JP2006289697A - Designable laminated sheet and metal sheet coated with the sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a designable resin-coated metal sheet having an embossment inside which does not use a halogen-containing resin, has good processability, makes the inside embossment visible through its smooth, transparent surface, and has a design with a feeling of depth and a three-dimensional feeling and to provide a designable resin-coated metal sheet which passes a boiling water immersion test and can be used for a modular bath. <P>SOLUTION: The laminated sheet comprises at least three layers of a transparent oriented polyester resin layer (layer A) 38-125 μm in thickness as a surface layer, an adhesive layer (layer B) as an intermediate layer, and as a substrate layer a layer (layer C) which has an embossed uneven design on the surface laminated with the layer B and contains a pigment-containing unoriented polyester resin as a main component. The layer B has a thickness which can completely embeds the embossment projections of the layer C and is composed of a mixture comprising an ultraviolet curable adhesive of at least 50 to below 96 mass% and an isocynate-terminal urethane prepolymer of at least 4 to below 50 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a designable laminated sheet used for building interior materials and the like, and a designable laminated sheet-covered metal plate coated with the designable laminated sheet. More specifically, the present invention relates to a design laminate sheet that is excellent in processability and design properties, does not use a halogen-containing resin, and is environmentally friendly, and a design laminate sheet-coated metal sheet coated with the design laminate sheet.

  Conventionally, as a design resin-coated metal plate used for a building interior material, a so-called mirror surface design type and an emboss design type have been used. As a type called a mirror surface design, a printed pattern is imparted on a sheet such as soft polyvinyl chloride (hereinafter may be abbreviated as “PVC”) colored by the addition of a pigment, and further on the sheet. The thing of the structure which coat | covered the resin film with transparency and favorable smoothness was used. Moreover, what gave embossing to the surface of the single layer soft PVC sheet was generally used as a type called an embossing design.

  However, in recent years, the design resin-coated metal plate used for building interior materials is required to have more excellent design properties, and as a configuration that can obtain a sense of depth, a three-dimensional effect, etc., transparent, or There is an increasing demand for a design-coated resin-coated metal plate in which a concavo-convex pattern (embossed pattern) existing inside can be visually recognized through a surface layer having a translucent and smooth surface. Called "composition" etc.).

Regarding the configuration using soft PVC, as in Patent Document 1, the surface of embossed colored soft PVC sheet is coated with a transparent PVC paste or the surface is embossed as in Patent Document 2. In addition, it was possible to obtain the above-mentioned internal embossing structure by a method such as filling an ultraviolet curable adhesive between the uneven surface of the printed colored soft PVC sheet and the transparent surface layer.
Japanese Patent Laid-Open No. 01-14050 Japanese Patent No. 3384508

  However, what is obtained by Patent Document 2 is a boiling point that is generally included as an evaluation item 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 water immersion test at the same time. In other words, it is difficult to obtain good processability when using a hard material as a cured product property of an ultraviolet curable adhesive, and passing a boiling water immersion test when using a flexible material. It was difficult. In recent years, the use of soft PVC resins has been limited due to various environmental problems.

  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 colored polyolefin-type resin sheet is marketed, a good thing is not obtained about the thing of an internal embossing structure.

  As the reason, in order to strengthen the sense of depth and stereoscopic effect, it is necessary to give deep embossment by using a thick colored resin layer, but when polyolefin resin is used as the colored resin layer, In the processing after the resin-coated metal plate was formed, there was a problem that bending whitening was likely to occur.

  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 ultraviolet curable adhesive was used, a problem occurred in the boiling water immersion property as in the case of using soft PVC.

  If a normal solvent-based curable adhesive is used in place of the UV curable adhesive, it is difficult to coat thickly because the dry film becomes thin as the solvent evaporates. Furthermore, it was not possible to secure a coating thickness sufficient to 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. In addition, with this cyanate curable adhesive, it takes time to cure after application, so that there is no deviation between the transparent surface layer and the colored resin layer until it is cured, or in the adhesive layer. Since problems in the process, such as the need to hold the deformation so as not to cause deformation such as depression due to external force, also occur, those having practical productivity and performance have not been obtained.

  Therefore, the present invention has a design with a sense of depth and three-dimensionality that has good workability without using a halogen-containing resin, and can visually recognize internal embossing through a smooth and transparent surface. It is an object to provide a design resin-coated metal sheet having an internal embossed structure and to provide a design resin-coated metal sheet that can be used for unit bath use without causing a problem even in a boiling water immersion test. To do.

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

  The first aspect of the present invention is a transparent stretched polyester resin layer (A layer) (10) having a thickness of 38 μm or more and 125 μm or less as a surface layer, an adhesive layer (B layer) (20) as an intermediate layer, and a base layer. A laminated sheet having at least three layers of a layer (C layer) (30) comprising a non-oriented polyester resin as a main component, which has an uneven design by embossing on the surface to be laminated with the B layer and contains a pigment. The B layer (20) has a thickness greater than or equal to the thickness at which the embossed protrusions of the C layer (30) are completely buried, and the B layer (20) has an ultraviolet curable adhesive of 50% by mass or more and 96% by mass. % Is a mixture of 4% by mass or more and less than 50% by mass of an isocyanate-terminated urethane prepolymer.

