JP4994870B2 - Designable laminated sheet and designable laminated sheet-coated metal plate - Google Patents

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 excellent in productivity, workability, and design properties, and a design laminate sheet-coated metal plate 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 of soft polyvinyl chloride (hereinafter abbreviated as “PVC”) colored by the addition of a pigment, and further, it is transparent and smooth. The thing of the structure which coat | covered the good resin film 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 a high demand for a design-resin-coated metal plate having a structure in which an uneven pattern (embossed pattern) existing inside can be visually recognized through a surface layer having a semi-transparent and highly smooth surface (such a structure is described as “ Called “internal embossing configuration” etc.).

With respect to the design resin-coated metal plate having such an internal embossed structure, as disclosed in Patent Document 1, a method of coating a concavo-convex surface of a colored soft PVC sheet having an embossed surface with a transparent PVC paste, or Patent Document 2 A method of filling and curing a solvent-free curable resin on the surface of a thermoplastic resin sheet embossed on the surface, and a dry lami adhesive on the surface of the thermoplastic resin sheet embossed as in Patent Document 3 A transparent thermoplastic resin layer, a UV-curable adhesive between the uneven surface of a colored soft PVC sheet embossed and printed on the surface and a transparent surface layer as in Patent Document 4 and Patent Document 5 It was possible to obtain the above-mentioned internal embossing structure by a method such as filling a transparent top film and coating a transparent top film.
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.

  Since the solvent-free two-component curable resin layer is the outermost surface, it is necessary to make the layer have good scratch resistance, and the resin-coated metal plate Because it is necessary to secure secondary workability, especially bending workability, it is necessary to design a very difficult material as an adhesive to be applied to resin-coated metal sheet applications, and as a result, the product is inexpensive. It becomes difficult to get. Further, since it takes time to cure, productivity is extremely poor.

  According to Patent Document 3, a thermoplastic resin film is used as the outermost layer, and therefore, by appropriately selecting the surface layer such as using a biaxially stretched PET film, both the scratchability and workability as a resin-coated metal plate are compatible. However, the dry laminating adhesive is solvent-based and cannot be applied too thickly, and therefore cannot provide a deep internal embossing design.

  Those obtained by Patent Documents 4 and 5 are generally included as evaluation items for processability (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.

  If a normal solvent-based curable adhesive is used instead of the UV curable adhesive, the coating thickness after drying becomes thin, so thick coating is difficult. A coating thickness sufficient to obtain smoothness on the surface of the transparent surface layer could not be secured.

  In addition, since solvent-free isocyanate curable adhesives require time for curing after application, there is no misalignment between the transparent surface layer and the colored resin layer until curing, or adhesion Problems with processes such as requiring a device to hold the agent layer so as not to cause deformation such as a depression due to an external force also occur, so that a product having practical productivity and performance has not been obtained.

  Therefore, the present invention has a good productivity and workability, and the internal embossing structure having a design with a sense of depth and three-dimensionality that allows the internal embossing to be visually recognized through a smooth and transparent surface. It is an object of the present invention to provide a laminated sheet and a metal plate coated with the sheet that can be used for a unit bath without causing a problem even in a boiling water immersion test.

  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.

  In the first aspect of the present invention, a transparent stretched polyester resin layer (A layer) (10), an adhesive layer (B layer) (20), and a thermoplastic resin layer (C layer) (30) as a base material layer from the surface layer side. ), And the C layer (30) has an uneven design by embossing on the surface on the side laminated with the B layer (20), and includes a pigment having a thickness of 100 μm or more and 300 μm or less. A non-solvent type adhesive 40 comprising a layer B (20) having a thickness exceeding the thickness at which the embossed protrusion of the C layer (30) is completely filled, and comprising a terminal isocyanate group-containing urethane prepolymer and a polyol. -80 mass% and acrylate oligomer and / or acrylate monomer 60-20 mass%, and the acrylate monomer is acryloylmorpholine, dimethylacrylamide, diethylamine. It is a designable laminated sheet (100) characterized by being one or more acrylate monomers selected from chloramide, diisopropylacrylamide, and isobornyl acrylate. In addition, the code | symbol 100 is used as a high-order concept containing the designable lamination sheet (100A-100D).

