blend composition containing the above PBT-based resin, it is possible to form a film in a crystallized state without requiring any special device, and by setting the B layer 20 to a predetermined thickness, the laminated sheet of the present invention can be formed. In the present invention, the PBT resin having the above melting point is used because it is easy to obtain a preferable storage elastic modulus.

  Other reasons for using PBT-based resins are that good processability can be obtained even in a crystallized state compared to PET-based resins, and in recent years, the use of extrusion film-forming grades has become active, and various grades It is mentioned that it became easy to obtain the raw material of PBT resin. In addition, there is a polytrimethylene terephthalate (PTT) resin as a resin having a melting point in the same temperature range and a high crystallization rate, but it is as low as the PBT resin in terms of cost, freedom of grade selection, and stable supply. Absent.

  The B layer 20 contains the PBT resin at a ratio of 75 to 95% by mass, based on the mass of the entire resin component in the B layer 20 (100% by mass). If this ratio is too small, even if the sheet is obtained in a crystallized state, a considerable B layer 20 thickness is required to obtain a preferable storage elastic modulus, and the total thickness of the sheet is limited. The degree of freedom of the thickness of other layers is restricted, which is not preferable. Further, the purpose of providing the C layers 30a and 30b is dilute. On the other hand, when this ratio is too large, the warp of the laminated sheet becomes remarkable and the handleability deteriorates, which is not preferable. Further, the B layer 20 may contain a small amount of the above-described additives described in the A layer 10 and other general-purpose resins.

  As a PBT resin having a melting point of 210 to 230 ° C., a so-called homo PBT resin using terephthalic acid as a dicarboxylic acid component, or dimethylterephthalic acid and a single component of 1.4-butanediol as a diol component It is preferable to use (an unintended copolymer component may be contained). This is because the homo PBT resin has a melting point of about 225 ° C., which is advantageous in terms of cost and stable supply. In addition to homo-PBT resins, those obtained by substituting a part of the acid component with dicarboxylic acid such as isophthalic acid and having a melting point not lower than 210 ° C., or those obtained by copolymerizing polytrimethylene glycol (PTMG) are used. be able to. Moreover, when producing a sheet | seat by an extrusion film forming method, it is common to use the PBT resin whose raw material IV value is about 1.0-1.4.

  As the resin component other than the PBT resin of the B layer 20, it is preferable to use a polyester resin that is substantially amorphous. As the substantially amorphous polyester resin, the same polyester resin as the substantially amorphous polyester used as the main component of the A layer 10 described above can be used. This is because when a highly crystalline resin such as homo-PET is used as the resin component other than the PBT resin in the B layer 20, the crystallization of the PET resin progresses over time, and the crystal phase of the PET resin This is because the workability of the B layer 20 is inferior because of the inferior workability of the crystalline phase of the PBT resin, and as a result, the workability of the laminated sheet and the metal plate covered thereby may be reduced. is there.

The preferable thickness of the B layer 20 is such that the storage elastic modulus at 190 ° C. in the dynamic viscoelastic tension method 10 Hz of the laminated sheet is 1 × 10 ⁷ Pa or more with respect to the MD direction of the sheet using the B layer 20 in the above composition range. Although it will be said thickness, it is preferable that it is the range of 20-200 micrometers from the point of the ease of the handleability of a lamination sheet.

  A color pigment may be added to the B layer 20 for imparting design properties or concealing the base metal. When the printed pattern (D) is applied and the E layer is not applied, it is preferable to add a color pigment mainly to the B layer. The pigment used and the amount added are the same as in the case of adding to the A layer.

[Resin etc. for forming C layers 30a and 30b]
The purpose of applying the C layers 30a and 30b to the laminated sheet of the present invention is to adhere the laminated sheet to the heated metal part (heating drum) when the embossed pattern is transferred to the laminated sheet with an embossing machine. To prevent this, and when laminating B layer 20 containing a relatively large amount of polybutylene terephthalate resin having a melting point of 210 ° C. to 230 ° C. of 75 to 95% directly on a metal plate, it is necessary to set the laminating temperature higher. This is because a layer capable of obtaining sufficient adhesion at a relatively low temperature as compared with the B layer 20 is provided.

  Further, the C layers 30a and 30b should not have any problems when the metal plate coated with the laminated sheet is subjected to a boiling water immersion test, and does not adversely affect the workability as a resin-coated metal plate. It is. Furthermore, it is preferable that the B layer 20 can be laminated with the B layer 20 by heat fusion lamination or in-die lamination by a coextrusion film forming method without applying a special adhesive.

  Of these, non-adhesiveness to heated metal rolls and non-crystalline polyesters that can be made by calendering by adding a large amount of lubricant, etc., for lamination to metal plates at relatively low temperatures This can also be achieved by using a resin as the main component of the C layer. In this case, when a boiling water immersion test is performed on a metal plate coated with a sheet, the elastic modulus of the C layer is significantly reduced. Since a remarkable change in appearance occurs, it may not be used depending on the application, which is not preferable.

  In order to achieve the above object, in the present invention, the polybutylene having a melting point of 210 to 230 ° C. is used as the C layer 30a of the first form, based on the mass of the entire resin component in the C layer 30a (100% by mass) A non-oriented resin layer having a thickness of 5 μm or more and containing 55 to 70% by mass of a terephthalate (PBT) resin and 45 to 30% by mass of a substantially amorphous polyester resin is used.