  In this laminated sheet (100), by using the above-mentioned adhesive component as the B layer (20), it is possible to achieve both folding workability and boiling water immersion, and sufficient adhesion between the layers. Can be. In addition, since this adhesive component is a solvent-free adhesive, even if the surface of the C layer (30) is relatively deeply provided with unevenness due to embossing, it is completely filled with a transparent surface layer. It is easy to secure a coating thickness sufficient to obtain smoothness on the surface of the film. 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.

  In said designable laminated sheet (100), it is preferable that the glass transition temperature of the said ultraviolet curable adhesive of B layer (20) is the range of -30-80 degreeC.

  Thereby, the workability of the metal plate (60) covered with the designable laminated sheet (100) can be made better, and the interlayer adhesion of the designable laminated sheet (100) can be made better. You can also

  In the above designable laminated sheet (100), the C layer (30) is a polybutylene terephthalate (PBT) having a mass of all resin components of the C layer (30) of 100 mass% and not less than 20 mass% and less than 80 mass%. It is preferable that the resin is a mixture of a resin based on polytrimethylene terephthalate (PTT) and a polyester resin that is substantially amorphous and less than 80% by weight amorphous.

  When it consists only of polyester resin which is substantially amorphous, there is an advantage that embossing etc. can be easily performed, but since the glass transition temperature is less than 100 ° C., the boiling water immersion test may be satisfied. However, by including PBT-based resin or PTT-based resin, this crystallizes and the C layer is maintained at a high elastic modulus up to near the crystalline melting point, causing a problem in the boiling water immersion test. It can not be.

  The substantially amorphous polyester-based resin in the C layer (30) is mainly composed of terephthalic acid or dimethyl terephthalic acid as the main component of the dicarboxylic acid component, and 20 to 80 mol. % Is preferably a copolyester composed of 1.4-cyclohexanedimethanol (1.4-CH and the remaining 80 to 20 mol.% Of ethylene glycol.

  As a substantially amorphous polyester-based resin for the C layer (30), it is widely used worldwide, and by using a commercially available material, it is possible to obtain the merit of stability of raw material supply and cost. Obtainable.

  In the above designable laminated sheet (100), it is preferable to use a biaxially stretched polyethylene terephthalate resin film having a thickness of 38 μm or more and 125 μm or less as the transparent stretched polyester resin layer (A layer) (10).

  By using a biaxially stretched polyethylene terephthalate resin film, which is a proven material that has been used for overlaying soft PVC, as the A layer (10), various surface properties are also available when used in the bathroom as a unit bath material. There is no risk of problems. Moreover, since it has favorable smoothness, what is called a mirror surface 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 above designable laminated sheet (100), the C layer (30) faces the B layer (20) side and is located on the side opposite to the C1 layer (32) containing the glitter pigment and the B layer side. Further, it may be configured by at least two layers of the C2 layer (34) containing a coloring pigment having a hiding power.

  Thereby, the visibility of the embossed shape given to the inside of the laminated structure becomes better. In addition, bright pigments are generally inferior in hiding power, so by placing a layer to which a coloring pigment with hiding power is added below, it is stable regardless of changes in the surface condition and color of the metal plate. The designable laminated sheet-coated metal plate (200) having the above-described color tone can be obtained.

  In said designable laminated sheet (100), between B layer (20) and C layer (30), between B layer (20) and C1 layer (32), or between C1 layer (32) and C2 layer Between (34), a printing layer (D layer) (40) may be provided. Thereby, in addition to the colored design, the surface smooth design, and the internal embossed design, a design of a pattern by printing and a design of color can be given.

  In addition, as a printing layer (D layer) (40), a printing layer containing a glittering pigment may be provided as a printing layer (D layer) (40) without providing a resin layer containing a glittering pigment as the C layer (30). Simultaneously with the provision of the printing layer containing the conductive pigment, the design of the pattern by printing and the design of the color may be imparted.

  2nd invention of this invention has said designable laminated sheet and metal plate (60), and the C layer (30) side surface of the said designable laminated sheet is laminated | stacked on the metal plate (60). , A decorative laminated sheet-coated metal plate (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.

  The third invention of the present invention is selected from the group consisting of a door material, a unit bath wall material, a unit bath ceiling material, a partition material, and a general wall material using the designable laminated sheet-coated metal plate (200). It is a building interior material.

Hereinafter, embodiments embodying the present invention will be described.
FIG. 1 is a schematic diagram showing the layer structure of the designable laminated sheet 100 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” in terms of the thickness range, but is generally referred to as “film” here. Concerning the range, the single name “sheet” is used 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.

<Layer (C layer) 30 mainly composed of non-oriented polyester resin>
The C layer 30 is a layer mainly composed of a non-oriented polyester resin, which has an uneven design by embossing on the surface to be laminated with the adhesive layer (B layer 20), and is colored by adding a pigment. .

  As the polyester-based resin used for the C layer 30, it is easy to give an uneven design by embossing, and processability as a designable laminated sheet-coated metal plate obtained by laminating the laminated sheet of the present invention is ensured. Any sheet can be used without limitation as long as the sheet is not likely to be deformed during immersion. Among these, as the polyester-based resin constituting the C layer 30, a polybutylene terephthalate (PBT) -based resin having a mass of 20 mass% to less than 80 mass% based on the mass of all resin components of the C layer 30 (100 mass%). Or a mixture of a polytrimethylene terephthalate (PTT) resin and a polyester resin that is 20% by mass to less than 80% by mass and is substantially amorphous, and is preferably 25% by mass to 80% by mass. It is more preferable to be a mixture of less than PBT resin or PTT resin and 20% by mass or more and less than 75% by mass of a substantially amorphous polyester resin.

