JP4885579B2 - Designable laminate sheet and design laminate sheet-coated metal plate - Google Patents

Description

  The present invention relates to a designable laminated sheet and a designable laminated sheet-coated metal plate. In particular, the present invention relates to a designable laminated sheet-covered metal plate that can be used as a unit bath member, a door material, a building interior material, and the like, and a designable laminate sheet that is a coating material for the metal plate.

  Conventionally, as a design resin-coated metal plate used for a building interior material or the like, a type provided with a so-called mirror surface design and a type provided with an embossed design have been used. As a type to which a mirror surface design is given, for example, a printed pattern is given on a sheet of soft polyvinyl chloride colored by adding a pigment (hereinafter, polyvinyl chloride may be abbreviated as “PVC”). In addition, a structure in which a transparent and smooth resin film is coated thereon has been used. In addition, as a type to which an embossed design is given, for example, a type in which emboss is given to the surface of a single layer flexible PVC sheet has been generally used.

  However, in recent years, changes in lifestyles and diversification of individual preferences have affected living spaces, and there is a need to create products that reflect them. Design-coated resin-coated metal plates used for building interior materials, etc. However, it is calculated | required to have the design property which was more excellent. And the request | requirement with respect to the designable resin-coated metal plate which has an internal embossing structure as a structure which can obtain a feeling of depth, a three-dimensional feeling, etc. is high. Here, an internal embossing structure means the structure which can visually recognize the uneven | corrugated pattern (embossing design) which exists inside through the surface layer which has a transparent or semi-transparent and highly smooth surface.

  Regarding such a design resin-coated metal plate having an internal emboss structure, Patent Document 1 describes a method of coating a concavo-convex surface such as a colored soft PVC sheet having an embossed surface with a transparent PVC paste or the like. . Patent Document 2 describes a method of filling and curing a solvent-free curable resin on the surface of a thermoplastic resin sheet embossed on the surface. Patent Document 3 describes a thermoplastic resin sheet provided with a transparent thermoplastic resin layer with a dry lami adhesive on the embossed surface of the thermoplastic resin sheet. In Patent Document 4 and Patent Document 5, an ultraviolet curable adhesive is filled between the uneven surface of a colored soft PVC sheet embossed and printed on the surface and a transparent surface layer, and a transparent top film is further provided. Methods such as coating are described.

JP-A-1-141050 JP-A-1-275138 Japanese Patent No. 2960173 Japanese Patent No. 3384508 Japanese Patent No. 3337176

  However, in the decorative sheet of Patent Document 1, after the PVC paste is further coated on the embossed soft PVC sheet, a baking process is required to gel the paste. At the same time, treatment such as passing between a pair of pressure rolls under heating is necessary to smooth the surface. Further, the embossing heat resistance of soft PVC is sufficient under normal use environments, but is not inherently very high. For this reason, emboss return occurs during the heating and pressurizing processes described above, and it is difficult to impart an internal embossed design with a sufficient depth to the final decorative sheet. Further, in recent years, in interior building materials, the use of volatile organic compounds (VOCs) and materials with a concern of having endocrine disrupting substances has been restricted. From this point, the use of soft PVC It has come to be restricted.

  Since the solvent-free curable resin layer is the outermost surface, it is necessary to improve the scratch resistance of the layer, and the resin-coated metal plate is obtained by Patent Document 2. Since it is necessary to secure secondary workability, especially bending workability, it is necessary to design a very difficult material as an adhesive that forms such an outermost surface to be applied to resin-coated metal sheets. It was difficult to obtain a product at a low price.

  According to Patent Document 3, a thermoplastic resin film is used for the outermost layer, so that the surface layer can be appropriately selected by using a biaxially stretched PET film or the like, so that scratch resistance and workability as a resin-coated metal plate can be achieved. However, the adhesive for dry laminating is solvent-based and cannot be thickly applied, and therefore cannot give a deep internal embossing design.

  Also, those obtained by Patent Documents 4 and 5 are generally included as evaluation items for workability (flexibility) as a resin-coated metal plate and unit bath use due to the physical properties of the ultraviolet curable adhesive. It was difficult to satisfy the boiling water immersion test. That is, it is difficult to obtain good processability when a hard material is used as a cured product of an ultraviolet curable adhesive, and when a flexible material is used, it may pass a boiling water immersion test. It was difficult.

  The study itself of replacing the soft PVC sheet for the resin-coated metal plate with a non-PVC thermoplastic resin sheet is proceeding, and the base sheet used for the mirror design and the embossed design sheet are already colored polyester-based resin sheets, Although what consists of a coloring polyolefin-type resin sheet is marketed, a good thing is not obtained about the thing of an internal embossing structure.

  The reason for this is that in order to enhance the sense of depth and three-dimensionality, it is necessary to use a colored resin layer that is thick to some extent, and deep embossing must be applied. When formed with a thickness, there is a problem that bending whitening is likely to occur in the processing after forming the resin-coated metal plate.

  Further, when a polyester resin is used as the colored resin layer, this problem is avoided, but there is a problem that there is no preferred coating agent that should be changed to the transparent PVC paste used to embed the emboss. Further, when the surface layer was covered with a transparent top film using an ultraviolet curable adhesive, a problem occurred in the boiling water immersion property or workability as in the above-mentioned Patent Documents 4 and 5.

  In addition, when a normal solvent-based curable adhesive is used in place of the ultraviolet curable adhesive, thick coating is difficult because the adhesive is a solution, and the solvent of the applied adhesive layer is difficult. Since the dried film thickness of the adhesive layer is further reduced by the volatilization, it was not possible to secure a coating thickness sufficient to fill deep embossing and obtain smoothness on the surface of the transparent surface layer.

  In addition, in the solventless cyanate curable adhesive, the viscosity of the adhesive becomes extremely high when trying to have the ability to withstand bending workability and boiling water immersion test as a resin-coated metal plate, The applicability of the adhesive has deteriorated. On the other hand, when the coatability is ensured, there is a problem that satisfactory cured product properties cannot be obtained. Further, with this cyanate curable adhesive, it takes time to cure after application, so that no deviation occurs between the transparent surface layer and the colored resin layer until it is cured, or the adhesive layer In order to prevent deformation such as dents due to external force, special measures are required. Therefore, in a method using a solventless cyanate curable adhesive, a product having practical productivity and performance has not been obtained.

  Therefore, the present invention does not use a halogen-containing resin, has good processability, and allows the internal embossing to be visually recognized through a smooth and transparent surface. Provided are a designable laminated sheet-covered metal plate that has a structure and can be suitably used in a unit bath application without causing a problem even in a boiling water immersion test, and a designable laminated sheet for producing the metal plate This is the issue.

  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.

1st this invention is a lamination sheet which has at least 3 layers of a base material layer (10), an adhesive bond layer (20), and a surface layer (30), and these layers are laminated | stacked in this order, The base material layer (10) has a polyester resin as a main component, contains a pigment, has an uneven design by embossing on the surface on the side laminated with the adhesive layer (20), is non-oriented, and has a thickness of 100 μm or more. 300 μm or less, and the adhesive layer (20) contains 50% by mass to 96% by mass of the ultraviolet curable adhesive and 4% by mass to 50% by mass of the isocyanate-terminated urethane prepolymer. The storage elastic modulus of the cured composition of the mixed composition as a main component and the dynamic viscoelastic tension method at 10 Hz is 2.0 × 10 ⁸ Pa or more, 2.0 × 10 ⁸ at 20 ° C. ⁹ Pa less and at 100 ° C., 2.0 10 ⁶ Pa or more, or less 4.0 × ¹⁰ 7 Pa, the thickness of a layer having embossed protrusions thickness or more thickness to completely fill the substrate layer (10), the surface layer (30), It is a designable laminated sheet (100a) which is a transparent stretched layer mainly composed of a polyester-based resin.

  In the first aspect of the present invention, the polyester resin constituting the base material layer (10) is a polybutylene terephthalate resin (hereinafter, referred to as 20% by mass or more and 80% by mass or less), with the mass of the entire polyester resin being 100% by mass. "May be abbreviated as" PBT resin ") and / or polytrimethylene terephthalate resin (hereinafter may be abbreviated as" PTT resin ") and the remaining 20% by mass. It is preferable that it is a mixture with the polyester-type resin of 80 mass% or less substantially amorphous. When the polyester resin constituting the base material layer (10) consists only of a substantially amorphous polyester resin, there is an advantage that embossing or the like can be easily performed on the design laminated sheet. Since the glass transition temperature of such a substantially amorphous polyester-based resin is less than 100 ° C., the designable laminated sheet may not be able to satisfy the boiling water immersion test. Therefore, by incorporating a PBT resin, a PTT resin, or a mixture thereof as the polyester resin, these resins crystallize, and the elasticity of the base material layer (10) is close to the crystal melting point. The rate can be maintained high, and no problem can be caused in the boiling water immersion test. In addition, the base material layer (10) is a layer laminated to the metal plate (50), and even when this lamination is performed in the same temperature range as when the conventional soft PVC was attached to the metal plate, Sufficient adhesive strength can be obtained.