  “Thickness exceeding the thickness at which the embossed convex portion of the C layer (30) is completely buried” means that the thickness of the B layer (20) in the portion beyond the embossed convex portion of the C layer (30) is B layer (20). It means 2% or more of the total thickness, preferably 5% or more.

  In the designable laminated sheet (100A) of the first aspect of the present invention, by using the above-mentioned adhesive component as the B layer (20), the productivity is extremely good, and the bending workability and boiling water soaking property at a low temperature are also achieved. It is possible to achieve both, and sufficient adhesion between layers can be achieved. In addition, since this adhesive component is a solvent-free adhesive, even if the surface of the C layer (30) is provided with unevenness by embossing relatively deeply, it is completely filled and further transparent A It is easy to ensure a coating thickness sufficient to obtain smoothness on the surface of the layer (10).

  In addition, when using a transparent stretched polyester resin film, which is a material that has been used for overlaying soft PVC, as the A layer (10), it is used in the bathroom as a resin-coated metal plate for a unit bath. There is no possibility of causing problems in various surface properties. 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 first aspect of the present invention, the C layer (30) faces the B layer (20) side and is located on the side opposite to the C layer (32) containing the glitter pigment and the B layer (20) side, and is concealed. It can be set as the layer comprised by providing at least 2 layers of C2 layer (34) containing a coloring pigment with strength. Thereby, the visibility of the embossed shape given to the inside of the laminated structure becomes better. In addition, since the luster pigment is generally inferior in hiding power, a layer to which a coloring pigment having hiding power is added underneath it is affected by changes in the surface state and color of the metal plate (60). Therefore, the designable laminated sheet-coated metal plate (200) having a stable color tone can be obtained.

  In the above designable laminated sheet, 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). A printing layer (D layer) (40) may be provided between the two. 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 this invention has said designable laminated sheet (100) and metal plate (60), The surface by the side of C layer (30) of the said designable laminated sheet is laminated | stacked on the metal plate (60). It is a designable lamination sheet covering metal plate (200).

  The designable laminated sheet-coated metal plate (200) of the second aspect 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. Is. 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.

  A third aspect of the present invention is an architecture 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 above-described designable laminated sheet-coated metal plate (200). It is an 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 sheets 100A to 100D 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.

<Thermoplastic resin layer (C layer) 30>
The C layer 30 is a layer mainly having a thermoplastic resin as a main component having an uneven design by embossing on the surface to be laminated with an adhesive layer (B layer 20) to be described later and colored by adding a pigment. Here, “main component” means that an additive such as a pigment may be contained in the C layer 30, and the mass of the entire C layer 30 is a reference (100% by mass). This means that the thermoplastic resin is contained in an amount of 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more.

  As the thermoplastic resin constituting the C layer 30, it is easy to give an uneven design by embossing, and the workability as the design laminated sheet-coated metal plate 200 laminated with 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. Examples of such a thermoplastic resin include PVC or non-oriented polyester resin, and the C layer 30 of the present invention is preferably a layer containing these as a main component.

  The PVC referred to in the present invention is produced from a hard, semi-rigid and soft vinyl chloride resin composition, and dioctyl phthalate (DOP), dibenzyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dibutyl fuma as a plasticizer. The rate is blended.

  In addition, examples of the polyester resin in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene isophthalate (PEI), polyethylene naphthalate (PEN), and polyethylene terephthalate / ethylene mainly composed of ethylene terephthalate units. Isophthalate copolymer (PETI), polybutylene terephthalate isophthalate copolymer (PBTI), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol-co-ethylene terephthalate (PETG), polybutylene naphthalate (PBN) and A blend resin obtained by mixing two or more of these resins is used.