  When the C layer 30 is composed only of an amorphous resin, the embossing method is not limited, and embossing with a depth can be easily applied, but an amorphous material available at a commercial level. Since the glass transition temperature of the conductive resin is lower than 100 ° C., when the designable laminated sheet-coated metal plate is subjected to a boiling water immersion test, the C layer 30 undergoes fluid deformation.

  On the other hand, if the C layer 30 is composed of only a crystalline resin such as PBT or PTT, the elasticity of the resin layer is maintained up to its melting point, so there is no problem in the boiling water immersion test. The embossing method is limited, and it is particularly difficult to provide embossing with a depth necessary for the present invention. In addition, in the case of a structure composed only of a crystalline resin, it is sufficient if the metal plate is not heated to a temperature slightly higher than the temperature condition when laminating the conventional soft PVC when laminating to the metal plate. Adhesive strength is not obtained, and it is necessary to change the coating material for the back side of the metal plate that has been used conventionally to be more heat resistant. Furthermore, in the configuration provided with a printing layer (D layer), the heat resistance is higher than before. Problems such as the need to use high printing inks arise.

  In the designable laminated sheet 100 of the present invention, as described above, the C layer 30 is a mixture of a PBT resin or a PTT resin and a polyester resin that is substantially amorphous, so The application is relatively easy and does not cause fluid deformation in the boiling water immersion test. In addition, when laminating with the metal plate 60, sufficient adhesive strength can be obtained within the range of temperature conditions of conventional soft PVC.

  In addition, PBT-based resins and PTT-based resins have better processability than PET-based resins even in a crystallized state, and a metal plate coated with a design laminate sheet 100 having a mixture containing them as a C layer 30 The workability of 60 can be improved. On the other hand, if the PET resin is used for the C layer 30, the melting point is high when the PET resin is crystallized, and sufficient with the metal plate 60 under the temperature condition in which the conventional soft PVC is laminated. In contrast, when the PET resin is in an amorphous state, the crystallization speed is slow, so that the C layer 30 is fluidly deformed when immersed in boiling water, resulting in poor appearance quality of the resin-coated metal plate. Will occur.

  As the PBT resin contained in the mixture constituting the C layer 30 in a preferred form, it is preferable to use a resin having a melting point in the range of 210 ° C to 230 ° C. A PBT resin having a melting point lower than this is not preferable because the crystallization rate is low and the dipping property of the design-laminated laminated sheet-coated metal plate 200 cannot be improved, and the raw material price is also expensive. Specifically, a so-called homo PBT resin (which includes an unintended copolymerization component) using terephthalic acid or dimetal terephthalic acid as a dicarboxylic acid component and each single component of 1.4-butanediol as a diol component is included. May be used). This homo PBT resin has a melting point of about 225 ° C., which is more advantageous than a copolymer PBT resin having a lower melting point in terms of cost and stable supply.

  In addition to homo PBT resins, PBT resins are those in which a part of the acid component is substituted with a dicarboxylic acid such as isophthalic acid, the melting point of which does not fall below 210 ° C., polytrimethylene glycol (PTMG) Copolymerized ones can be used. When producing a sheet of the C layer 30 by the extrusion film forming method, it is common to select a material having an IV value in the range of about 1.0 to 1.4, and obtain commercially available materials from each company. Can do.

  In addition, the PTT resin having a melting point similar to that of the PBT resin and having a high crystallization rate is also used in the present invention, although it does not reach the PBT resin in terms of cost, freedom of grade selection, and stable supply. It can be used for the layer 30.

  A substantially non-crystalline polyester resin contained in the mixture constituting the C layer 30 in a preferred form has a clear crystallization behavior or crystal melting behavior as measured by a differential scanning calorimeter (DSC). This includes not only those having no crystallinity but also those having crystallinity but having a very low crystallization rate and those having a very small amount of heat of crystal fusion that can be handled as a substantially amorphous polyester resin.

  Among these substantially amorphous polyester resins, terephthalic acid or dimethyl terephthalic acid is mainly used as a dicarboxylic acid component, and 20 to 80 mol. It is preferable to use a copolymer polyester in which% is 1.4-cyclohexanedimethanol (1.4-CH and the remaining 80 to 20 mol.% Is ethylene glycol.

  Here, “mainly” means 80 mol. Of terephthalic acid or dimethylterephthalic acid based on the whole dicarboxylic acid component (100 mol.%). % Or more, more preferably 90 mol. % Is included.

  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 heated C layer 30 using an embossing machine or the like. In some cases, crystallization proceeds and embossing may become difficult. Moreover, when crystallizing in this way, the workability of the resulting designable laminated sheet-coated metal plate 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” is about 30 mol. Of the diol component of polyethylene terephthalate resin. % Is a substantially amorphous polyester-based resin in which no thermal behavior due to crystallinity is observed by DSC, as determined by DSC.