  Further, the substantially amorphous polyester-based resin is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and the entire diol component is 100 mol%, and is 20 mol% to 80 mol% of the diol component. It is preferable that the following is 1.4-cyclohexanedimethanol (1.4-CHDM), and the remaining component is a copolyester composed of ethylene glycol. The substantially amorphous polyester resin having such a composition secures the effect of the base material layer (10) more suitably, is easily commercially available, and is stable in raw material supply and cost. It is preferable from the point of merit.

  In the first invention, it is preferable to use a transparent stretched polyester resin sheet as the surface layer (30). As the surface layer (30), by using a transparent stretched polyester resin sheet, which is a proven material that has been used as an overlay for soft PVC, various surfaces can be used when used in a bathroom as a laminated sheet-coated metal plate for a unit bath. It can be assumed that there is no possibility of causing a problem in physical properties. Moreover, since this resin sheet has favorable smoothness, what is called a mirror appearance can be obtained easily. In addition, since the material is widely used worldwide, it is possible to obtain advantages of supply stability and cost.

  In the first present invention, the base material layer (10) faces the adhesive layer (20) side and is opposite to the first base material layer (12) containing the glitter pigment and the adhesive layer (20) side. It can also be comprised from the at least 2 layer of the 2nd base material layer (14) located in the side and containing the coloring pigment with a concealing power. By adopting such a configuration, the effect of improving the shape visibility of the internal embossing by adding the glitter pigment can be sufficiently exerted, and the pigment can be applied to the metal plate (50) with a coloring pigment having a hiding power. When attached, it is possible to obtain the designable laminated sheet-coated metal plate (200) having a stable color tone without being influenced by the surface state or color change of the metal plate (50).

  In 1st this invention, between an adhesive bond layer (20) and a base material layer (10), between an adhesive bond layer (20) and a 1st base material layer (12), or a 1st base material layer ( A printing layer (40) may be provided between 12) and the second base material layer (14). Thereby, in addition to a coloring design, a surface smoothness design, and an internal embossing design, the design of a pattern and color by printing can also be provided. Further, a printing layer is provided between both the adhesive layer (20) and the first base material layer (12) and between the first base material layer (12) and the second base material layer (14). (40) may be formed.

  The printing layer (40) includes a first printing layer (42) formed with a printing ink containing a bright pigment and a second printing layer (44) formed with a printing ink containing a general coloring pigment. You may comprise from at least 2 layers. In this case, the shape visibility of the internal embossing can be improved by the first printed layer (42) containing the glitter pigment, and the design of the pattern and the color is imparted by the second printed layer (44). be able to.

  As shown in FIG. 1 (c), the first printed layer (42) and the second printed layer (44) have both printed layers interposed between the adhesive layer (20) and the base material layer (10). Alternatively, the first printed layer (42) may be formed between the adhesive layer (20) and the first base material layer (12), and the second printed layer (44) may be formed on the first group. You may form between a material layer (12) and a 2nd base material layer (14). Alternatively, the first printed layer (42) containing the glitter pigment may be provided as the printed layer (40) without providing the first substrate layer (12) containing the glitter pigment as the substrate layer (10). Good.

  2nd this invention has said designable laminated sheet (100) and metal plate (50), and the surface at the side of the base material layer (10) of a designable laminated sheet (100) is a metal plate (50). This is a laminated laminated sheet for designable laminated sheet (200).

  The designable laminated sheet-coated metal plate (200) of the present invention has a so-called internal embossing structure having a sense of depth and a three-dimensional effect since the internal embossing can be visually recognized through a smooth and transparent surface. . Moreover, since the designable laminated sheet-coated metal plate (200) of the present invention has the above-mentioned design and is excellent in scratch resistance and workability, it is also excellent in boiling water immersion resistance. It can be used suitably.

  3rd this invention is a building interior material selected from the group which consists of a door material, a unit bath member, a partition material, and a general wall material using the lamination sheet coating | coated metal plate (200) of 2nd this invention. is there. In addition, as a unit bath member, a unit bath wall material, a unit bath ceiling material, etc. are mentioned.

  In the designable laminated sheet (100) of the present invention, the adhesive layer (20) is mainly composed of a predetermined mixed composition, and the storage elastic modulus of the cured product of the mixed composition is within a predetermined range. As a result, it is possible to satisfy both the bending workability at low temperature and the boiling water immersion property, and the adhesion between layers can be made sufficient. Further, since the mixed composition constituting the adhesive layer (20) is a solvent-free adhesive, even if the surface of the base material layer (10) is relatively deeply embossed, It is easy to ensure a coating thickness sufficient to completely fill the surface and obtain smoothness on the surface of the transparent surface layer (30). Thereby, an internal embossing structure with a sense of depth and a three-dimensional feeling that can visually recognize the internal embossing through a smooth and transparent surface can be provided. Furthermore, since the above-mentioned adhesive composition can obtain sufficient initial curing by irradiation with ultraviolet rays, it is not necessary to devise special measures for curing as in the case of using a cyanate curable adhesive, and is excellent in productivity. Moreover, the designable laminated sheet (100) of the present invention is environmentally friendly without using a halogen-containing resin.

Hereinafter, embodiments embodying the present invention will be described.
FIG. 1 is a schematic diagram showing the layer structure of the designable laminated sheets 100a to 100f and the designable laminated sheet-coated metal plate 200 of the present invention.

  The resin “sheet” used as each layer of the designable laminated sheet 100 of the present invention is more correctly described as “film and sheet” from the viewpoint of the thickness range. The single name “sheet” is also used for the range called “for convenience”.

  In addition, the expression “non-oriented” means that the sheet was not intentionally subjected to an alignment treatment such as a stretching operation in order to impart some performance to the sheet, and is generated by drawing (drawing) with a casting roll during extrusion film formation. It does not mean that such an orientation does not exist.

  As the most basic configuration of the designable laminated sheet of the present invention, as shown in FIG. 1 (a), it has at least three layers of a base material layer 10, an adhesive layer 20, and a surface layer 30, and these The laminated sheet 100a has a configuration in which the layers are laminated in this order, that is, a configuration in which the adhesive layer 20 is provided on the base material layer 10 and the surface layer 30 is provided thereon. Hereinafter, each of these layers will be described in order.

<Base material layer 10>
The base material layer 10 is a layer mainly composed of a polyester-based resin, contains a pigment, has an uneven design by embossing on the surface to be laminated with the adhesive layer 20 described below, The layer is oriented and has a thickness of 100 μm or more and 300 μm or less.

  As the polyester-based resin used for the base material layer 10, it is easy to give an uneven design by embossing, and the workability as a designable laminated sheet-coated metal plate 200 obtained by laminating the laminated sheet 100 of the present invention is ensured. Any sheet can be used without limitation as long as it does not cause deformation of the sheet when immersed in boiling water. Among these, as a polyester-type resin which comprises the base material layer 10, 20 mass% or more and 80 mass% or less of PBT-type resin and / or PTT-type resin on the basis (100 mass%) of the whole polyester-type resin, It is preferable to use a mixture of the remaining component, which is 20% by mass or more and 80% by mass or less, of a substantially amorphous polyester resin. Also, based on the total mass of the polyester resin (100 mass%), 25 mass% or more and 80 mass% or less of PBT resin and / or PTT resin and the remaining components of 20 mass% or more and 75 mass% or less. It is further preferable to use a mixture with a substantially amorphous polyester resin.

  When the base layer 10 is composed of only the substantially amorphous polyester-based resin described above, it is possible to easily impart deep embossing, but it is substantially amorphous that is available on a commercial level. Since the glass resin temperature of the polyester resin, which is a property, is lower than 100 ° C., when the designable laminated sheet-coated metal plate 200 is subjected to a boiling water immersion test, the base material layer 10 undergoes fluid deformation.