  In the case where the design property is imparted to the C layer 30, the visual concealing effect of the metal plate 60 to be coated is improved, the visibility of the embossed design is improved, and further, the printing layer (D layer) 40 is imparted to the surface. A pigment is added for the purpose of improving the color development. 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 concealment 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 use, JIS K5600-4-1: 1999. It is preferable that the hiding ratio measured in accordance with “Paint General Test Method—Part 4: Visual Characteristics of Effective Coating Film—Section 1: Hiding power (for light-colored paint)” 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. It is good also as a structure provided with at least 2 layer of C2 layer 34 made. 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.

  Furthermore, since the luster pigment is generally inferior in hiding power, by disposing a layer to which a coloring pigment with hiding power is added below, the surface state of the metal plate 60 and the color change 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 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 printing layer (D layer) 40 described later may be provided between the C1 layer 32 containing the glitter pigment and the C2 layer 34 containing the color pigment (the form of FIG. 1 (c)). Moreover, you may provide between the C1 layer 32 containing a luster pigment, and the adhesive bond layer 20 (form of FIG.1 (d)).

  It should be noted that various general additives may be added to the C layer 30 in an appropriate amount 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. Further, when 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.

  A preferable thickness of the C layer 30 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. 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 thickness of the C layer 30 is better in that a deeper embossed pattern can be transferred, but if the thickness exceeds 300 μm, the design laminate The workability of the sheet-coated metal plate 200 is deteriorated, and the cost is disadvantageous. When the C layer 30 includes at least two layers of the C1 layer 32 and the C2 layer 34, it is preferable that the total thickness of these layers is in the above range.

<Adhesive layer (B layer) 20>
The B layer 20 is preferably composed of 40 to 80% by mass of a solventless adhesive composed of a terminal isocyanate group-containing urethane prepolymer and a polyol, and 60 to 20% by mass of an acrylate oligomer and / or an acrylate monomer.

(Terminal isocyanate group-containing urethane prepolymer)
The terminal isocyanate group-containing urethane prepolymer can be synthesized by reacting an organic polyisocyanate and an organic polyol to urethanize. Examples of the organic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Aliphatic diisocyanates such as diisocyanates, such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4 ′ -Methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexa Alicyclic diisocyanates such as diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate Aromatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethi Aromatic aliphatic diisocyanates such as benzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof, such as triphenylmethane-4,4 ', 4 "-triisocyanate, Organic triisocyanates such as 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, such as 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate Polyisocyanate monomer such as organic tetraisocyanate, dimer, trimer, biuret, allophanate derived from the above polyisocyanate monomer, 2,4,6-oxadia obtained from carbon dioxide and the above polyisocyanate monomer Such as polyisocyanate having a gintrione ring It is below.

  As the organic polyol, those having 2 to 6, particularly 2 to 4 functional groups and a molecular weight of 200 to 10,000, particularly 300 to 5,000 are preferable. More specifically, polyester polyol, polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil, polyurethane polyol or a mixture thereof can be mentioned.

  Examples of such polyester polyols include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or their dialkyl esters or mixtures thereof, such as ethylene glycol, propylene glycol, diethylene glycol, Butylene glycol, neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. Polyol polyol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolacto) obtained by reacting glycols of the above or a mixture thereof And polyester polyols obtained by ring-opening polymerization of lactones.

  Examples of polyether polyols include, for example, polymerization of oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators. Polyether polyols obtained in this way.

  Examples of the polyether ester polyol include, for example, reacting the above-mentioned polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or a dialkyl ester thereof or a mixture thereof. The polyether ester polyol obtained is mentioned.

  As an example of the polyester amide polyol, it can be obtained by using an aliphatic diamine having an amino group such as ethylene diamine, propylene diamine, hexamethylene diamine as a raw material in the polyesterification reaction.

  Examples of acrylic polyols include polymerizable monomers having one or more hydroxyl groups in one molecule, such as hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic hydroxybutyl, or the corresponding methacrylic acid derivatives thereof, For example, it can be obtained by copolymerizing acrylic acid, methacrylic acid or an ester thereof.

  Examples of the polycarbonate polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol-A, hydrogenated bisphenol- Examples thereof include those obtained by reacting one or more glycols selected from A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.