  However, the present invention is not limited to this, and “PCTG 5445” manufactured by Eastman Chemical Company, which can be handled as an amorphous resin under normal conditions, although it exhibits crystallinity under specific conditions, is used. You can also. The resin is 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 C layer 30 is provided with a design property, a visual concealing effect of the metal plate 60 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 of the C layer 30 is improved. A pigment is added for the purpose of improvement. 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 the chromatic coloring, a chromatic colored organic or inorganic pigment added in a small amount for adjusting the color can be used based on this titanium oxide pigment. 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.

  The C layer 30 is not a single layer, but faces the B layer 20 and is added with a C1 layer 32 to which a bright pigment is added, and a color pigment having a hiding power is added on the side opposite to the B layer 20 side. The C2 layer 34 may be composed of at least two layers. It is known that the shape visibility of the internal embossing is improved by adding a luster pigment, and the effect is particularly remarkable in the C layer 30 that is colored white, but the C layer 30 is a single layer. In this case, since the coloring pigment such as titanium oxide having a strong hiding power and the bright pigment are kneaded in the same layer, the effect of the bright pigment is likely to be insufficient. It is particularly preferable to use 30.

  In addition, bright pigments are generally inferior in hiding power, so by placing a layer to which a coloring pigment with hiding power is added underneath it, it is not affected by changes in the surface condition and color of the metal plate, and is stable. The designable laminated sheet-coated metal plate 200 having the 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 have been electrolessly plated with various metals such as silver, nickel, etc. 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.

  Further, the C layer 30 may have a multilayer structure as described in “Japanese Patent Application No. 2003-132182” and “Japanese Patent Application No. 2004-285225” for the purpose of giving embossing suitability by an embossing machine. As an example, in the case of using a laminated sheet excellent in embossing suitability in the embossing machine in the invention described in “Japanese Patent Application No. 2003-132182”, the layer configuration is shown in FIG. 1 (d) and FIG. 1 (e). One embodiment is shown. The C layer 30 is composed of three layers: a layer 32 containing a bright pigment, a layer 34 containing a colored pigment, and a layer 36 to which no pigment is added. In addition, the printing layer 40 described later may be provided between the layer 32 containing the glitter pigment and the layer 34 containing the color pigment (the form shown in FIG. 1 (d)). You may provide between the layer 32 and the adhesive bond layer 20 (form of FIG.1 (e)).

  Various amounts of various additives may be added to the C layer 30 as long as the properties are not impaired.

  General additives include phosphorus, phenol and other antioxidants, lactones, phenol acrylate and other process stabilizers, heat 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 C layer 30 is mainly composed of a polyester-based resin, a terminal carboxylic acid sealing agent such as a carbodiimide-based, epoxy-based, or oxazoline-based, or a so-called hydrolysis inhibitor may be added.

  The preferable thickness of the C layer 30 is in the range of 100 to 300 μm. If it is thinner than this, it is necessary to add a large amount of pigment to ensure the visual concealment of the base, and as a result, processability may be reduced, and the embossed plate type that can be applied is limited. This makes it difficult to transfer an embossed pattern rich in three-dimensionality and depth. The embossing applied to the C layer 30 preferably has a maximum height (Rmax) 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 thicker the C layer 30 is, the better it can transfer a deeper embossed pattern, but if the thickness exceeds 300 μm, how much adhesive Even if the composition of the layer (B layer) 20 is devised, the workability of the design-use laminated sheet-coated metal plate 200 is deteriorated. In addition, it becomes difficult to use a molding die that has been used for molding such as bending of a soft PVC resin-coated metal plate, and it becomes necessary to create a new die.

<Adhesive layer (B layer) 20>
The B layer 20 is a mixture of 50% by mass or more and less than 96% by mass of the ultraviolet curable adhesive and 4% by mass or more and less than 50% by mass of the urethane terminal prepolymer having an isocyanate terminal.

  The ultraviolet curable adhesive constituting the B 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. 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.

  In addition, as an ultraviolet curable adhesive, 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 (manufactured by Negami Kogyo Co., Ltd.) However, it is not limited to these.

  The B layer 20 has a thickness that is equal to or greater than the thickness at which the embossed protrusions provided on the surface of the C layer 30 are completely buried. This is to prevent the portion corresponding to the embossed convex portion of the C layer 30 from being raised when the B layer 20 is cured by ultraviolet irradiation even if the shrinkage in the thickness direction of the B layer 20 occurs. It is. As a result, a smooth state is maintained on the surface of the transparent stretched polyester resin layer (A layer) 10 without reflecting the bulge caused by the embossed protrusions of the C layer 30, and the surface of the A layer 10 is mirror-finished. Sex can be ensured.

  When the coating thickness of the B layer 20 is lower than the height of the embossed protrusions of the C layer 30, smoothness cannot be imparted to the surface of the A layer 10, and problems such as bubbles are generated. Even when the coating thickness of the B layer 20 is substantially equal to the height of the embossed protrusions of the C layer 30, the surface of the A layer 10 is smooth when a slight volume shrinkage occurs in the thickness direction when the B layer 20 is cured. Sex cannot be imparted.

  As described above, in order to obtain a three-dimensional effect by the embossed design of the C layer 30, the embossed imparted to the C layer 30 is preferably 50 μm or more at the maximum height (Rmax). Therefore, the B 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 B layer 20, a mixture of 50% by mass or more and less than 96% by mass of the ultraviolet curable adhesive and 4% by mass or more and less than 50% by mass of the isocyanate-terminated urethane prepolymer is used.