  Since the PBT resin in the melting point range has a relatively high crystallization rate, in the blend composition containing 55% by mass or more of the PBT resin, by appropriately setting the casting roll temperature during extrusion film formation, and / or Alternatively, the C layer can be easily crystallized by an extrusion film forming line by installing several heat treatment rolls behind the casting roll. Thereby, the non-adhesiveness to the heating metal roll of an embossing machine can be ensured.

  If the content of the PBT resin is too small, the crystallization speed of the blend composition becomes slow, and it is necessary to reduce the line speed of extrusion film formation or to perform a heat treatment in a subsequent process, thereby reducing productivity. It is not preferable. On the other hand, if the content of the PBT resin is too large, the crystallinity becomes so high that a relatively high temperature is required when laminating to the metal plate, which is not preferable, and the purpose of providing the C layer is dilute.

  When a non-contact type heater is used in combination, the heated metal roll of the embossing machine is used as sheet preheating prior to the heater. Moreover, when embossing is provided to a conventional soft PVC sheet, the set temperature of the heated metal roll is often used at about 100 ° C to 140 ° C. Therefore, the C layer is required to be crystallized and to have a melting point higher than the set temperature of the roll and be non-adhesive to the roll.

  As the PBT resin having a melting point of 210 ° C. to 230 ° C., the same PBT resin as that used for the B layer 20 can be used. In addition, a so-called homo PBT resin (which may include an unintended copolymerization component) using terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component and each single component of 1.4-butanediol as a diol component. .) Is particularly preferable from the viewpoints of cost and stable supply, since the melting point is about 225 ° C.

  As the substantially amorphous polyester resin used by blending with the PBT resin in the C layer 30a, the same polyester resin as the substantially amorphous polyester mainly used in the A layer 10 may be used. preferable.

  The C layer 30b of the second form contains 70-100% by mass of a polybutylene terephthalate (PBT) resin having a melting point of less than 210 ° C., based on the mass of the entire resin component in the C layer 30b (100% by mass). A non-oriented resin layer having a thickness of 5 μm or more is used.

  Since the PBT resin having this melting point has a slower crystallization rate than the PBT resin used for the C layer 30a of the first form, the content of the PBT resin in the C layer 30b of the second form is 70% by mass. It is necessary to do it above. If the content of the PBT resin is small, it is not preferable because a special heat treatment or the like is required in order to impart crystallinity that does not stick to the heated metal roll with an embossing machine.

  In addition, since the melting point of the PBT resin that is the main component of the C layer 30b is sufficiently lower than the conventional metal plate temperature when laminating to the metal plate, 100 mass% of the resin component of the C layer 30b is reduced. PBT resin may be used. Further, since the thickness of the C layer 30b is relatively smaller than that of the B layer 20, even if the PBT resin is used at 100% by mass, the influence of the warp generated in the B layer 20 is difficult to occur.

  As the PBT resin having a melting point of less than 210 ° C., one obtained by substituting a part of the acid component with a dicarboxylic acid such as isophthalic acid can be used, but the lower the melting point, the slower the crystallization rate. Is preferably selected in the range of 180 ° C. or higher.

  In the second layer C layer 30b, the resin used by blending with the PBT resin may be the same as the substantially amorphous polyester resin used as the main component of the A layer 10 described above. it can.

  The preferable thickness of the C layers 30a and 30b is 5 to 25 μm, and more preferably 10 to 20 μm. If the thickness is too thin, there may be a problem in extrusion stability when laminated in the die by the co-extrusion film formation method with the B layer 20, and if the thickness is too thick, it is necessary for the C layers 30a and 30b. Since the functions are saturated and the total thickness of the laminated sheet is limited, the degree of freedom in designing the other layers is affected.

  In the C layers 30a and 30b, various additives similar to those in the A layer 10 and the B layer 20 may be added in appropriate amounts, or coloring pigments may be added. Further, an appropriate amount of lubricant may be added in order to further strengthen the non-adhesiveness with the heated metal, which is the purpose to which the C layers 30a and 30b are applied. As the lubricant, those commonly used for addition to polyester resins can be used. As an example, “Lycowax OP” (manufactured by Clariant Japan Co., Ltd.), which is a montanic acid-based lubricant, is mentioned. be able to. The C layers 30a and 30b use a PBT resin having a lower ratio of PBT resin than the B layer 20 or a lower melting point and a slightly slower crystallization rate. Therefore, the crystallization rate can be improved by adding a crystal nucleating agent. You may plan.

[Print pattern (D) 40]
In the laminated sheet of the present invention, the A layer 10 may be substantially transparent, and a printed pattern (D) 40 may be provided between the A layer 10 and the B layer 20 by printing. . The printed pattern (D) 40 is applied by a known method such as gravure printing, offset printing, or screen printing, and an arbitrary pattern such as a stone pattern, a wood pattern, a geometric pattern, or an abstract pattern is applied.

  The printed pattern (D) 40 may be formed by printing on the surface of the B layer 20 to be laminated with the A layer 10, or on the surface of the A layer 10 to be laminated with the B layer 20. It may be formed by printing. Further, when the E layer 50 described below is provided, it may be formed on the surface of the E layer 50 to be laminated with the A layer 10 or the A layer 10 to be laminated with the E layer 50. It may be formed on the surface. In general, forming the printed pattern (D) 40 on the surface of the B layer 20 and the E layer 50 results in printing on a laminated sheet including a layer having high crystallinity. Handling is easy and preferable.