  The polyurethane polyol is a polyol having a urethane bond in one molecule. For example, NCO / OH is a combination of a polyether polyol, a polyester polyol, a polyether ester polyol, etc. having a molecular weight of 200 to 5,000 and the organic polyisocyanate described above. It is obtained by reacting at 1.5 to 2.5. When the equivalence ratio is less than 1.5, the urethane prepolymer has a high viscosity, and when it exceeds 2.5, the urethane prepolymer has a low viscosity, which is not preferable in terms of coating work. The free isocyanate group (NCO) content of the urethane prepolymer is usually 1 to 15%.

  The viscosity (25 ° C.) of the terminal isocyanate group-containing urethane prepolymer in the present invention is usually from 50 to 10,000 Pa · s. When the viscosity is less than 50 Pa · s, the coating thickness is non-uniform, and when it exceeds 10,000 Pa · s, the coating workability is deteriorated, for example, unevenness tends to occur on the coated surface.

(Polyol)
Examples of the polyol that is a curing agent include the same organic polyols as described above, and may be a terminal hydroxyl group-containing derivative of the polyol. Further, the organic polyol and the terminal hydroxyl group-containing derivative may be used as a mixture.

  The number average molecular weight of the polyol is usually 1,000 to 3,000, preferably 1,100 to 2,500. If the number average molecular weight is less than 1,000, there is a problem that the flexibility of the resulting adhesive layer (B layer) 20 is lowered, and if it exceeds 3,000, the adhesion to the C layer 30 as a substrate is lowered. To do.

  Examples of the terminal hydroxyl group-containing derivative of a polyol include a partially or completely hydrogenated polyol, a modified product of a polyol with an isocyanurate ring-containing polyisocyanate, and a modified product of a polyol with a burette bond-containing polyisocyanate. Examples of partially or completely hydrogenated polyols include partially or completely hydrogenated polyols.

  The modified product of the polyol with the isocyanurate ring-containing polyisocyanate is obtained by reacting the above-mentioned organic polyol with the isocyanurate ring-containing polyisocyanate. The isocyanurate ring-containing polyisocyanate is prepared, for example, by using the above-mentioned organic polyisocyanate as a catalyst [for example, alkoxide (sodium methylate, etc.), amine (triethylamine, etc.), carboxylate (calcium naphthenate, etc.), organometallic compound (dibutyltin dilaurate). Etc.), etc.] alone or in combination of two or more, and the reaction temperature is usually 50 to 150 ° C. The reaction equivalent ratio of the hydroxyl group of the polyol and the isocyanate group of the isocyanurate ring-containing polyisocyanate in the modified product is usually 1: (0.1 to 0.7), preferably 1: (0.2 to 0.6). ). The reaction temperature is usually 50 to 100 ° C. In the reaction, a known urethane polymerization catalyst (such as dibutyltin dilaurate) can be added as necessary to promote the reaction. The modified product has an OH equivalent of usually 500 to 3,000, preferably 700 to 2,500.

  Moreover, the modified product of the polyol with a burette bond-containing polyisocyanate can be obtained by reacting the organic polyol with the burette bond-containing polyisocyanate. The buret bond-containing polyisocyanate can be obtained, for example, by a method in which 3 mol or more of water is used with respect to 1 mol of polyisocyanate to remove excess isocyanate after a burette conversion reaction. The reaction can usually be obtained by reacting a strong base (tertiary amine such as triethyldiamine, etc.) or an organometallic compound (dibutyltin dilaurate etc.) at a reaction temperature of usually 50 to 150 ° C. The reaction equivalent ratio of the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate containing a burette bond in the modified product is usually 1: (0.1 to 0.7), preferably 1: (0.2 to 0.6). ). The reaction temperature is usually 50 to 100 ° C. In the reaction, a known urethane polymerization catalyst (such as dibutyltin dilaurate) can be added as necessary to promote the reaction. The modified product has an OH equivalent of usually 500 to 3,000, preferably 700 to 2,500.