  The isocyanate-terminated urethane prepolymer used in the B layer 20 by mixing with an ultraviolet curable adhesive is prepared by an organic polyisocyanate (a1) and a polyol (a2) in an excess of the organic polyisocyanate by an ordinary method. Urethane prepolymer.

  As organic polyisocyanate (a1), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidized diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, naphthalene Aromatic diisocyanates such as diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate A mixture of two or more of these may be used.

  Examples of the polyol (a2) include polyether polyol, polyester polyol, and other polyols, and a mixture of two or more of these can also be used. As the polyol (a2), for example, a polyol produced using a double metal cyanide complex as a catalyst can be used.

  Examples of polyether polyols 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, butylene. Examples thereof include polyols obtained by adding one or more of oxides, styrene oxides, and the like, and polyoxytetramethylene polyols.

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

  The mixing ratio of the ultraviolet curable adhesive to the isocyanate-terminated urethane prepolymer is such that the isocyanate-terminated urethane prepolymer is 4% by mass or more and less than 50% with respect to 50% by mass or more and less than 96% by mass of the ultraviolet curable adhesive. There must be.

  When the amount of the isocyanate-terminated urethane prepolymer added is too small, it is difficult to obtain adhesion between the B layer 20 and the A layer 10 described below. Moreover, when there is too much addition amount of an isocyanate terminal urethane prepolymer, there exists a possibility that problems, such as being inferior in external quality, may appear, such as B layer 20 foaming after boiling water immersion.

  In addition, it is preferable that the glass transition temperature of an ultraviolet curable adhesive is the range of -30 degreeC-80 degreeC. If the glass transition temperature is too high, the adhesiveness between the B layer 20 and the A layer 10 tends to be inferior, or the workability when the design laminated sheet-coated metal plate 200 is used tends to be inferior. Is too low, the adhesion between the B layer 20 and the A layer 10 after immersion in boiling water tends to be inferior, and the B layer 20 itself softens and deforms in flow when immersed in boiling water. The appearance of the sheet-coated metal plate 200 tends to deteriorate.

  It should be noted that various additives such as a solvent, an inorganic filler, a small amount of process oil, a plasticizer, a thixotropic agent, a pigment, and an anti-UV agent and a stabilizer for maintaining and improving weather resistance are optionally added to the B layer 20. In addition, a catalyst or the like may be included.

<Transparent stretched polyester resin layer (A layer) 10>
The purpose of providing the A layer 10 is to obtain a high-smooth design appearance called a mirror-like appearance, and because the embossed design applied to the C layer 30 through the A layer 10 and the B layer 20 is visually recognized. This is to obtain a design (internal embossing configuration) with a sense of depth and a three-dimensional appearance. As the A layer 10, 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, and the improvement of various physical properties on the surface of the resin-coated metal plate For example, the same transparent stretched polyester resin sheet that has been used for such purposes can be used.

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

  The thickness of the A layer 10 is preferably 38 to 125 μm, and more preferably 50 μm to 100 μm. If the thickness of the A layer 10 is too thin, it is difficult to suppress a decrease in smoothness due to the curing shrinkage of the B layer 20, and if the thickness of the A layer 10 is too thick, it is sufficient as the design laminated sheet-coated metal plate 200. It becomes difficult to obtain a good workability.

  As the biaxially stretched polyethylene terephthalate resin film, 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, as long as the embossed design imparted to the C layer 30 is not obstructed, it is possible to use a back-printed print called a back print, which is similarly provided with a matting agent to provide a matte property. A biaxially stretched polyethylene terephthalate resin film or the like may be used.

  When an embossed design is also required for the surface of the A layer 10 instead of a smooth surface design called a mirror-like appearance, what is called an easily processable biaxially stretched polyethylene terephthalate 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 (D) 40>
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 C layer 30 which is a colored layer does not have the C1 layer 32 to which the bright pigment is added, the visibility of the internal embossing is improved by providing the printing layer 40 using the bright pigment. In addition, both printing with a bright pigment and normal pattern printing may be applied.

  The print layer 40 is applied between the B layer 20 and the C layer 30, between the B layer 20 and the C1 layer 32, or between the C1 layer 32 and the C2 layer 34. The C layer 30 is formed as a smooth sheet with no embossed pattern, and after printing on the surface, the embossed machine is used to emboss the printed surface. Layer 40 can be formed and embossed. Further, when the C1 layer 32 and the C2 layer 34 are not laminated and integrated in the die by the coextrusion method, either one or both surfaces of the C1 layer 32, or the side of the C2 layer 34 on the side laminated with the C1 layer 32 is used. A print layer may be provided on the surface.

<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 C layer 30, 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 productivity of the sheet are not particularly limited. From the viewpoint of the above, an extrusion casting method using a T die is preferable.

  As a method for applying an embossed pattern to the C layer 30, a method of directly applying an embossed pattern to a resin that has flowed out in a molten state from a T-die using a stamped embossed plate as a casting roll during extrusion film formation, a post-process Re-melting the C layer 30 by heating when laminating the C layer 30 formed without transfer of the embossed pattern on the metal plate 60 The pattern can be transferred with an embossing roll, and then the B layer 20 and the A layer 10 can be laminated, or any other method can be used without particular limitation so long as embossing is imparted to the thermoplastic resin sheet. Among these, when the D layer 40 is applied to the laminated sheet, the latter two or similar methods are preferable.