[Resin etc. forming E layer 50]
In the laminated sheet of the present invention, the A layer 10 is substantially transparent, and a printed pattern (D) 40 is provided between the A layer 10 and the B layer 20. D) A non-oriented resin layer (E layer) 50 mainly composed of a polyester-based resin that is substantially amorphous can be arranged between 40 and the B layer 20.

  The E layer 50 is a layer made of a substantially amorphous polyester resin, and is a layer to which the embossed pattern is transferred by being softened by heating and pressed by an embossing plate roll in the same manner as the A layer 10. In this embodiment, since the thickness of the A layer 10 can be reduced, in the configuration in which the printed pattern (D) 40 is provided under the A layer 10, the transparency of the printed pattern (D) 40 is greatly reduced. A deep embossed pattern can be transferred without doing so. Further, since the polyester resin is a resin that is relatively susceptible to light yellowing, if the thickness of the transparent A layer 10 is too thick, yellowing over time may become conspicuous. This is also preferable.

  Therefore, the substantially amorphous polyester resin that is the main component of the E layer 50 can be the same as that of the A layer 10. Further, the blend of 20 to 40% by mass of the PBT resin, the pigment, and the additive are the same as those of the A layer 10.

  In the case of a relatively shallow embossed pattern that can be applied even when the thickness of the embossing layer (A layer 10 or A layer 10 + E layer 50) is 100 μm or less, the E layer 50 is not provided and the thickness of the A layer 10 is set to 100 μm. However, when a thickness of about 150 μm or more is necessary, the thickness of the A layer 10 is set to 100 μm or less, and the transparency of the printed pattern (D) 40 is prevented from being lowered. It is preferable that the E layer 50 having a set thickness is combined so that the total thickness of the embossing layer is about 150 μm or more.

  Further, the B layer 20 is a highly crystalline resin layer mainly composed of a PBT resin for that purpose, whereas the E layer 50 is composed mainly of a non-crystalline polyester resin. The thermal fusion suitability between sheets with the layer 10 is also considered to be better than that of the B layer 20, and the B layer 20 and the E layer 50 are integrally formed by co-extrusion film formation. D) When 40 is set as partial printing, it is possible to obtain strong heat-fusibility between the E layer 50 and the A layer 10 and to reduce the possibility of peeling between the layers.

  An appropriate amount of various additives similar to those of the A layer 10, the B layer 20, and the C layers 30a and b may be added to the E layer 50, and a printed pattern (D) 40 is applied to the surface of the E layer 50. In this case, it is particularly preferable to add a color pigment to the E layer 50 in order to improve printing color.

  A preferable thickness of the entire laminated sheet (100a to 100d) is in the range of 70 to 300 μm. When the thickness of the laminated sheets (100a to 100d) is too thin, it is necessary to add a large amount of pigment to each layer in order to ensure the visual concealment of the base, and as a result, the processability may be lowered. On the other hand, when the thickness of the laminated sheet (100a to 100d) is too thick, it becomes difficult to use a molding die that has been conventionally used for molding such as bending of a flexible PVC resin-coated metal plate. There is a risk of problems in secondary workability itself.

  Regarding the visual hiding effect of the base metal plate required for the entire laminated sheet, the degree of importance varies depending on the application. However, in the case of an embossed design sheet-covered metal plate for interior building materials, JIS K5400 7.2 “Paint” It is preferable that the concealment ratio measured in accordance with “General Test Method / Concealment Ratio” is 0.95 or more in the configuration of the laminated sheet.

  If the concealment ratio is lower than this, the color of the base material such as a metal plate is reflected in the color of the laminated sheet, and when these colors change, the color observed from the surface of the laminated sheet Is also undesirable because it 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.

[Lamination sheet, embossed design sheet, embossed design sheet coated metal plate manufacturing method]
As a method for producing the laminated sheet 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 adopted, and the resin composition of the A layer 10 is substantially non-existent. When it consists only of polyester-type resin which is crystalline, the A layer 10 can also be formed with the calender film-forming equipment used for the conventional film formation of PVC-type resin.

  After each layer is formed alone, it may be laminated and integrated in a later step to form a laminated sheet. However, in the configuration not including the printed pattern (D) 40 shown in FIGS. 1A and 1B, “A It is most efficient and preferable to form three layers of “layer 10 + B layer 20 + C layer 30a, b” integrally by a co-extrusion film forming method using three extruders and a feed block or a multi-manifold die.

  In the configuration having the printed pattern (D) 40 shown in FIG. 2A and FIG. 2B, the A layer 10 is formed as a single layer, and the “B layer 20 + C” is formed integrally by the coextrusion method. It is preferable to laminate and integrate the printed pattern (D) 40 on the surface of the “layer 30a, b” or “E layer 50 + B layer 20 + C layer 30a, b”. In this case, the printed pattern (D) 40 may be applied to the surface of the A layer 10 on the side laminated with the B layer 20 or the E layer 50. The type of the resin binder of the printed pattern (D) 40 is not particularly limited, but by appropriately selecting the binder type, lamination integration between the A layer 10 and the B layer 20 or the A layer 10 and the E layer 50 is performed. Can be heat-sealed. Alternatively, at the time of applying the printed pattern (D) 40, a heat-fusible coating layer can be simultaneously applied to perform heat-fusion lamination. The integration of the A layer 10 and other layers by heat fusion lamination is preferably carried out in the process of introducing into the heating roll of the embossing machine.