  On the contrary, if the base material layer 10 is made of only a crystalline resin such as PBT resin or PTT resin, the elastic modulus of the base material layer 10 is maintained up to the melting point of these resins. The test does not cause any problems, but is limited by the method of applying embossing, and it is particularly difficult to provide embossing with the depth necessary for the present invention. Further, in the case of a configuration made of only a crystalline resin, when laminating to the metal plate 50, the metal plate 50 must be heated to a temperature slightly higher than the temperature condition where conventional soft PVC is laminated. Sufficient adhesive strength cannot be obtained, and it is necessary to change the conventionally used coating for the back surface of the metal plate to one having higher heat resistance. In addition, the metal plate back surface coating here is applied for the purpose of anticorrosion on the back surface. Furthermore, in the configuration provided with the printing layer 40 described below, there arises a problem that it is necessary to use a printing ink having higher heat resistance than a general ink conventionally used.

  In the designable laminated sheet 100 of the present invention, as described above, the base material layer 10 is a mixture containing a PBT resin or PTT resin and a substantially amorphous polyester resin in a predetermined composition. By doing so, embossing becomes relatively easy, and flow deformation does not occur in the boiling water immersion test. In addition, sufficient adhesive strength can be obtained in the temperature range where conventional soft PVC is laminated when laminating with the metal plate 50.

  In addition, the PBT resin and the PTT resin have good processability compared to the PET resin even in a non-oriented and crystallized state, and the design laminate sheet 100 using the mixture containing them as the base layer 10 The workability of the coated metal plate 200 can be improved. On the other hand, when a non-oriented PET-based resin is used for the base material layer 10, the melting point becomes too high in the crystallized state of the PET-based resin, and under the temperature conditions in which soft PVC has been laminated conventionally. Sufficient adhesive strength with the metal plate 50 cannot be obtained, and it is difficult to improve the workability of the resin-coated metal plate coated with this sheet. Further, when the PET-based resin is in an amorphous state, the crystallization rate is slow, so that the base material layer 10 is fluidly deformed when immersed in boiling water, resulting in poor appearance quality of the resin-coated metal plate.

  As the PBT resin constituting the base material layer 10, it is preferable to use a resin having a melting point of 210 ° C. or higher and 230 ° C. or lower. A PBT resin having a melting point lower than this is not preferable because the crystallization rate is slow, and the dipping property of the design-laminated laminated sheet-coated metal plate 200 may not be improved, and the raw material price is expensive. Specifically, a so-called homo PBT resin (which includes an unintended copolymerization component) using terephthalic acid or dimethyl terephthalic acid as a dicarboxylic acid component and 1.4-butanediol as a diol component. May be used). This homo PBT resin has a melting point of about 225 ° C., which is advantageous from the viewpoint of cost and stable supply than a copolymerized PBT resin having a lower melting point.

  In addition to the above-mentioned homo PBT resin, the PBT resin is one in which a part of the acid component is substituted with a dicarboxylic acid such as isophthalic acid, and has a melting point of 210 ° C. or higher, polytrimethylene glycol (PTMG) Copolymerized ones can be used. When a sheet of the base material layer 10 is produced by an extrusion film forming method, it is common to select a material having an intrinsic viscosity of about 1.0 to 1.4, and commercially available materials are obtained from each company. can do.

  Further, although not as good as PBT resins in terms of cost, freedom of grade selection, and stable supply, PTT resins having a melting point similar to PBT resins and having a high crystallization rate are also the basis of the present invention. It can be used for the material layer 10.

  The substantially amorphous polyester-based resin constituting the base material layer 10 is not only a resin having no clear crystallization behavior or crystal melting behavior as measured by a differential scanning calorimeter (DSC), Although crystallinity is recognized, the crystallizing rate is extremely slow, the heat of crystal melting is very small, and the material can be handled as a substantially amorphous polyester resin.

  Among these substantially non-crystalline polyester resins, terephthalic acid or dimethyl terephthalic acid is the main component of the dicarboxylic acid component, and the entire diol component is 100 mol%, and the diol component is 20 mol% or more and 80 mol% or less. It is preferable to use a copolymerized polyester composed of ethylene glycol with 1.4-cyclohexanedimethanol (hereinafter sometimes abbreviated as 1.4-CHDM).

  Here, "mainly" means that terephthalic acid or dimethyl terephthalic acid is contained in an amount of 80 mol% or more, more preferably 90 mol% or more, based on the whole dicarboxylic acid component (100 mol%).

  If the amount of the copolymerized diol component 1.4-CHDM is too small, the crystallinity of the copolymerized polyester becomes remarkable, and the embossed pattern is transferred to the base material layer 10 heated using an embossing machine or the like. When performing, crystallization may progress and embossing may become difficult. Moreover, when crystallizing in this way, the workability of the resulting designable laminated sheet-coated metal plate 200 is lowered, which is not preferable. On the other hand, when the amount of 1.4-CHDM is too large, the crystallinity of the copolyester becomes remarkable and the same problem occurs, which is not preferable.

  As an example of a substantially amorphous polyester-based resin having the above composition range, it is widely used worldwide, is easily available commercially, and has a high production volume, so that the cost is reduced. The so-called PET-G can be mentioned. As PET-G, for example, “Easter PET-G • 6763” manufactured by Eastman Chemical Company is preferably used.

  “Easter PET-G · 6763” has a structure in which about 30 mol% of the diol component of polyethylene terephthalate resin is substituted with 1.4-CHDM, and the thermal behavior due to crystallinity is measured by DSC. It is a substantially amorphous polyester resin that is not recognized.

  As another example, “PCTG 5445” manufactured by Eastman Chemical Company, which shows crystallinity under specific conditions but can be handled as an amorphous resin under normal conditions, can also be used. The resin has a structure in which about 65 mol% of the diol component of the polyethylene terephthalate resin is substituted with 1.4-CHDM. In addition to this, a substantially non-crystalline PET copolymer resin in which a part of the diol component is substituted with neopentyl glycol, and a low crystallinity PET resin copolymerized with isophthalic acid. A polyester-based resin having a composition in which crystallization is inhibited by the copolymer component can also be used.

  The base material layer 10 is provided with a design property, a visual concealing effect for the metal plate 50 to be coated, an improvement in the visibility of the embossed design, and when the printed layer 40 is provided on the surface, the color development. A pigment is added for the purpose of improving the quality. 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. As an example of the pigment, a white-based coloring can use a titanium oxide pigment that has a high concealing effect and has a fine particle size and thus has little influence on the processability of the laminated sheet. In addition, in white chromatic coloring, a chromatic organic or inorganic pigment added in a small amount for adjusting the color tone based on this titanium oxide pigment can be used. As a method for improving the visibility of the embossed design, a bright pigment or the like may be added.

  Regarding the visual hiding effect of the base, the degree of importance differs depending on the use and cannot be specified unconditionally. However, as one guideline, in the design laminated sheet-coated metal sheet 200 for interior building materials, JIS K5400 7.2 “Paint in general It is preferable that the concealment ratio measured in accordance with “Test method / Concealment ratio” is 0.98 or more.

  As shown in FIG. 1 (d), the base material layer 10 is not a single layer, but faces the adhesive layer 20, the first base material layer 12 to which the glitter pigment is added, the adhesive layer 20, May be located on the opposite side and may be composed of at least two layers of the second base material layer 14 to which a coloring pigment having a hiding power is added. It is known that the shape visibility of the internal embossing is improved by adding a bright pigment, and the effect is particularly remarkable in the base material layer 10 that is colored white, but the base material layer 10 is a single layer. In this case, a coloring pigment such as titanium oxide having a strong hiding power and a bright pigment are kneaded in the same layer, and the effect of the bright pigment tends to be insufficient. It is particularly preferable to use the base material layers 12 and 14.

  Furthermore, since the luster pigment is generally inferior in hiding power, by disposing a layer to which a coloring pigment having hiding power is added below, the surface state of the metal plate 50 and the change in color are not affected, The designable laminated sheet-coated metal plate 200 having a stable color tone can be obtained.

  As bright pigments, various pearl pigments, such as so-called pearl mica, with surface modification such as titanium coat, and metal flakes such as glass flakes and aluminum flakes that are electrolessly plated with various metals such as silver and nickel Finely cut metal foil such as aluminum foil, finely cut metal foil such as aluminum foil surface-treated with epoxy resin, finely cut resin sheets treated with electroless plating of various metals, etc. Can be used.