  The viscosity (25 ° C.) of the polyol (curing agent) is usually 50 to 800 Pa · s, preferably 80 to 600 Pa · s. When the viscosity of the curing agent is less than 50 Pa · s, the thickness of the adhesive layer becomes partially non-uniform when the film is wound after laminating various plastic films, and when it exceeds 800 Pa · s, the coating surface becomes uneven. Workability is reduced.

  The terminal isocyanate group-containing urethane prepolymers and polyols and / or terminal hydroxyl group-containing derivatives of the polyols are commercially available from Mitsui Takeda Chemical, Toyo Ink, Dainippon Ink and others.

  The compounding ratio of the terminal isocyanate group-containing urethane prepolymer and the polyol and / or the terminal hydroxyl group-containing derivative of the polyol is preferably NCO / OH = 1.0 to 1.4 in terms of an equivalent ratio.

  The solventless adhesive comprising the above-mentioned terminal isocyanate group-containing urethane prepolymer and polyol is in the range of 40% by mass or more and 80% by mass or less based on the mass of the entire composition forming the B layer 20 (100% by mass). It is blended with.

(Acrylate oligomer)
The acrylate oligomer in the present invention is a compound having one to several acryloyl group (CH ₂ ═CHCO—) or methacryloyl group (CH ₂ ═CCH ₃ CO—) in the molecule and having a molecular weight of several hundred to several hundreds. Yes, representative examples include mono (meth) acrylates such as epoxy, epoxidized oil, urethane, polyester, and polyether, di (meth) acrylate, tri (meth) acrylate, and polyfunctional (meth) acrylate.

  As such acrylate oligomer, Aronix (manufactured by Toagosei Co., Ltd.), Art Resin (manufactured by Negami Kogyo Co., Ltd.), NK Oligo (manufactured by Shin Nakamura Chemical Co., Ltd.), New Frontier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. ing.

(Acrylate monomer)
The acrylate monomer used in the present invention is one or more selected from the group consisting of acryloylmorpholine, dimethylacrylamide, diethylacrylamide, diisopropylacrylamide, and isobornyl acrylate. Among these, a commercial product of acryloylmorpholine includes ACMO (manufactured by Kojin Co., Ltd.), and a commercial product of dimethylacrylamide includes DMAA (manufactured by Kojin Co., Ltd.).

  The amount of the acrylate oligomer and / or acrylate monomer added is in the range of 20% by mass or more and 60% by mass or less based on the mass of the entire composition forming the B layer 20 (100% by mass). If the addition amount of the acrylate oligomer and / or acrylate monomer exceeds 60%, the initial processability immediately after curing is good, but the embossing of the underlying sheet is caused by curing shrinkage, and the appearance such as conspicuous unevenness is deteriorated. The problem comes out. On the other hand, if it is less than 20%, the adhesiveness immediately after the lamination is lowered, so that the adhesive layer protrudes when it is cut.

  The blending ratio of the acrylate oligomer and / or the acrylate monomer is not particularly limited, but the acrylate oligomer is 30 to 70% by mass with respect to 30 to 70% by mass of the acrylate oligomer due to problems of adhesive properties and workability of the composition. A range of 70 to 30% by mass of the monomer is preferable.

  The composition forming the adhesive layer (B layer) 20 can be cured with active energy rays such as visible light, ultraviolet rays, electron beams, and X-rays. In the case of curing with ultraviolet rays, it is preferable to use an ultraviolet sensitive photopolymerization initiator. Examples of the ultraviolet-sensitive 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- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino - propan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like. Commercially available products include IRUGACURE184, 651, 500, 907, CG1369, CG24-61 (above, manufactured by Ciba Geigy), Lucirine LR8728 (manufactured by BASF), Darocure 1116, 1173 (above, manufactured by Merck), Ubekrill P36 (UCB) Manufactured).

  When curing with visible light, it is preferable to use a visible light sensitized photopolymerization initiator such as camphorquinone.

  In addition, the sensitivity of photopolymerization can be improved by adding an additive having a sensitizing action. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate. Commercially available products include Ubekrill P102, 103, 104, 105 (above, manufactured by UCB).