  However, the lamination and integration of the A layer and the other layer is not necessarily performed by heat fusion lamination with an embossing machine, and heat fusion lamination may be performed in another process. Moreover, regarding the adhesion between other layers other than the adhesion between these layers, lamination with a dry lamination adhesive or the like can also be performed.

  FIG. 3 shows an example of an embossing machine 200 that has been generally used to give an embossed pattern to a soft PVC sheet. The embossing machine 200 according to the illustrated embodiment includes a heating roll 210, a take-off roll 220, an infrared heater 230, a nip roll 240, an embossing roll 250, and a cooling roll 260. In the form shown in FIG. 2, a two-layer sheet of A layer formed as a single layer and B layer + C layer subjected to a printed pattern (D) is supplied and heated by the heating roll 210 of the embossing machine as described above. Fusion lamination is performed.

  The laminated sheets 100a to 100d of the present invention can be provided with an embossed pattern by an embossing machine 200 in the same manner as a conventional soft PVC sheet. Since the C layers 30 a and 30 b have the characteristics of the present invention, the C layers 30 a and 30 b are non-adhesive to the heating roll 210 heated to about 100 ° C. to 140 ° C. Even at a certain 160 ° C. to 190 ° C., the B layer 20 has the characteristics of the present invention, so that the laminated sheets 100a to 100d are not reduced in width, wrinkled or broken, and the A layer 10 has good embossing. The embossed design sheet with embossing having a good appearance can be obtained by having the imparting suitability.

  As the metal plate used for the embossed design sheet-coated metal plate of the present invention, various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, stainless steel plate, aluminum plate, aluminum alloy A board etc. can be used and you may use these, after giving a normal chemical conversion treatment. The thickness of the base metal plate varies depending on the use of the resin-coated metal plate, but can be selected in the range of 0.1 mm to 10 mm.

  The method for laminating the embossed design sheet on the base metal plate is not particularly limited, but laminating with an adhesive is common. Examples of the adhesive include generally used thermosetting adhesives such as an acrylic adhesive, an epoxy adhesive, a urethane adhesive, and a polyester adhesive. Among these, since a sheet | seat consists of a polyester-type resin, it is preferable to use a polyester-type adhesive agent. As a method of obtaining an embossed design sheet-coated metal plate, the adhesive film after drying is applied to the metal surface on which the embossed design sheet is bonded using a commonly used coating facility such as a reverse coater or kiss coater. The thermosetting adhesive is applied so that the thickness is about 2 to 10 μm.

  Next, the coated surface is dried and heated with an infrared heater and / or a hot-air heating furnace, and the surface temperature of the metal plate is maintained at a temperature of about 220 ° C. to 250 ° C., and the embossed design sheet is immediately used using a roll laminator. An embossed design sheet-covered metal plate can be obtained by coating and cooling so that the C layers 30a and b side are bonded surfaces.

  Moreover, the embossed design sheet-covered metal plate of the present invention has good workability, and is a building material such as a door material, a unit bath wall material, a unit bath ceiling material, a partition material and a panel material, a steel furniture member, It can be suitably used as a housing member for home appliances such as AV equipment and air conditioner covers.

  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.

[Create laminated sheet]
<Examples 1-10, Comparative Examples 1-3>
In the laminated sheets of Examples 1 to 10 and Comparative Examples 1 to 3, the resin flowed out from the T-die was cast with a casting roll by co-extrusion using a feed block method using three twin-screw kneading extruders with a diameter of 65 mm. A three-layer laminated sheet was obtained by a general method of pulling. For each layer, layer A is a layer having the resin composition shown in Table 1, the amount of pigment added (a white pigment based on titanium oxide was added as a pigment), and a layer thickness, and layer B was Easter 6763. 10% by mass, 90% by mass of NOVADURAN 5020S, and a layer thickness of 45 μm. C layer has 40% by mass of Easter 6763, 60% by mass of NOVADURAN 5020S, and a layer thickness of 15 μm. Is a layer. Table 1 shows the total thickness of the laminated sheets.

<Examples 11-22, Comparative Examples 4-12>
For the laminated sheets of Examples 11 to 22 and Comparative Examples 4 to 12, the A layer is a layer having 75% by mass of Easter 6763, 25% by mass of Novaduran 5020S, and a layer thickness of 90 μm, and B layer Is a layer having a resin composition and a layer thickness shown in Table 2, and the C layer is a layer having 35% by mass of Easter 6763, 65% by mass of Novaduran 5020S, and a layer thickness of 10 μm. Except for this, a three-layer laminated sheet was obtained in the same manner as in Example 1 above. Table 2 shows the total thickness of the laminated sheets.

<Examples 23 to 33, Comparative Examples 13 to 18>
Regarding the laminated sheets of Examples 23 to 33 and Comparative Examples 13 to 18, the A layer is a layer having 75% by mass of Easter 6763, 25% by mass of Nova Duran 5020S, and a layer thickness of 90 μm, and the B layer However, 15% by weight of Easter 6763, 85% by weight of Novaduran 5020S and a layer thickness of 45 μm, and layer C is a layer having the resin composition and layer thickness shown in Table 3. Except for the above, a three-layer laminated sheet was obtained in the same manner as in Example 1 above. Table 3 shows the total thickness of the laminated sheets.