  Moreover, the base material layer 10 is good also as a multilayer structure as described in "WO04 / 098883" or "Japanese Patent Application No. 2004-285225" for the purpose of giving the embossing suitability by an embossing machine. As an example, FIG. 1 (e) and FIG. 1 (f) show an embodiment of the layer structure in the case of using a laminated sheet excellent in embossing suitability in the embossing machine in the invention described in “WO04 / 098883”. showed that. In these configurations, the base material layer 10 includes a layer 15 (upper layer) containing a glitter pigment, 20 to 40% by mass of a PBT-based resin, and 80 to 60% by mass of a substantially amorphous polyester resin. It is composed of three layers: a layer 16 (middle layer) made of a mixture composition and containing a color pigment, and a layer 17 (lower layer) mainly composed of a PBT resin. Moreover, in these structures, the resin composition of the layer 15 containing a luster pigment is also a mixture composition of 20 to 40% by mass of a PBT resin and 60 to 80% by mass of a substantially amorphous polyester resin. It is preferable to do. Further, the printed layer 40 described later may be provided between the layer 15 containing the glitter pigment and the layer 16 containing the color pigment (in the form shown in FIG. 1 (e)), or contains the glitter pigment. You may provide between the layer 15 and the adhesive bond layer 20 (form of FIG.1 (f)).

  Various amounts of various additives may be added to the base material layer 10 as long as the properties are not impaired. General additives include phosphorus, phenol and other antioxidants; lactone and phenol acrylate process stabilizers; thermal stabilizers, UV absorbers, hindered amine radical scavengers, and various processing aids. , Metal deactivators, lubricants, antibacterial / antifungal agents, antistatic agents, flame retardants, pigment dispersibility improving agents, filling / extending agents, and the like. Furthermore, since the base material layer 10 is mainly composed of a polyester-based resin, a carbodiimide-based, epoxy-based, oxazoline-based terminal carboxylic acid sealing agent, or a so-called hydrolysis inhibitor may be added.

  A preferable thickness of the base material layer 10 is in a range of 100 μm or more and 300 μm or less. If it is thinner than this, the type of embossing that can be imparted is limited, making it difficult to transfer an embossed pattern rich in three-dimensionality and depth, and as a result, it is difficult to impart depth to the laminated sheet 100. Become. In addition, it is preferable that the emboss provided to the base material layer 10 has a maximum height (Ry) of 50 μm or more, and more preferably 75 μm or more.

  In order to express the design of depth and three-dimensional effect more strongly, the thickness of the base material layer 10 is better in that a deeper embossed pattern can be transferred. However, if the thickness exceeds 300 μm, how much adhesion is possible? Even if the composition of the agent layer 20 is devised, the workability of the design-oriented laminated sheet-coated metal plate 200 is deteriorated. In addition, it becomes difficult to use a molding die that has been conventionally used for a molding process such as a bending process for a soft PVC resin-coated metal plate, and a new mold needs to be produced.

<Adhesive layer 20>
The adhesive layer 20 is mainly composed of a mixed composition containing an ultraviolet curable adhesive in an amount of 50% by mass to 96% by mass and an isocyanate-terminated urethane prepolymer in an amount of 4% by mass to 50% by mass, The storage elastic modulus at 10 Hz of the dynamic viscoelastic tension method for the cured product of the mixed composition is 2.0 × 10 ⁸ Pa or more, 2.0 × 10 ⁹ Pa or less at 20 ° C., and 2 at 100 ° C. 0.0 × 10 ⁶ Pa or more and 4.0 × 10 ⁷ Pa or less, and the thickness thereof is a layer having a thickness equal to or greater than the thickness at which the embossed convex portion of the base material layer 10 is completely buried.

When the storage elastic modulus at 20 ° C. of the cured product of the mixed composition constituting the adhesive layer 20 is too high, the folding workability of the laminated sheet-coated metal plate 200 at a low temperature is not sufficient. If it is too low, the adhesion strength with the base material layer 10 tends to be insufficient, and there is a concern that a peeling failure at the interface between the base material layer 10 and the adhesive layer 20 may occur during use as the laminated sheet-coated metal plate 200. is there. In addition, when the storage elastic modulus at 20 ° C. is too low, there is a concern that the adhesive layer 20 may be plastically deformed and have a poor appearance when a long-time stress is applied from the surface of the laminated sheet-coated metal plate 200. is there. From the viewpoint of bending workability at low temperatures, the storage elastic modulus at 20 ° C. is more preferably 2.0 × 10 ⁸ Pa or more and 1.0 × 10 ⁹ Pa or less.

  In addition, when the storage elastic modulus at 100 ° C. of the cured product of the mixed composition constituting the adhesive layer 20 is too low, the adhesive layer 20 may cause flow deformation in the boiling water immersion test, as a result. Appears to be poor in appearance. Moreover, when the storage elastic modulus at 100 ° C. is too high, it is difficult to set the storage elastic modulus at 20 ° C. within a preferable range.

  The ultraviolet curable adhesive constituting the adhesive layer 20 is composed of ordinary monomers and oligomers, polymers, photopolymerization initiators, and organic solvents that are polymerized by irradiation with active energy rays to form a cured film. . As this monomer and oligomer, for example, monomers and oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are used. Some of these include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate. Examples thereof include monofunctional and polyfunctional acrylic monomers, methacrylic monomers, and vinyl monomers having one or more carbon-carbon double bonds, such as methacrylate, isoamyl acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, and N-vinylpyrrolidone.

  Among these monomers, monofunctional monomers include, for example, acrylamide derivatives such as dimethylacrylamide, diethylacrylamide and diisopropylacrylamide, acryloylmorpholine, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl. N-alkyl (meth) acrylates such as oxyethyl acrylate, benzyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, isoalkyl (meth) acrylates such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate Rate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, 2-acryloyloxyethyl succinic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylic , Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) Acrylate, ethoxydiethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, tricyclo Decanyl (meth) acrylate, bornyl (meth) acrylate, diacetone acrylamide, isobutoxymethyl (meth) acrylic Luamide, N-vinylpyrrolidone, N-vinylcaprolactam, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate Can be mentioned.

  Examples of polyfunctional monomers include polyethylene glycol di (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol Lumpur diglycidyl ethers of A (meth) epoxy obtained by adding acrylate (meth) acrylate.

  Specific examples of the UV curable adhesive include commercially available Aronix (manufactured by Toa Gosei Co., Ltd.), Dicure (manufactured by Dainippon Ink & Chemicals), New Frontier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Art Resin (Negami Kogyo Co., Ltd.) Etc.), but is not limited thereto.

  The glass transition temperature of the ultraviolet curable adhesive is preferably in the range of −40 ° C. to 100 ° C. If the glass transition temperature is too high, the adhesiveness between the resulting adhesive layer 20 and the surface layer 30 tends to be inferior, or the workability when the laminated laminate sheet-coated metal plate 200 is made tends to be poor, and the glass If the transition temperature is too low, the adhesion between the adhesive layer 20 and the surface layer 30 after immersion in boiling water tends to be inferior, and the adhesive layer 20 itself is softened and fluidly deformed during immersion in boiling water. There exists a tendency for the external appearance of the designable lamination sheet covering metal plate 200 to worsen.

  Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Thioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino - propan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like. Moreover, as a commercial item, IRUGACURE184, 651, 500, 907, CG1369, CG24-61, Darocure 1116, 1173 (above, made by Ciba Specialty Chemicals), Lucirine LR8728 (made by BASF), Ubekrill P36 (made by Daicel-Cytec), etc. Can be mentioned. When curing with visible light, it is preferable to use a visible light sensitized photopolymerization initiator such as camphorquinone. The photopolymerization initiator is preferably blended in an amount of 0.1 to 10% by mass based on the mass of the ultraviolet curable adhesive (100% by mass).

In addition, the sensitivity of photopolymerization can be improved by adding an additive having a sensitizing action. As the photosensitizer, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate,
Examples include ethyl 4-dimethylaminobenzoate and isoamyl 4-dimethylaminobenzoate, and commercially available products include Ubekryl P102, 103, 104, and 105 (above, manufactured by UCB). These photosensitizers are preferably blended in an amount of 0.001 to 10% by mass based on the mass of the ultraviolet curable adhesive (100% by mass).

  The adhesive layer 20 has a thickness equal to or greater than the thickness at which the embossed convex portion provided on the surface of the base material layer 10 is completely buried. This is because when the adhesive layer 20 is cured by ultraviolet irradiation, even if the shrinkage in the thickness direction of the adhesive layer 20 occurs somewhat, the portion corresponding to the embossed convex portion of the base material layer 10 is raised. This is to prevent reflection on the surface. By giving the adhesive layer 20 more than the thickness at which the embossed convex portion of the base material layer 10 is completely buried, the surface layer 30 is not reflected on the surface due to the embossed convex portion of the base material layer 10, A smooth state is maintained, and specularity can be secured on the surface of the surface layer 30.