  The method for applying the B layer 20 to the embossed C layer 30 is not particularly limited, and can be performed according to a known method according to the viscosity. For example, the B layer 20 is formed by coating on the surface on the side where the A layer 10 is laminated by using a temperature-adjustable two-component supply device, a mixer, a die coater, a squeeze coater, or the like. The method of affixing to 30 or the method of forming the B layer 20 by application | coating to the surface of the side by which the unevenness | corrugation by embossing of the C layer 30 was provided can be mentioned.

  The A layer 10 and the C layer 30 coated with the B layer 20, or the C layer 30 and the A layer 10 coated with the B layer 20 are interleaved with the B layer 20 coated with a sufficient thickness. The surface of the A layer 10 is not in direct contact with the surface of the A layer 10, and the outermost surface of the A layer 10 is smoothed by passing between a pair of rubber rolls having a certain clearance. Are laminated and integrated so as to maintain a stable state. Thereafter, an ultraviolet irradiation lamp is irradiated from the surface of the A layer 10 side, and the B layer 20 is cured.

  The method of laminating the designable laminated sheet 100 obtained as described above to the metal plate 60 is not particularly limited, but laminating with a thermosetting adhesive 50 is common. The adhesive 50 is a thermosetting adhesive that has been used for the purpose of laminating a soft PVC sheet to a metal plate, such as an acrylic adhesive, an epoxy adhesive, a urethane adhesive, and a polyester adhesive. An agent can be mentioned. Among these, since the C layer 30 is made of a polyester-based resin, it is preferable to use a polyester-based adhesive from the viewpoint of easily obtaining an adhesive force. As an example of a specific laminating method, an adhesive after drying is applied to a metal surface on which the design laminate sheet 100 is bonded using a commonly used coating facility such as a reverse coater or a kiss coater on the metal plate 60. The thermosetting adhesive is applied so that the film 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 60 is maintained at a temperature of about 230 ° C. to 250 ° C., and a design lamination is immediately performed using a roll laminator. By covering and cooling the sheet 100 so that the C layer 30 side of the sheet 100 becomes an adhesive surface, the designable laminated sheet-coated metal plate 200 can be obtained.

  As the metal plate 60 to be the subject 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 60 varies depending on the use of the designable laminated sheet-coated metal plate 200, but can be selected in the range of 0.1 mm to 10 mm. As an example, the thickness of the metal bath 60 is 0.3 mm to 0.00 mm. Often, a thickness of 8 mm is used.

  The designable laminated sheet-coated metal plate 200 of the present invention has good workability as the metal plate 60 covered with the designable laminated sheet 100 having an internal embossed structure with a sense of depth and three-dimensionality, and is a door material, Although it can be suitably used for building interior materials such as partition materials and general wall materials, since it does not cause a problem in the boiling water immersion test, it can be particularly suitably used for unit bath wall materials, unit bath ceiling materials, etc. Is.

  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 shown in the Example and the comparative example are as follows.

(Appearance evaluation)
The resin layer of the designable laminated sheet-coated metal plate 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”.

(Processability evaluation and Eriksen test)
Using an Erichsen test device specified in “JIS K-6744”, a 60 mm × 60 mm coated laminated sheet-coated metal plate is subjected to a 6 mm overhanging process so that the coated laminated sheet coated side is convex, and a resin layer The situation was visually observed. As a result, `` ○ '' indicates that no abnormality such as peeling is observed between the resin layers, `` △ '' indicates that slight peeling is observed between the resin layers, or a slight roughness is observed on the surface layer, Those with significant delamination were evaluated as “x”.

(Boiling water immersion resistance)
Using an Erichsen test apparatus defined in “JIS K-6744” on a 60 mm × 60 mm designable laminated sheet-coated metal plate, after applying a 6 mm overhanging process so that the designable laminated sheet-coated side is convex, It was immersed in boiling water for 3 hours, and the state of the resin layer was visually observed. 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 strength with metal plate)
Using a 20 mm × 100 mm design laminated sheet-coated metal plate as a test piece, a peel strength measurement in accordance with “JIS Z-0237, Adhesive Tape, Adhesive Sheet Test Method—180-degree Peeling Adhesive Strength to Test Specimen” is measured. The adhesive strength between the designable laminated sheet and the metal plate 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. In addition, about the adhesive force with this metal plate, it measures only about Examples 5-20 which are changing C layer, and Comparative Examples 5 and 6. FIG.

(Creation of a design laminate sheet)
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 having a thickness of 150 μm and a bright layer having a thickness of 50 μm, and the resin composition of each layer is the same. The concealing layer contains 16 parts by weight of titanium white and titanium yellow as colored pigments, and the glittering layer contains 5 parts by weight of pearl mica pigment as a glittering pigment (each of which has a total amount of resin components of 100 parts). It is a value in mass parts.)

  These co-extruded sheets use an embossed plate with an abstract pattern with a maximum height (Rmax) of 85 μm engraved as a casting roll, and by pulling with the casting roll at the same time as extrusion, the bright layer side The embossed pattern was transferred.