<Comparative Example 19>
The laminated sheet of Comparative Example 19 was divided into two layers by a general method in which the resin flowing out from the T-die was taken up by castin gall by feed block type co-extrusion using two twin-screw kneading extruders having a diameter of 65 mm. A laminated sheet was obtained. For each layer, layer A is a layer having 75% by weight of Easter 6763, 25% by weight of Nova Duran 5020S and a layer thickness of 90 μm, and layer B is 15% by weight of Easter 6763 and 85% by weight of Nova Duran 5020S. %, And the layer thickness is 45 μm. Table 3 shows the total thickness of the laminated sheets.

<Examples 34 to 39, Comparative Examples 20 to 23>
The laminated sheets of Examples 34 to 39 and Comparative Examples 20 to 24 were formed by a two-layer laminated sheet of B layer and C layer or three layers of E layer, B layer, and C layer by coextrusion film formation of a feed block method. A layer laminated sheet is formed, and an abstract printed pattern (D) is printed on the surface of the B layer side or the E layer side by gravure printing, and then the A layer formed as a single layer is shown in FIG. It was produced by laminating and integrating by heat fusion lamination at a heating roll portion of an embossing machine as shown. The layer A has the resin composition and layer thickness shown in Table 4, the layer E has the resin composition, pigment addition amount and layer thickness shown in Table 4, and the layer B has Table 5 The resin composition, pigment addition amount and layer thickness shown are used, and the layer C has the resin composition and layer thickness shown in Table 5. Table 5 shows the total thickness of the laminated sheets.

<Comparative Example 24>
The laminated sheet of Comparative Example 24 was formed into a two-layer laminated sheet of E layer and B layer by feed block co-extrusion film formation, and an abstract pattern (D) was printed on the surface of the E layer by gravure printing. After that, the A layer formed as a single layer was laminated and integrated by heat fusion lamination at a heating roll portion of an embossing machine as shown in FIG. Table 5 shows the total thickness of the laminated sheets.

The raw materials used in the above examples and comparative examples are as follows.
(Easter PETG · 6763)
A non-crystalline polyester resin manufactured by Eastman Chemical Company. The dicarboxylic acid component is terephthalic acid, which is about 30 mol. % Is 1.4-cyclohexanedimethanol, about 70 mol. % Is ethylene glycol. Melting point: none, glass transition temperature: 78 ° C.

(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, which is about 65 mol. % Is 1.4-cyclohexanedimethanol, about 35 mol. % Is ethylene glycol. Melting point: none, glass transition temperature: 86 ° C.

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

(Juranex 500JP)
It is an isophthalic acid copolymerized polybutylene terephthalate resin manufactured by Wintech Polymer. The melting point is 204 ° C.

(Unipet RT-580)
This is a (homo) polyethylene terephthalate resin manufactured by Nippon Unipet. The melting point is 254 ° C.

(BK-2180)
This is an isophthalic acid copolymerized polyethylene terephthalate resin manufactured by Mitsubishi Chemical Corporation. The melting point is 247 ° C.

[Embossing on laminated sheet]
The embossed pattern was transferred using an embossing machine 200 generally used for embossing a soft vinyl chloride sheet as shown in FIG. Moreover, regarding the sheet | seat which has a printed pattern (D), the heat-fusion lamination | stacking is performed by the heating roll part of an embossing machine as mentioned above. As an outline of the process of the embossing machine, first, the sheet is preheated by contact-type heating using a heating roll 210, and then the sheet is heated to an arbitrary temperature by non-contact type heating using an infrared heater 230, The embossed design sheet is obtained by transferring the embossed pattern by the embossing roll 250.

  In this example and the comparative example, the heating roll 210 was set to 110 ° C., and then heated by the infrared heater 230 so that the sheet surface temperature immediately before contacting the embossing roll 250 became 180 ° C. The embossing roll 250 was adjusted to 90 ° C. by a hot water circulator, and a satin pattern with Rmax = 50 μm was used. Only the comparative example 12 uses the laminated sheet having the same composition and thickness structure as the comparative example 5, and the embossing pattern is imparted by setting the sheet temperature just before contacting the embossing roll 250 to 140 ° C.

[Creation of embossed design sheet metal sheet]
A commercially available polyester adhesive for polyvinyl chloride coated metal plate is applied to the metal surface to which the laminated sheet is bonded so that the adhesive film thickness after drying is about 2 to 4 μm, then an infrared heater and hot air The coated surface is dried and heated in a heating furnace, and the sheet temperature is immediately covered with a roll laminator while maintaining the surface temperature of a galvanized steel sheet with a thickness of 0.45 mm at three levels of 235 ° C, 230 ° C, and 225 ° C. -The embossed design sheet coating metal plate was obtained by cooling.

[Evaluation of laminated sheet and embossed design sheet coated metal sheet]
The following items were evaluated for the laminated sheet and the embossed design sheet-covered metal plate obtained in the above Examples and Comparative Examples. The results are summarized in Tables 6-9.

(1) Measurement of storage elastic modulus It measured about the MD direction of the lamination sheet with the viscoelasticity spectrometer made from Iwamoto Seisakusho. The measurement method was in accordance with the usual tensile method / temperature dispersion measurement method, the temperature was increased from −100 ° C. at a rate of temperature increase of 3 ° C./min, the measurement was performed up to 250 ° C., and the storage elastic modulus at 190 ° C. was read. .