  When the coating thickness of the adhesive layer 20 is lower than the height of the embossed convex portion of the base material layer 10, smoothness cannot be imparted to the surface of the surface layer 30, and when the adhesive layer 20 is applied or the surface layer 30. When laminating, problems such as bubbles are generated. Even when the coating thickness of the adhesive layer 20 is substantially equal to the height of the embossed protrusions of the base material layer 10, the surface of the surface layer 30 can be obtained when a slight volume shrinkage occurs in the thickness direction when the adhesive layer 20 is cured. The smoothness cannot be imparted. That is, regarding the thickness of the adhesive layer 20 in the present invention, the “thickness greater than the thickness at which the embossed convex portion of the base material layer is completely buried” is based on the surface of the surface layer 30 even after the adhesive layer 20 is cured. Even if the adhesive layer 20 shrinks when the adhesive layer 20 is formed on the base material layer 10 and cured, the adhesive layer 20 is not bonded. The thickness is such that the convex shape of the base material layer 10 does not appear on the surface of the agent layer 20.

  As described above, in order to obtain a three-dimensional effect due to the embossed design of the base material layer 10, the embossing imparted to the base material layer 10 is preferably 50 μm or more in maximum height (Ry). Therefore, the adhesive layer 20 must be applied with a thickness exceeding this. Such thick coating is difficult with solvent-based adhesives, and it is necessary to use solvent-free adhesives. However, conventional thermosetting adhesives and UV-curable adhesives have satisfactory performance. The thing was not obtained.

  Therefore, in the present invention, as the adhesive layer 20, the ultraviolet curable adhesive is 50% by mass to 96% by mass and the isocyanate-terminated urethane prepolymer is based on the mass of the entire mixed composition (100% by mass). The main component is a mixed composition containing the remaining components in a proportion of 4% by mass to 50% by mass. The urethane terminal prepolymer having an isocyanate terminal is more preferably 5% by mass or more and 30% by mass or less.

  When the addition amount of the isocyanate-terminated urethane prepolymer is too small, it is difficult to obtain adhesion between the adhesive layer 20 and the surface layer 30 described below. Moreover, when there is too much addition amount of the urethane terminal polymer of an isocyanate terminal, there exists a possibility that problems, such as being inferior in external quality, may arise, such as the adhesive bond layer 20 foaming after boiling water immersion.

  In the adhesive layer 20, an isocyanate-terminated urethane prepolymer used by mixing with an ultraviolet curable adhesive is a urethane prepared by a conventional method with an excess of organic polyisocyanate and polyol. It is a prepolymer.

  Organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidized diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene A diisocyanate, an isophorone diisocyanate, a xylylene diisocyanate, a hydrogenated xylylene diisocyanate, a hydrogenated diphenylmethane diisocyanate, a cyclohexane diisocyanate and the like can include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. It may be used as a mixture.

  Examples of the polyol include polyether polyol, polyester polyol, and other polyols, and a mixture of two or more of these can also be used. As the polyol, for example, a polyol produced using a composite metal cyanide complex as a catalyst can also be used.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, and one or more polyhydric alcohols such as sucrose, propylene oxide, ethylene oxide. , Polyols obtained by adding one or more of butylene oxide, styrene oxide and the like, polyoxytetramethylene polyol, and the like.

  Examples of the polyester polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane and other low molecular polyols, glutaric acid, and adipic acid. , Pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid, or other low molecular dicarboxylic acid or oligomeric acid condensation polymer and propiolactone, Examples thereof include ring-opening polymers such as caprolactone and valerolactone.

Examples of other polyols include polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, and acrylic polyol. In addition, low molecular polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol glycerin, trimethylolpropane, glucose, sorbitol, and shoelace.

  In addition, various additives such as a solvent, an inorganic filler, a small amount of process oil, a plasticizer, a thixotropic agent, a pigment, an ultraviolet ray preventing agent for stabilizing and improving weather resistance, and a stabilizer are added to the adhesive layer 20 as necessary. An agent, a catalyst, etc. may be included.

<Surface layer 30>
The purpose of the surface layer 30 is that the embossed design applied to the base material layer 10 is visually recognized through the surface layer 30 and the adhesive layer 20 in order to obtain a highly smooth design appearance called a mirror surface appearance. This is to obtain a design (internal embossing configuration) having a sense of depth and three-dimensionality.

  As the surface layer 30, the transparent stretched polyester resin sheet used for the soft PVC resin-coated metal plate, that is, the protection of the printing layer applied to the surface of the soft PVC, the improvement of various physical properties of the surface of the resin-coated metal plate, etc. The same transparent stretched polyester resin sheet that has been used for the purpose can be used.

  Among them, a biaxially stretched polyethylene terephthalate resin sheet is preferably used from the viewpoint of transparency, smoothness, resistance to various chemicals such as surface scratch resistance, and alkali resistance.

  The thickness of the surface layer 30 is preferably 38 μm or more and 125 μm or less, and more preferably 50 μm or more and 100 μm or less. If the thickness of the surface layer 30 is too thin, it is difficult to suppress a decrease in smoothness due to curing shrinkage of the adhesive layer 20, and if the thickness of the surface layer 30 is too thick, it is sufficient as the designable laminated sheet-coated metal plate 200. It becomes difficult to obtain processability.

  As the biaxially stretched polyethylene terephthalate resin sheet, those commercially available from various companies can be used, and a highly transparent grade, an easy adhesion treatment grade, or the like may be used as appropriate. Moreover, in the range which does not prevent visual recognition of the embossed design given to the base material layer 10, you may use what gave the back surface printing called a back print, and a matting agent etc. are mix | blended similarly and it is matte. A given biaxially stretched polyethylene terephthalate resin sheet or the like may be used.

  If an embossed design is also required for the surface of the surface layer 30 instead of a smooth surface design called a mirror-like appearance, a so-called biaxially stretched polyethylene terephthalate or the like may be used. This does not impair the basic performance as a biaxially stretched polyethylene terephthalate sheet such as chemical resistance, and can achieve embossing suitability in a state where a flexible resin layer is laminated on the lower layer by controlling the orientation. Examples of such easily processable biaxially stretched polyethylene terephthalate include “Teflex” manufactured by Teijin DuPont Films, Inc. and “New Conceptle Mirror” manufactured by Toray Industries, Inc.

<Print layer 40>
As shown in FIG. 1B, the printed layer 40 can be formed between the adhesive layer 20 and the base material layer 10 in the designable laminated sheet 100 of the present invention. The print layer 40 is applied by a known printing method such as gravure printing, offset printing, or screen printing. The pattern of the printing layer 40 is arbitrary, and examples thereof include a stone pattern, a wood grain, a geometric pattern, and an abstract pattern. The printing may be partial printing or full solid printing, and both the partial printing layer and the solid printing layer may be applied. Moreover, when the base material layer 10 which is a colored layer does not have the 1st base material layer 12 to which the bright pigment was added, you may add a bright pigment to the printing layer 40, and FIG. As shown in the layer configuration in (c), two of the first printing layer 42 formed of a printing ink containing a bright pigment and the second printing layer 44 formed of a printing ink containing a general coloring pigment. It is good also as a structure which consists of a layer. Thus, the visibility of internal embossing can be improved by adding a luster pigment to a printing layer. FIG. 1C shows a configuration in which the first print layer 42 is stacked on the second print layer 44, and this configuration is a basic configuration from the viewpoint of improving the visibility of the internal embossing. However, depending on the print design to be obtained, the second print layer 44 may be stacked on the first print layer 42.

  The printing layer 40 is between the adhesive layer 20 and the base material layer 10, between the adhesive layer 20 and the first base material layer 12, or between the first base material layer 12 and the second base material layer 14. Can be granted. The base material layer 10 is formed as a smooth sheet with no embossed pattern formed thereon, and after printing on the surface, the base material layer 10 is embossed on the printing surface with an embossing machine. The printing layer 40 can be formed on the substrate, and embossing can be formed.

  Moreover, after giving an embossed pattern to the base material layer 10, you may carry out by the method of printing on an uneven surface with an ink jet type printing apparatus etc. Alternatively, when the first base material layer 12 and the second base material layer 14 are not laminated and integrated in a die by a coextrusion method, either one or both surfaces of the first base material layer 12, or The printed layer 40 may be applied to the surface of the second substrate layer 14 on the side laminated with the first substrate layer 12.