  The C-13 sheet is an example in which a laminated sheet excellent in embossing suitability in an embossing machine in the invention described in “Japanese Patent Application No. 2003-132182” is used as the C layer. The method for producing the C-13 sheet will be described below. The C-13a layer containing the glitter pigment was extruded as a single layer to form a single layer sheet having a thickness of 50 μm. Then, the C-13b layer and the C-13c layer 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 a layer containing a pigment having a thickness of 100 μm (C-13b layer) and a layer having no pigment added having a thickness of 50 μm (C-13c layer). 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 C-13b layer side by a gravure method so that the printed side of the coextruded sheet is in contact with the single layer sheet of C-13a. And then introduced into the off-line embossing machine shown in FIG. In the embossing machine, the surface on the C-13c layer side is brought into contact with the heating drum of the embossing machine, heat fusion lamination is integrated, and at the same time, the surface on the C-13a layer side has a maximum height (Rmax). The embossed pattern was transferred with an embossed plate roll on which an embossed plate with an abstract pattern of 85 μm 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, 5 parts by mass of a pearl mica pigment is used (the total amount of resin components is 100 parts by mass, respectively). Value.)

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. I. V. It is a standard grade for extrusion film formation with a value 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 for the A layer, the thickness and grade shown in Table 2 were used.

  As the adhesive composition of the B layer, an adhesive composition in which an ultraviolet curable adhesive and an isocyanate-terminated urethane prepolymer were blended in the ratios shown in Table 3 was used.

As the adhesive composition described in Table 3, the following were specifically used.
As the “ultraviolet curable adhesive”, New Frontier R1303 (Daiichi Kogyo Seiyaku Co., Ltd.) was used. This is a non-yellowing type and consists of about 60% by weight urethane acrylate composition and about 40% by weight N, N-dialkylacrylamide. Tg is 20 ° C.
As the “isocyanate-terminated urethane prepolymer”, solvent-free Takenate A95 (manufactured by Mitsui Takeda Chemical Co., Ltd.) was used.
“Solvent-free adhesive” is a mixture of Takelac A695 as the main agent and Takenate A95 (both made by Mitsui Takeda Chemical Co., Ltd.) as the main agent in a mass ratio of 6:10 (main agent: hardener). did.

Examples 1-4 and Comparative Examples 1-4
A design laminate sheet was prepared using A-4 as the A layer, C-6 as the C layer, and the adhesive composition shown in Table 4 as the B layer. As a specific production method, the bilayer stretched polyester film of the A layer is continuously applied to the surface of the C layer to which embossing is applied, simultaneously with the application of the B layer adhesive composition using a die coater. In the state where the embossed convex portion of the C layer does not directly contact the A layer and the B layer is interposed by passing between the pair of silicone rubber rolls that can be appropriately adjusted and the roll gap can be adjusted appropriately. The layers were laminated and integrated, and the B layer was cured by an ultraviolet irradiation device disposed immediately thereafter to produce a designable laminated sheet. The irradiation intensity of the ultraviolet irradiation device is the same in all examples and comparative examples.

Examples 5 to 20, Comparative Example 5 and Comparative Example 6
Using the materials shown in Table 5 as the A layer and C layer, and the same B-4 as in Example 2 as the B layer, a designable laminated sheet was produced in the same manner as described above.

(Preparation of a designable laminated sheet-coated metal plate)
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. Then, the coated surface is dried and heated with a hot air heating furnace and an infrared heater, the surface temperature of the steel sheet is set to 240 ° C., and immediately using the roll laminator, the designed laminate sheet prepared above is coated and air-cooled. A designable laminated sheet-coated metal plate was produced by cooling. The type and application conditions of the adhesive used for laminating with the steel plate 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 4 and 5.

(Evaluation results)
The following evaluation results were obtained from Tables 4 and 5.
In Comparative Example 1, only an ultraviolet curable adhesive was used as the adhesive composition of the B layer. However, when Erichsen processing was performed, cohesive peeling occurred inside the B layer. It is considered that the cohesive strength of the adhesive is insufficient. The appearance deteriorated further in the boiling water immersion test.

  Compared to Comparative Example 1, Comparative Example 2 shows an improvement, and it can be said that there is an effect of mixing an isocyanate-terminated urethane prepolymer in this respect. Even if Erichsen processing was performed, the flocculent peeling inside the B layer did not occur, but peeling occurred when the boiling water immersion test was performed.

  Comparative Example 3 is a case where the amount of the isocyanate-terminated urethane prepolymer is larger than the range of the present invention, and the excess isocyanate reacts with moisture when immersed in boiling water to cause a foaming phenomenon, resulting in a remarkable appearance defect.

  Comparative Example 4 is a case where a solventless adhesive is used without using an ultraviolet curable adhesive, but cohesive peeling of the adhesive layer is caused by Erichsen processing. Moreover, in the boiling water immersion test, foaming occurred in the adhesive layer in the same manner as in Comparative Example 3, resulting in a remarkable appearance defect. Further, Examples 1 to 4 and Comparative Examples 1 to 3 obtained practical strength simultaneously with the irradiation of the ultraviolet lamp, whereas Comparative Example 4 required curing for about 24 hours.