(2) Handling property of laminated sheet: strength of warpage The laminated sheet was cut out to 15 cm (TD direction) x 30 cm (MD direction), placed on a surface plate, and the degree of warping was observed. When the warpage is strong and it becomes completely cylindrical, or when it becomes an arch shape with a height of 10 cm or more from the surface plate surface, the handling property is bad, and “x” is less than 10 cm, but the warpage is 5 cm or more. Is “△”, and in the case of warping less than that, the handling is good and “◯” is given. The “TD direction” refers to the width direction of the sheet (Transverse direction), which is a direction orthogonal to the MD direction.

(3) Embossing suitability: Adhesion resistance When embossing was applied with the embossing machine shown in FIG. 3, the laminated sheet adhered to the heating roll 210 and became difficult to peel, and peeling was possible. “×” indicates that the sheet was prominently stretched and deformed, and although slight adhesion was observed, the work could be continued, and the sheet stretched and deformed within a range that had no practical problems. ”, Those that did not adhere are indicated by“ ◯ ”. Moreover, subsequent evaluation is not implemented about the thing which the lamination sheet adhered to the heating roll and it became difficult to peel.

(4) Embossing suitability: Fusing resistance When embossing is applied with the embossing machine shown in FIG. 3, the sheet is melted while the sheet is heated by the heater 230, and the sheet is noticeably stretched or wrinkled. “×” indicates that the sheet was slightly stretched / width-shrinked, etc., but was within the practical range, and “△” indicates that these problems did not occur. . No further evaluation was performed for those evaluated as “x” in this evaluation.

(5) Embossing suitability: Transferability The sheet embossed with the embossing machine shown in FIG. 3 is visually observed, and “○” indicates that the embossed pattern is transferred cleanly. “△” indicates that the surface is shallow, and “×” indicates that the transfer is poor and has a shallow embossed pattern, or that the surface is simply rough regardless of the embossed pattern. No further evaluation was performed for those evaluated as “x” in this evaluation.

(6) Embossing heat resistance: high temperature air heat resistance The metal plate laminated with the embossed sheet by the embossing machine shown in Fig. 3 was left in a 105 ° C hot air circulating oven for 3 hours and then visually observed. , “○” indicates that the shape of the emboss is almost unchanged compared to before being put into the oven, “△” indicates that the embossed return has occurred slightly compared to this, and if the embossed return is significant, Alternatively, “x” indicates that the embossed pattern has completely disappeared and the surface is simply rough. Embossing heat resistance of the metal plate laminated at a heating temperature of 235 ° C. was evaluated.

(7) Embossing heat resistance: resistance to boiling water immersion Before immersing the metal plate laminated with the embossed sheet in the embossing machine shown in FIG. Compared with, the shape of the emboss is almost unchanged “○”, when the embossed return is slightly compared to “△”, when the embossed return is noticeable, or the embossed pattern is completely Those that have disappeared and have a rough surface are indicated by “x”. Embossing heat resistance of the metal plate laminated at a heating temperature of 235 ° C. was evaluated.

(8) Workability An impact adhesion bending test was performed on the embossed design sheet-coated metal plate, and the surface state of the laminated sheet in the bent portion was visually determined. Was evaluated as “Δ”, and those with cracks were evaluated as “x”. The impact adhesion bending test was performed as follows. Samples of 50 mm x 150 mm were prepared from the length direction and width direction of the embossed design sheet-coated metal plate, kept at 23 ° C for 1 hour or longer, and then bent to 180 ° (inner bending radius 2 mm) using a bending tester. A cylindrical weight having a diameter of 75 mm and a mass of 5 kg was dropped on the sample from a height of 50 cm. Workability of the metal plate laminated at a heating temperature of 235 ° C. was evaluated.

(9) Metal plate adhesion strength Using a 20 mm x 100 mm embossed design sheet coated metal plate as a test piece, peel strength in accordance with JIS Z-0237 "Adhesive tape / adhesive sheet test method-180 degree peel adhesion to the test piece" The measurement was performed with a measurement width of 20 mm, and the adhesive strength between the resin film and the base metal was measured. “◯” indicates that the adhesive strength is sufficient (40 N / 20 mm or more), “△” indicates that the adhesive strength is relatively inferior but is practically satisfactory, and the adhesive strength is further low The thing (less than 20N / 20mm) was made into "x". Lamination was performed under three stages of temperature conditions of 235 ° C., 230 ° C., and 225 ° C., and the adhesive strength was measured.

<Examples 1-10, Comparative Examples 1-3>
The laminated sheet of Comparative Example 1 is a case where the resin composition of the A layer contains 50% by mass of PBT resin, and Comparative Example 2 contains 60% by mass. In either case, it is difficult to transfer the embossed pattern on the embossing machine. In Comparative Example 3, the resin composition of the A layer is mainly composed of amorphous polyester, but since the thickness of the A layer is thin, good transfer is not obtained. On the other hand, in Examples 1 to 10 of the present invention, good embossed pattern transfer was obtained.