<The manufacturing method of the designable laminated sheet 100 and the designable laminated sheet covering metal plate 200>
Next, the manufacturing method of the designable laminated sheet 100 and the designable laminated sheet-coated metal plate 200 of the present invention will be described. As a method for forming the base material layer 10, a known method such as an extrusion casting method using a T-die or an inflation method can be employed, and the film forming property and stable production of the sheet are not particularly limited. The extrusion casting method using a T die is preferable from the viewpoint of properties.

  As a method for applying an embossed pattern to the base material layer 10, a method in which an embossed pattern is engraved as a casting roll during extrusion film formation and a method for directly applying an embossed pattern to a resin flowing out from a T die in a molten state, The method of re-heating the sheet formed by the embossing machine in the process to give the embossed pattern, the base material layer 10 by heating when laminating the base material layer 10 formed without transferring the embossed pattern on the metal plate 50 Can be used without particular limitation as long as it is a method of re-melting and transferring the pattern with an embossing roll and then laminating the adhesive layer 20 and the surface layer 30 and other methods of embossing the thermoplastic resin sheet. it can. Among these, when the printing layer 40 is applied to the laminated sheet, since the workability is better when printing is performed on a smooth sheet, the latter two or similar methods are preferable, and the base material layer 10 is referred to as “WO04 / 098883”. ”And“ Japanese Patent Application No. 2004-285225 ”as a multi-layer structure, it is possible to transfer the pattern on the embossing machine by applying appropriateness to the embossing machine. Is particularly preferred.

FIG. 3 is an explanatory view showing the state of embossing in the case where the base material layer 10 has a multilayer structure composed of the upper layer 15, the middle layer 16 and the lower layer 17. In the embossing machine 300, the sheet material wound up in the order of the laminated sheet composed of the middle layer 16 and the lower layer 17 and the single layer sheet of the upper layer 15 on the heating roll 310 is heated in the infrared via the take-off roll 320. A predetermined process is performed by the heater 330, and further, the nip roll 340, the embossing roll 350, and the cooling roll 360 are sent.

  The method of applying the adhesive layer 20 to the embossed base material layer 10 is not particularly limited, and may be performed according to a known method according to the viscosity of the mixed composition of the adhesive layer 20. it can. For example, the adhesive layer 20 is formed by coating on the surface of the surface layer 30 to be laminated by using a temperature-adjustable two-component supply device, a mixer, a die coater, a squeeze coater, or the like. Examples thereof include a method of attaching to the layer 10, a method of supplying the adhesive layer 20 to the surface of the base material layer 10 on which the unevenness due to embossing is provided, and further covering the surface layer 30.

  The surface layer 30 and the base material layer 10 to which the adhesive layer 20 is applied, or the base material layer 10 and the surface layer 30 to which the adhesive layer 20 is applied are interposed by the adhesive layer 20 applied with a sufficient thickness. The outermost surface of the surface layer 30 is formed such that the embossed convex portion of the base material layer 10 and the surface of the surface layer 30 on the laminated side are not in direct contact with each other, and further passed between a pair of rubber rolls having a certain clearance. Are integrated so as to be maintained in a smooth state. Thereafter, the adhesive layer 20 is cured by irradiating an ultraviolet irradiation lamp from the surface 30 side surface.

  The method for laminating the designable laminated sheet 100 obtained as described above to the metal plate 50 is not particularly limited, but laminating with a thermosetting adhesive 60 is common. As the adhesive 60, a thermosetting type that has been used for the purpose of laminating a soft PVC sheet such as an acrylic adhesive, an epoxy adhesive, a urethane adhesive, and a polyester adhesive on the metal plate 50. Mention may be made of adhesives. Among these, since the base material layer 10 is made of a polyester-based resin, it is preferable to use a thermosetting polyester-based adhesive from the viewpoint of easily obtaining adhesion. As an example of a specific laminating method, the adhesive after drying is applied to the metal surface on which the design laminate sheet 100 is bonded to the metal plate 50 using commonly used coating equipment such as a reverse coater or a kiss coater. The thermosetting adhesive 60 is applied so that the film thickness is about 2 to 10 μm.

  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 50 is maintained at a temperature of about 230 to 250 ° C., and immediately using a roll laminator, -Designable laminated sheet covering metal plate 200 can be obtained by covering and cooling so that the base material layer 10 side of G 100 becomes an adhesive surface.

  As the metal plate 50 that is an object of the present invention, those conventionally used for resin-coated metal plates can be used without particular limitation, for example, cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel Various steel plates such as steel plate, hot dip zinc / aluminum alloy plated steel plate, hot dip zinc / aluminum / magnesium alloy plated steel plate, tin plated steel plate, tin free steel, stainless steel plate, aluminum alloy plate, nickel alloy plate, titanium alloy plate, etc. Can be used.

  The thickness of the metal plate 50 varies depending on the use of the designable laminated sheet-coated metal plate 200, but can be selected in the range of 0.1 to 10 mm. As an example, the thickness of the metal plate 50 is 0.3 to 0.00. Often, a thickness of 8 mm is used.

  The designable laminated sheet-coated metal plate 200 of the present invention is a designable material having an internal embossed structure with a sense of depth and three-dimensionality, and also has good workability, so that it is a door material, partition material, and general wall material. It can use suitably for building interior materials, such as. Moreover, since it does not cause a problem in the boiling water immersion test, it can be used particularly suitably as a unit bath wall material, a unit bath ceiling material, or the like.

  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. In addition, the measurement standard and the test method of the physical property of the designable lamination sheet coating metal plate 200 shown in the Example and the comparative example are as follows.

<Measurement standard, test method>
(Storage elastic modulus measurement about the hardened | cured material of the mixed composition which comprises the contact bonding layer 20)
The resin composition after curing of the adhesive layer 20 was measured with a viscoelastic spectrometer manufactured by Iwamoto Seisakusho. The measurement method was in accordance with the usual tensile method and temperature dispersion measurement, and the temperature was increased from −100 ° C. to 3 ° C./min. After measuring to 200 ° C., the storage elastic modulus at 20 ° C. and 100 ° C. was read. It was. In addition, preparation of the hardened | cured material of the adhesive bond layer 20 mixes and drops each composition of the adhesive bond layer 20 on the biaxially-stretched polyethylene terephthalate film with which the release property was provided on the surface, and also on it. The film was covered with a biaxially stretched polyethylene terephthalate film imparted with mold releasability, spread while being pressed with a hand roll to make the thickness uniform, then cured with an ultraviolet irradiation device, and further cured at 23 ° C. for 24 hours. Thereafter, the sample was peeled off from the releasable PET film to obtain a measurement sample. The thickness of the measurement sample was about 100 μm.

(Appearance evaluation)
The resin layer of the designable laminated sheet-coated metal plate 200 was visually observed in a flat plate state. “Good” indicates that good surface smoothness is obtained, “Fair” indicates that the surface is slightly rough, such as corrugation, and is inferior in smoothness. Those with no feeling were evaluated as “x”.

(Evaluation of low-temperature workability and bending workability test at 0 ° C)
Evaluation of the V bending method prescribed | regulated by "JISZ-2248" was performed to the designable lamination sheet coating metal plate 200 of 40 mm x 60 mm. In the V-bending method, a screw bending test apparatus 400 whose general view is shown in FIG. The screw bending test apparatus 400 includes an upper mold lifting handle 410, an upper mold lifting screw 420, an upper mold installation portion 430, and a lower mold installation portion 440. By manually turning the upper die lifting handle 410 provided at the upper portion of the upper die lifting screw 420, the upper die lifting screw 420 is moved in the vertical direction, and accordingly, provided at the lower end of the upper die lifting screw 420. The upper mold installation part 430 moves up and down. Further, as shown in an enlarged view of the V-bending portion in FIG. 4B, the upper die installation portion 430 is provided with a V-bending upper die 450, and the lower die installation portion 440 is provided with a V-bending lower portion. A mold 460 is provided. Then, by operating the upper die lifting handle 410, the V bending upper die 450 provided in the upper die installation portion 430 is moved downward, and the test piece 480 is sandwiched between the V bending lower die 460. As a result, the test piece 480 is deformed into a V shape. The test piece is placed so that the resin-coated surface becomes the outer surface after being bent, and the test apparatus is placed in a temperature-controlled room kept at 0 ° C., and the measurement test piece is also kept at 0 ° C. for 1 hour or longer. It is used for bending and screw contact bending.