  These photopolymerization initiators are preferably blended in an amount of 0.1% by mass or more and 10% by mass or less based on the mass of the entire composition forming the B layer 20 (100% by mass).

  The liquid curable adhesive / adhesive composition forming the adhesive layer (B layer) 20 can be produced by mixing the above-mentioned components by a conventional method. The viscosity of the composition thus prepared is usually 100 to 1,000,000 cps / 25 ° C., preferably 200 to 10,000 cps / 25 ° C.

  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. Here, the thickness exceeding the thickness at which the embossed convex portion is completely buried means that the thickness of the B layer 20 in the portion beyond the embossed convex portion of the C layer 30 is 2% or more of the total thickness of the B layer 20, preferably 5 % Or more.

  This is because the portion corresponding to the embossed convex portion of the C layer 30 bulges on the surface of the A layer 10 even when curing shrinkage in the thickness direction of the B layer 20 occurs when the B layer 20 is cured by ultraviolet irradiation. This is to prevent reflection. By providing the B layer 20 beyond the thickness at which the embossed convex portion of the C layer 30 is completely buried, the surface of the transparent stretched polyester resin layer (A layer) 10 is caused by the embossed convex portion of the C layer 30. A smooth state is maintained without reflection of swell, and mirror surface properties are secured on the surface of the A layer 10.

  When the coating thickness of the B layer 20 is lower than the height of the embossed convex portion of the C layer 30, smoothness cannot be imparted to the surface of the A layer 10, and when the B layer 20 is applied, Problems such as air bubbles occur during lamination. 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.

  It should be noted that the B layer 20 may have various additives such as an inorganic filler, a small amount of process oil, a plasticizer, a thixotropic agent, a pigment, an anti-ultraviolet agent and a stabilizer for maintaining and improving weather resistance, and a catalyst. Etc. 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 as the A layer 10 from the viewpoints of transparency, smoothness, surface resistance to various chemicals such as scratch resistance, and alkali resistance.

  The thickness of the A layer 10 is preferably 12 μm to 200 μm, and more preferably 20 μm to 150 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 designable 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 layer) 40>
The printing layer (D 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. Also good. Moreover, both printing with a luster pigment and normal pattern printing may be provided.

  The D 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.

  Moreover, after giving an embossed pattern to C layer 30, you may carry out by the method of printing on an uneven surface with an ink jet type printing apparatus etc. Alternatively, when the C1 layer 32 and the C2 layer 34 are not laminated and integrated in a die by the coextrusion method, the C1 layer 32 is laminated with one or both surfaces of the C1 layer 32 or the C1 layer 32 in the C2 layer 34. A printed layer may be applied to the surface 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, since the workability is better when the smooth sheet is printed, the latter two or similar methods are preferable, and the C layer 30 is referred to as “Japanese Patent Application 2003-2003”. Appropriateness to the embossing machine as a multi-layer structure as described in “132182” and “Japanese Patent Application No. 2004-285225”, and making it possible to perform pattern transfer with the embossing machine is compatible with small lots. This is particularly preferable.

  The method of 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 of the composition forming the B layer 20. 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. 30 or a method of supplying the B layer 20 to the surface of the C layer 30 on which the unevenness due to embossing is provided, and further covering the A layer 10.

  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, when the C layer 30 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, 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 μm 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 laminator is immediately used 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, those conventionally used for resin-coated metal plates can be used without any particular limitation. For example, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, hot-dip zinc / aluminum Various steel plates such as alloy-plated steel plates, hot-dip zinc / aluminum / magnesium alloy-plated steel plates, tin-plated steel plates, tin-free steel and stainless steel plates, aluminum alloy plates, nickel alloy plates, titanium alloy plates and the like 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 design laminated sheet-coated metal plate 200 of the present invention has good workability as a coated laminate sheet having an embossed structure with a sense of depth and a three-dimensional effect, and includes door materials, partition materials, It can use suitably for building interior materials, such as a general wall material. Moreover, since it does not cause a problem in the boiling water immersion test, it can be particularly suitably used for a unit bath wall material, a unit bath ceiling material, and 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 shown in the Example and the comparative example are as follows.