<Examples 11-22, Comparative Examples 4-12>
In the laminated sheet of Comparative Example 4, the composition of the B layer was 100% by mass of PBT resin, and there was no hindrance to the series of embossing transfer operations in the embossing machine, but the warping of the laminated sheet was remarkable, and embossing was applied. Difficulty in passing sheets to the machine. Comparative Examples 5 to 9 are cases where the storage elastic modulus at 190 ° C. is lower than the preferred value of the present invention due to the composition of the B layer or the thickness of the B layer, both of which are non-contact heaters in an embossing machine The width of the laminated sheet was reduced, wrinkled, and broken by heating.

  Comparative Example 11 is a case where 100% by mass of homo-PET resin, which is a crystalline polyester, is used as the composition of the B layer, but the structure of the laminated sheet is caused by the slow crystallization rate compared to the PBT resin. At that time, the B layer was not crystallized so much, and as a result, the laminated sheet was broken by heating with a non-contact heater in an embossing machine. In Comparative Example 10, the total thickness of the laminated sheet is large, causing a problem in workability.

  Comparative Example 12 is a case where a laminated sheet having the same composition and thickness structure as Comparative Example 5 was transferred by an embossing machine at a sheet temperature of 140 ° C., and the storage elastic modulus at 140 ° C. was high. As shown, there is no problem in the series of operations with the embossing machine, but the embossing heat resistance of the coated metal plate coated with the laminated sheet is poor.

  On the other hand, in Examples 11-22 of this invention, there is no problem in the operativity with an embossing machine, and the thing which is excellent also in the embossing heat resistance of the metal plate which coat | covered these laminated sheets is obtained. However, in Example 11, the total thickness of the laminated sheet was the upper limit of the preferred range of the present invention, and the workability was slightly low. Further, in Example 20, the thickness of the B layer is the lower limit of the preferred range of the present invention, and the non-contact heater heating in the embossing machine is a level that is judged to be practically satisfactory, but the elongation of the laminated sheet Caused width shrinkage.

<Examples 23 to 33, Comparative Examples 13 to 19>
Comparative Examples 13, 14, 16, and 17 are cases where the resin composition of the C layer is out of the preferred range of the present invention, and the addition amount of the PBT resin is small, and the laminated sheet sticks to the heating roll of the embossing machine. As a result, it became difficult to transfer the embossed pattern. In Comparative Example 15, the resin composition of the C layer is within the preferred range of the present invention, but the thickness is thin, there is no hindrance to the operation with a series of embossing machines, and a good embossed pattern transfer is obtained. Also, the heat resistance of the embossing was good, but when laminating to a metal plate, good adhesive strength was obtained at a heating temperature of 235 ° C. The coating that was present produced a slight thermal discoloration. Therefore, when the laminating temperature was lowered to 230 ° C. and further to 225 ° C. to prevent thermal discoloration of the back surface paint, the adhesive strength of the laminated sheet was significantly lowered.

  Comparative Example 18 is a case where 100% by mass of isophthalic acid copolymerized PET resin was used as the composition of the C layer, but due to the slow crystallization rate compared to the PBT resin, the configuration of the laminated sheet At that time, the C layer was not crystallized so much, and as a result, the heating roll of the embossing machine became sticky, making it difficult to transfer the embossed pattern.

  Comparative Example 19 is a case where the layer C does not exist in the laminated sheet, there was no hindrance to the operation with a series of embossing machines, a good embossed pattern transfer was obtained, and the heat resistance of the embossing was also good. However, when laminating to a metal plate, good adhesive strength was obtained at a heating temperature of 235 ° C., but the coating applied to the back surface of the metal plate due to heating to this temperature caused thermal discoloration. Therefore, when the laminating temperature was lowered to 230 ° C. and further to 225 ° C. to prevent thermal discoloration of the back surface paint, the adhesive strength of the laminated sheet was significantly lowered.

  On the other hand, in Examples 23 to 33 of the present invention, there is no problem in operability in the embossing machine, the embossing heat resistance of the metal plate coated with these laminated sheets is good, and 230 ° C., Good adhesive strength is also obtained when a resin-coated metal plate is used at a laminating temperature of 225 ° C., which is slightly lower than the conventional one.

<Examples 34 to 39, Comparative Examples 20 to 24>
In Comparative Example 20, the total thickness of the laminated sheet was thick outside the preferred range of the present invention, and there was a problem in workability. Comparative Example 21 has a structure in which an E layer is present in addition to the A layer as a layer to which the embossed pattern is transferred. However, the total thickness of the A layer and the E layer is thinner than the preferred range of the present invention, and good emboss transferability is obtained. Not obtained. Comparative Example 22 uses 100% by mass of isophthalic acid copolymerized PET resin as the composition of C layer as in Comparative Example 18, and at the time when the laminated sheet was configured, the C layer was not crystallized so much. As a result, the heating roll of the embossing machine became sticky, making it difficult to transfer the embossed pattern.

  In Comparative Example 23, the resin composition of the B layer deviates from the preferred range of the present invention, and the amount of PBT resin added is small. Therefore, the storage elastic modulus at 190 ° C. is low, and non-contact heater heating with an embossing machine The remarkable elongation and width shrinkage of the laminated sheet occurred. Comparative Example 24 is a case where the layer C does not exist in the laminated sheet as in Comparative Example 18, and a good embossed pattern transfer was obtained and the heat resistance of the embossing was good. Good adhesion strength was obtained at a heating temperature of 235 ° C. where there was a concern that the paint on the back surface of the metal plate was thermally discolored, but good adhesion strength was not obtained at a lamination temperature of 230 ° C. and 225 ° C.