(Boiling water immersion resistance)
The 60 mm × 60 mm designable laminated sheet-covered metal plate 200 was subjected to an overhanging process of 6 mm using the Erichsen test apparatus defined in “JIS K-6744” so that the designable laminate sheet 100 coating side was convex. Then, it immersed in boiling water for 3 hours, and the state of the resin layer was observed visually. As a result, "○" for those that did not change at all, those that slightly peeled between the layers of the resin layer, "△" that slightly roughened the surface, those that caused significant delamination, The case where deformation such as significant swelling occurred in the resin layer was evaluated as “x”.

(Adhesive force between the surface layer 30 and the base material layer 10)
Using a 20 mm × 100 mm designable laminated sheet-coated metal plate 200 as a test piece, measurement width is measured according to “JIS Z-0237, Adhesive Tape, Adhesive Sheet Test Method—180 Degree Peeling Adhesive Strength to Test Specimen” The adhesive force between the surface layer 30 and the base material layer 10 with the adhesive layer 20 interposed therebetween was evaluated at 20 mm. “○” indicates that the adhesive strength is 10 N / 20 mm or more and sufficient adhesive strength is obtained. The adhesive strength is greater than 5 N / 20 mm and less than 10 N / 20 mm, and the adhesive strength is relatively low. Evaluation was made as “Δ” when it was determined that there was no problem, and “X” when the adhesive strength was determined to be insufficient at 5 N / 20 mm or less.

(Adhesive force between the designable laminated sheet 100 and the metal plate 50)
Using a 20 mm × 100 mm designable laminated sheet-coated metal plate 200 as a test piece, measurement width is measured according to “JIS Z-0237, Adhesive Tape, Adhesive Sheet Test Method—180 Degree Peeling Adhesive Strength to Test Specimen” The measurement was performed at 20 mm, and the adhesive force between the laminated sheet and the base metal was evaluated. “○” indicates that the adhesive strength is 40 N / 20 mm or more and sufficient adhesive strength is obtained. Adhesive strength is greater than 20 N / 20 mm and less than 40 N / 20 mm. Evaluation was made as “Δ” when it was determined that there was no problem, and “X” when the adhesive strength was 20 N / 20 mm or less and the adhesive strength was determined to be insufficient.

(Production of the designable laminated sheet 100)
A sheet mainly composed of a polyester resin composed of two layers having a resin composition shown in Table 1 and a total thickness of 200 μm by a co-extrusion film forming method by a feed block method using two twin-screw kneading extruders (C -1 to C-12) were formed. The breakdown of the two layers is a concealing layer (second base material layer 14) having a thickness of 150 μm and a bright layer (first base material layer 12) having a thickness of 50 μm, and the resin composition of each layer is the same. Concerning the concealing layer, a total of 16 parts by mass of titanium white and titanium yellow are included as coloring pigments, and regarding the glittering layer, 3 parts by mass of a pearl mica pigment having a particle diameter of 5 to 15 μm is included as the glittering pigment (respectively And the total amount of the resin components is 100 parts by mass.)

  For these co-extruded sheets, by using a casting roll in which an embossed plate of an abstract pattern having a maximum height (Ry) of 85 μm is engraved, by being extruded from a T-die and taking up with the casting roll, The embossed pattern was transferred to the glitter layer side.

  The sheet of C-13 is an example in which a laminated sheet excellent in embossing suitability in the embossing machine in the invention described in “Japanese Patent Application No. 2003-132182” is used as the base material layer 10. The method for producing the C-13 sheet will be described below. The upper layer 15 containing the glitter pigment was extruded as a single layer by a biaxial kneading extruder to form a single layer sheet having a thickness of 50 μm. Then, the middle layer 16 and the lower layer 17 were formed into a coextruded sheet composed of two layers having a total thickness of 150 μm by a coextrusion film forming method by a feed block method using two twin-screw kneading extruders. The breakdown of the two layers is an intermediate layer 16 containing a colored pigment having a thickness of 100 μm and a lower layer 17 to which no pigment having a thickness of 50 μm is added. The resin composition of each layer is shown in Table 1.

  Next, an abstract pattern print is printed on the surface of the coextruded sheet on the middle layer 16 side by a gravure printing method so that the printed side of the coextruded sheet is in contact with the single layer sheet of the upper layer 15. Laminated and introduced into the off-line embossing machine shown in FIG. In the embossing machine, the lower layer 17 side surface is brought into contact with the heating drum 310 of the embossing machine 300, and heat fusion lamination is integrated. At the same time, the upper layer 15 side surface has a maximum height (Ry) of 85 μm. The embossed pattern was transferred with an embossed plate roll 350 on which an embossed version of an abstract pattern was engraved. In addition, as a coloring pigment, a total of 24 parts by mass of titanium white and titanium yellow is used, and as a bright pigment, 3 parts by mass of a pearl mica pigment having a particle diameter of 5 to 15 μm is used (respectively resin components). The total amount is 100 parts by mass.)

Specifically, the following resin compositions were used as described in Table 1.
“Easter PET-G · 6763” is manufactured by Eastman Chemical Company, the dicarboxylic acid component is terephthalic acid, about 30 mol% of the diol component is 1.4-cyclohexanedimethanol, and about 70 mol% is ethylene glycol. Is a substantially amorphous copolymerized polyethylene terephthalate resin. The glass transition temperature is 78 ° C., and no melting point is observed.
“PCTG 5445” is manufactured by Eastman Chemical Company, the dicarboxylic acid component is terephthalic acid, about 65 mol% of the diol component is 1.4-cyclohexanedimethanol, and about 35 mol% is ethylene glycol. It is a copolymerized polyethylene terephthalate resin that is substantially amorphous. The glass transition temperature is 86 ° C. and no melting point is observed.
“Novaduran 5020S” is a polybutylene terephthalate (homo PBT) resin manufactured by Mitsubishi Engineering Plastics. It is a standard grade for extrusion film formation having an intrinsic viscosity of 1.2, and its melting point is 225 ° C.
“Cortera CP509200” is a polytrimethylene terephthalate (homo PTT) resin manufactured by Shell. The melting point is 225 ° C.

  As the transparent stretched polyester resin sheet of the surface layer 30, for all Examples and Comparative Examples, a biaxially stretched polyethylene terephthalate resin film “Tetron SG-2” manufactured by Teijin DuPont Films with a thickness of 75 μm was used. .

  As the adhesive composition of the adhesive layer 20, an adhesive composition in which an ultraviolet curable adhesive and an isocyanate (NCO) -terminated urethane prepolymer were blended in the ratios shown in Table 2 was used.

As the ultraviolet curable adhesives described in Table 2, the following were specifically used.
“New Frontier R1213” is a non-yellowing type UV curable adhesive manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which contains about 50% by mass of a urethane acrylate composition and 50% by mass of a monofunctional acrylate monomer. Is -39 ° C.
“New Frontier R1303” is a non-yellowing type ultraviolet curable adhesive manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which contains about 60% by mass of a urethane acrylate composition and 40% by mass of a monofunctional acrylate monomer. Is 20 ° C.
“New Frontier R1304” is a non-yellowing type UV curable adhesive manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which contains 65 to 75 mass% of urethane acrylate composition and 25 to 35 mass% of alkanediol acrylate. , Tg is 60 ° C.
“Art Resin NPC18” is a non-yellowing type ultraviolet curable adhesive manufactured by Negami Kogyo Co., Ltd., containing 100% by mass of an ultraviolet curable urethane acrylate composition, and Tg is −15 ° C.

  Each adhesive composition contains 3 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photosensitizer (with the amount of the UV curable adhesive being 100 parts by mass).

  In Example 5, 18% by mass of dimethylacrylamide (DMAA) (manufactured by Kojin Co., Ltd.) is blended as an ultraviolet curable reactive dilution monomer.

Examples 1-5 and Comparative Examples 1-5
The designable laminated sheet 100 was produced using C-6 as the base material layer 10 and using the adhesive composition shown in Table 2 as the adhesive layer 20. As a specific manufacturing method, the adhesive composition of the adhesive layer 20 is continuously applied to the surface of the base layer 10 to which embossing is applied using a die coater, and at the same time, the biaxial stretching of the surface layer 30 is performed. An adhesive layer having a thickness in which the embossed convex portion of the base material layer 10 does not directly contact the surface layer 30 by continuously supplying a polyester film and passing between a pair of silicone rubber rolls whose roll gap can be appropriately adjusted. The surface layer 30 was laminated and integrated with 20 interposed therebetween, and the adhesive layer 20 was cured by an ultraviolet irradiation device disposed immediately thereafter to produce a designable laminated sheet 100. The irradiation intensity of the ultraviolet irradiation device is the same in all examples and comparative examples.