  Although the comparative example 5 is a case where a thing thinner than the preferable thickness of this invention is used as transparent stretched polyester-type resin of A layer, the smoothness of the surface was not obtained. It is considered that the effect of curing shrinkage slightly generated in the B layer is reflected as a poor appearance on the surface of the laminated sheet-coated metal plate when the thickness of the A layer is too thin.

  The comparative example 6 is a case where the transparent stretched polyester resin of the A layer is thicker than the preferred thickness of the present invention, and the rigidity of the A layer was too high, so that it could not endure the Eriksen process.

On the other hand, good results were obtained in the examples of the present invention.
Example 5 is a case where the transparent stretched polyester resin of the A layer has a thickness near the lower limit of the preferred thickness of the present invention, and the surface smoothness is slightly inferior.
Example 16 is a case where a resin composition of the C layer having a large proportion of PBT resin was used, and the conventional soft PVC sheet lamination conditions resulted in slightly weak adhesion strength to the metal plate.
In Example 17, a C layer made of only PTT resin was used, and the adhesive strength with the metal plate was further reduced as compared with Example 16. When using the same temperature condition as laminating a conventional soft PVC sheet, it is preferable not to use these C layers.
Example 19 is a case where only a substantially amorphous polyester was used as the resin composition of the C layer, and the C layer was deformed in the boiling water immersion test, resulting in rough appearance.
In Example 20, the boiling water immersion property was improved more than this, but some surface roughness was caused.
In Examples 5 to 18, no problem occurred in the boiling water immersion test, and it is preferable not to use the C layer of Example 19 and Example 20 for unit bath use in which the test is included as an evaluation item.

  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 schematic diagram which shows the layer structure in one Embodiment 100a of the designable lamination sheet of this invention. It is a schematic diagram which shows the layer structure in one Embodiment 100b of the designable lamination sheet of this invention. It is a schematic diagram which shows the layer structure in one Embodiment 100c of the designable lamination sheet of this invention. It is a schematic diagram which shows the layer structure in one Embodiment 100d of the designable lamination sheet of this invention. It is a schematic diagram which shows the layer structure in one Embodiment 100e of the designable lamination sheet of this invention. It is a schematic diagram which shows the layer structure in one Embodiment 200 of the designable lamination sheet coating metal plate of this invention. It is a figure which shows the embossing machine used to provide embossing to the C-13 sheet which is C layers 32, 34, and 36. FIG.

Explanation of symbols

100a to e Designable laminate sheet 200 Designable laminate sheet-coated metal plate 10 Transparent stretched polyester resin layer (A layer)
20 Adhesive layer (B layer)
30 Layer mainly composed of polyester resin (C layer)
32 Layer containing highly regulated pigment (C1 layer)
34 Layer containing colored pigment (C2 layer)
36 Layer without added pigment 40 Printing layer (D layer)
DESCRIPTION OF SYMBOLS 50 Adhesive layer 60 Metal plate 300 Embossing machine 310 Heating roll 320 Take off roll 330 Infrared heater 340 Embossing roll 350 Nip roll 360 Cooling roll

Claims (9)

As a surface layer, a transparent stretched polyester resin layer (A layer) having a thickness of 38 μm or more and 125 μm or less,
As an intermediate layer, an adhesive layer (B layer),
As a base material layer, it has an uneven design by embossing on the surface to be laminated with the B layer, and contains a pigment, a layer mainly composed of a non-oriented polyester resin (C layer),
A laminated sheet having at least three layers,
The B layer has a thickness equal to or greater than the thickness at which the embossed convex portion of the C layer is completely buried,
The designable laminated sheet in which the B layer is a mixture of 50% by mass or more and less than 96% by mass of the ultraviolet curable adhesive and 4% by mass or more and less than 50% by mass of the urethane terpolymer having an isocyanate terminal.   The designable laminated sheet according to claim 1, wherein a glass transition temperature of the ultraviolet curable adhesive of the B layer is in a range of -30 to 80 ° C.   The C layer is a polybutylene terephthalate (PBT) resin or a polytrimethylene terephthalate (PTT) resin of 20% by mass or more and less than 80% by mass, with the mass of all the resin components of the C layer being 100% by mass, The designable laminated sheet according to claim 1 or 2, which is a mixture with a polyester resin having a substantially amorphous content of 20% by mass or more and less than 80% by mass.   The substantially amorphous polyester resin comprises terephthalic acid or dimethylterephthalic 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 80-20 mol. The designable laminated sheet according to claim 3, wherein% is a copolyester comprising ethylene glycol.   The designable laminated sheet according to any one of claims 1 to 4, comprising a printing layer (D layer) between the B layer and the C layer.   The C layer comprises at least two layers of a C1 layer facing the B layer side and containing a bright pigment, and a C2 layer located on the opposite side of the B layer side and containing a coloring pigment having a hiding power. The designable laminated sheet according to any one of 1 to 5.   The designable laminated sheet according to any one of claims 1 to 6, further comprising a printing layer (D layer) between the B layer and the C1 layer, or between the C1 layer and the C2 layer.   The designable laminated sheet covering metal plate which has the designable laminated sheet and metal plate in any one of Claims 1-7, and the surface by the side of the C layer of the said designable laminated sheet is laminated | stacked on the metal plate. 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 general wall material using the designable laminated sheet-coated metal plate according to claim 8.

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