  On the other hand, in Examples 34 to 39 of the present invention, there is no problem in operability in the embossing machine, the embossing heat resistance of the metal plate coated with these laminated sheets is good, and 230 ° C., Good adhesive strength is also obtained when a resin-coated metal plate is used at a laminating temperature of 225 ° C., which is slightly lower than the conventional one.

  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 an interior of the building accompanying such changes Materials and the like should also be understood as being included in the technical scope of the present invention.

Fig.1 (a) and FIG.1 (b) are schematic sectional drawings which show one Embodiment of the lamination sheet of this invention of a structure which does not have a printed pattern (D). Fig.2 (a) and FIG.2 (b) are schematic sectional drawings which show one Embodiment of the lamination sheet of this invention of a structure which has a printed pattern (D). It is the schematic diagram of the embossing machine generally used in order to provide an embossed pattern to the sheet | seat of soft PVC conventionally.

Explanation of symbols

10 A layer 20 B layer 30a, b C layer 40 Print pattern (D)
50 E layer 100a to 100d Laminated sheet 200 Embossing machine 210 Heating roll 220 Take-off roll 230 Infrared heater 240 Nip roll 250 Embossing roll 260 Cooling roll

Claims (14)

A layered sheet comprising at least three layers of A layer, B layer and C layer, and at least B layer and C layer are integrally formed by coextrusion film forming method,
The A layer is a non-oriented resin layer having a thickness of 45 μm or more mainly composed of a substantially amorphous polyester resin,
The B layer contains 75 to 95% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C., based on the mass (100% by mass) of the entire resin component in the B layer. A non-oriented resin layer having a thickness of 20 to 200 μm,
The C layer is substantially 55 to 70% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C. based on the mass of the entire resin component in the C layer (100% by mass). A non-oriented resin layer having a thickness of 5 μm or more, comprising 45 to 30% by mass of an amorphous polyester resin,
A laminated sheet having a total thickness in the range of 70 to 300 μm. A layered sheet comprising at least three layers of A layer, B layer and C layer, and at least B layer and C layer are integrally formed by coextrusion film forming method,
The A layer is a non-oriented resin layer having a thickness of 45 μm or more mainly composed of a substantially amorphous polyester resin,
The B layer contains 75 to 95% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of 210 to 230 ° C., based on the mass (100% by mass) of the entire resin component in the B layer. A non-oriented resin layer having a thickness of 20 to 200 μm,
The C layer contains 70 to 100% by mass of a polybutylene terephthalate (PBT) resin having a melting point (Tm) of less than 210 ° C., based on the mass of the entire resin component in the C layer (100% by mass). A non-oriented resin layer having a thickness of 5 μm or more,
A laminated sheet having a total thickness in the range of 70 to 300 μm. The substantially non-crystalline polyester resin of the A layer and the C layer is mainly composed of terephthalic acid or dimethyl terephthalic acid as a main component of a dicarboxylic acid component, and 20 to 80 mol. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining 80 to 20 mol. The laminated sheet according to claim 1, wherein% is a copolyester comprising ethylene glycol. The substantially non-crystalline polyester resin of the A layer is mainly composed of terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component, and 20 to 80 mol. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining 80 to 20 mol. The laminated sheet according to claim 2, wherein% is a copolyester comprising ethylene glycol. The laminated sheet according to any one of claims 1 to 4, wherein a storage elastic modulus at 190 ° C in a dynamic viscoelastic tension method 10 Hz measured as a laminated sheet is 1 x 10 ⁷ Pa or more in the MD direction of the sheet.   A polybutylene terephthalate (PBT) resin having a melting point (Tm) of 20 to 40% by mass of 210 to 230 ° C. is blended in the A layer, based on the mass (100% by mass) of the entire resin component in the A layer. The laminated sheet according to any one of claims 1 to 5.   The laminated sheet according to any one of claims 1 to 6, wherein the A layer is substantially transparent, and a printed pattern (D) by printing is provided between the A layer and the B layer.   The A layer is substantially transparent, and a printed pattern (D) by printing is applied between the A layer and the B layer, and further, the printed pattern (D) and the B layer The laminated sheet according to any one of claims 1 to 7, wherein a non-oriented resin layer (E layer) mainly composed of a substantially amorphous polyester-based resin is disposed therebetween. The substantially amorphous polyester-based resin of the E layer is mainly composed of terephthalic acid or dimethyl terephthalic acid as a main component of a dicarboxylic acid component, and 20 to 80 mol. % Is 1.4-cyclohexanedimethanol (1.4-CHDM) and the remaining 80 to 20 mol. The laminated sheet according to claim 8, wherein% is a copolyester comprising ethylene glycol.   The embossed design sheet which has the embossed pattern which heated the laminated sheet of Claims 1-9 to the range of 160-190 degreeC, and was formed in the said A layer side surface by the embossing plate roll.   An embossed design sheet-covered metal plate, wherein the surface on the C layer side of the embossed design sheet according to claim 10 is laminated on a metal plate using an adhesive.   A building interior material selected from the group consisting of a door material, a unit bath wall material, a unit bath ceiling material, a partition material and a panel material, using the embossed design sheet-covered metal plate according to claim 11.   A steel furniture member using the embossed design sheet-coated metal plate according to claim 11.   A household electrical appliance housing member using the embossed design sheet-coated metal plate according to claim 11.

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