Examples 6-17
Using the one shown in Table 1 as the base material layer 10 and using the same adhesive composition as in Example 1 as the adhesive layer 20, the designable laminated sheet 100 was produced in the same manner as described above.

(Preparation of a design-oriented laminated sheet-coated metal plate 200)
Polyester adhesive generally used for polyvinyl chloride coated metal plate is coated on the surface of galvanized steel sheet (thickness: 0.45 mm) so that the adhesive film thickness after drying is about 2 to 4 μm. Apply, then dry and heat the coated surface with a hot air heating furnace and an infrared heater, set the surface temperature of the steel sheet to 240 ° C and 245 ° C, and immediately use the roll laminator to create the design laminate sheet produced above 100 was coated and air-cooled and cooled to produce a designable laminated sheet-coated metal plate 200. The type and application conditions of the adhesive used for laminating with the steel plate 50 are the same in all examples and comparative examples. Each item mentioned above was evaluated with respect to the obtained metal plate. The evaluation results are shown in Tables 3 and 4.

(Evaluation results)
The following evaluation results were obtained from Tables 3 and 4.
Comparative Example 1 is a case in which the storage elastic modulus at 20 ° C. and 100 ° C. is higher than the range of the present invention as the adhesive composition of the adhesive layer 20, respectively, and the surface layer 30 is poor in low-temperature workability. As a result, the biaxially stretched PET film was broken at the bent portion.

  The comparative example 2 is a case where the 20 degreeC storage elastic modulus of the adhesive bond layer 20 is lower than the range of this invention, and the peeling strength became inadequate. The form of peeling was interfacial peeling between the biaxially stretched PET film as the surface layer 30 and the adhesive layer 20.

  Comparative Example 3 is a case where only an ultraviolet curable adhesive is used without blending an isocyanate-terminated urethane prepolymer, and the storage elastic modulus at 20 ° C. and 100 ° C. is within the range of the present invention, but boiling In the water immersion test, the appearance deteriorated significantly.

  Although the comparative example 4 showed some improvement regarding the external appearance after a boiling water immersion test compared with the comparative example 3, it could not be said that it was sufficient improvement effect. This is because the mixing amount of the isocyanate-terminated urethane prepolymer is recognized, but the mixing amount is less than the range of the present invention.

  Comparative Example 5 was a case where the amount of the isocyanate-terminated urethane prepolymer was larger than the range of the present invention, and there was no problem with the low-temperature processability and the peel strength between the surface layer 30 / base material layer 10, but the excess isocyanate Reacts with moisture when immersed in boiling water to cause a foaming phenomenon, resulting in remarkable appearance defects.

  On the other hand, good results were obtained in the examples (Examples 1 to 17) of the present invention. In Example 1, the storage elastic modulus at each temperature of the adhesive layer 20 is in the range of the present invention, and the value at 20 ° C. is in a particularly preferable range, so the processability at low temperature is also good. On the other hand, in Example 2, the storage elastic modulus at 20 ° C. of the adhesive layer 20 is within the scope of the present invention, but is slightly higher, and fine cracks enter the surface layer 30 by bending at low temperature, Slight whitening was observed.

  Example 4 was a case where the addition amount of the isocyanate-terminated urethane prepolymer was close to the upper limit of the range of the present invention, which caused a slight foaming phenomenon when immersed in boiling water, resulting in a slightly poor appearance.

  Example 6 is a case where only a substantially amorphous polyester is used as the resin composition of the base material layer 10, and the base material layer 10 undergoes fluid deformation in the boiling water immersion test, resulting in significant appearance roughness. . Example 6 is considered not suitable for unit bus applications.

  In Example 7, the PBT, which is a crystalline polyester resin, was blended, so that the immersion in boiling water was improved as compared with Example 6, but some surface roughness was caused.

  In Examples 8 to 17, no problem occurred in the boiling water immersion test, and it can be particularly suitably used for a unit bath application (in the unit bath application, the test is included as an evaluation item).

  Example 15 is a case where the resin composition of the base material layer 10 has a high PBT resin ratio, and under the conventional soft PVC sheet lamination conditions, the adhesive strength with the metal plate 50 is somewhat weak. became. Example 16 is a case where the base material layer 10 made only of the PTT resin was used, and the adhesive force with the metal plate 50 was further reduced as compared with Example 15. Therefore, when using the same temperature condition as laminating the conventional soft PVC sheet, it is preferable not to use the base material layer 10 used in Example 15 and Example 16. However, when the temperature of the metal plate 50 at the time of lamination was 5 ° C. higher than the conventional temperature, good adhesive force could be obtained in these respects.

  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. However, it is possible to appropriately change the invention within the scope and spirit of the invention that can be read from the claims and the entire specification, and the design laminated sheet and the design sheet-coated metal plate accompanying such a change are also included in the present invention. Should be understood as being included in the technical scope of

It is a conceptual diagram which shows the layer structure of the designable lamination sheet 100 of this invention. It is a conceptual diagram which shows the layer structure of the designable lamination sheet coating metal plate 200 of this invention. 3 is a conceptual diagram of an embossing machine 300. FIG. 1 is a conceptual diagram of a screw bending test apparatus 400. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base material layer 20 Adhesive layer 30 Surface layer 40 Printing layer 15 Upper layer 16 Middle layer 17 Lower layer 50 Metal plate 60 Adhesive 100 Designable laminated sheet 200 Designable laminated sheet covering metal plate 300 Embossing machine 400 Screw bending test apparatus

Claims (10)

A laminated sheet having at least three layers of a base material layer, an adhesive layer, and a surface layer, and these layers are laminated in this order,
The base material layer includes a polyester resin as a main component, includes a pigment, has an uneven design by embossing on the surface laminated with the adhesive layer, and has a non-oriented thickness of 100 μm to 300 μm. The polyester resin constituting the base material layer is a polybutylene terephthalate (PBT) resin of 20% by mass to 80% by mass with respect to 100% by mass of the entire polyester resin, and / or It is a mixture of a polytrimethylene terephthalate (PTT) resin and a polyester resin that is 20% by mass or more and 80% by mass or less which is a remaining amorphous component,
The substantially amorphous polyester-based resin is mainly composed of terephthalic acid or dimethyl terephthalic acid as a main component of the dicarboxylic acid component, and the entire diol component is defined as 100 mol%, and 20 mol% or more and 80 mol% or less of the diol component. 1.4-cyclohexanedimethanol (1.4-CHDM), a copolymerized polyester having 20 to 80 mol% of the remaining components as ethylene glycol,
The adhesive layer is composed mainly of a mixed composition containing an ultraviolet curable adhesive in an amount of 50% by mass to 96% by mass and an isocyanate-terminated urethane prepolymer in an amount of 4% by mass to 50% by mass, The storage elastic modulus at 10 Hz of the dynamic viscoelastic tension method for the cured product of the mixed composition is 2.0 × 10 ⁸ Pa or more, 2.0 × 10 ⁹ Pa or less at 20 ° C., and 2 at 100 ° C. 0.0 × 10 ⁶ Pa or more and 4.0 × 10 ⁷ Pa or less, the thickness of which is a layer having a thickness equal to or greater than the thickness at which the embossed convex portion of the base material layer is completely buried,
The surface layer is a transparent stretched layer mainly composed of a polyester-based resin.
Design laminate sheet. Wherein between the adhesive layer and the base layer has a printed layer, design of the laminated sheet according to claim 1. The printing layer is made of the first printed layer and at least two layers of the second printed layer formed by printing ink including general color pigment formed by printing ink containing the bright pigment, in claim 2 The designable laminate sheet described. The base material layer faces the adhesive layer side and includes a first base material layer containing a glitter pigment, and a second base material that is located on the opposite side of the adhesive layer side and contains a coloring pigment having a hiding power The designable laminated sheet according to any one of claims 1 to 3 , comprising at least two layers of material layers. The design property of Claim 4 which has a printing layer between the said adhesive bond layer and the said 1st base material layer, and / or between the said 1st base material layer and the said 2nd base material layer. Laminated sheet. The designable laminated sheet according to any one of claims 1 to 5 , wherein the embossing imparted to the base material layer has a maximum height (Ry) of 50 µm or more. The designable laminated sheet covering metal plate which has the designable laminated sheet and metal plate in any one of Claims 1-6 , and the surface at the side of the base material layer of the said designable laminated sheet is laminated | stacked on the metal plate. . A unit bus member using the designable laminated sheet-coated metal plate according to claim 7 . A door material using the designable laminated sheet-coated metal plate according to claim 7 . A building interior material using the designable laminated sheet-coated metal plate according to claim 7 .

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