(State immediately after lamination)
After applying the composition of the B layer 20 having a predetermined composition shown in Table 1 on the C layer 30 of the C layer 30-coated metal plate, laminating the PET film of the A layer 10 and curing it with ultraviolet rays, When there was no dent on the surface when pressed with a finger, “◎”, when there was a slight but practically no problem, “◯”, and when there was a practical problem, “×”.

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

(Evaluation of low-temperature workability: bending workability test at 0 ° C)
Evaluation of the V bending method prescribed | regulated by JISZ2248 was performed to the laminated sheet coating metal plate 200 of 40 mm x 60 mm. In the V-bending method, a screw bending test apparatus 300 whose general view is shown in FIG. 2 is used. The screw bending test apparatus 300 includes an upper mold lifting handle 310, an upper mold lifting screw 320, an upper mold installation portion 330, and a lower mold installation portion 340. By manually turning the upper die lifting handle 310 provided on the upper portion of the upper lifting screw 320, the upper lifting screw 320 is moved in the vertical direction, and accordingly, provided at the lower end of the upper lifting screw 320. The upper mold installation part 330 moves in the vertical direction. Further, as shown in the enlarged view of the V-bending portion in FIG. 2B, the upper die installation portion 330 is provided with a V-bending upper die 350, and the lower die installation portion 340 is provided with a V-bending lower portion. A mold 360 is provided. Then, by operating the upper mold lifting handle 310, the V bending upper mold 350 provided in the upper mold installation portion 330 is moved downward, and the test piece 380 is sandwiched between the V bending lower mold 360. As a result, the test piece 380 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 maintained at 0 ° C., and the test piece is also tested after being kept at 0 ° C. for 1 hour or longer. To serve.

(Boiling water immersion resistance)
Using an Erichsen test apparatus defined in JIS K6744, a 60 mm × 60 mm designable laminated sheet-coated metal plate 200 was subjected to a 6 mm overhanging process so that the designable laminated sheet coated side was convex, and then in boiling water. It was immersed 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”.

(Ericsen processability)
According to JIS K6744, when the Erichsen process was performed with an extrusion amount of 6 mm, the case where the PET film (A layer 10) was lifted was indicated as “X”, and the case where there was no peeling was indicated as “◯”.

(Comprehensive evaluation)
In each of the above evaluations, one with x was evaluated as “x”, and one without x was evaluated as “◯”.

<Examples 1-6, Comparative Examples 1-5>
(Preparation of C layer 30)
Using two twin-screw kneading extruders, two layers comprising a total thickness of 200 μm consisting of 60% by mass of Easter 6763 (manufactured by Eastman Chemical) and 40% by mass of Novaduran 5020S (manufactured by Mitsubishi Engineering Plastics) by a feed block method. A sheet was formed. The breakdown of the two layers is a concealing layer (C2 layer) having a thickness of 150 μm and a bright layer (C1 layer) having a thickness of 50 μm, and the resin composition of each layer is the same.

  The concealing layer contains 16 parts by mass of titanium white and titanium yellow as coloring pigments, and the glittering layer contains 3 parts by mass of a pearl mica pigment having a particle diameter of 5 μm to 15 μm (respectively resin). (This is the value where the total amount of the components is 100 parts by mass.)

  These co-extruded sheets use a casting roll engraved with an embossed plate with an abstract pattern having a maximum height (Rmax) of 85 μm, and are extruded from a T-die and simultaneously taken up by the casting roll. The embossed pattern was transferred to the side.

(Adhesion between C layer 30 and metal plate 60)
A polyester adhesive generally used for a polyvinyl chloride coated metal plate is coated on the surface of a galvanized steel sheet (thickness: 0.45 mm) so that the adhesive film thickness after drying is about 2 μm 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 245 ° C., and immediately using the roll laminator, the embossed C layer prepared above is applied. C layer 30-coated metal plate was prepared by coating 30 and cooling with air. The type and application conditions of the adhesive used for laminating with the steel plate are the same in all examples and comparative examples.

(Preparation of A layer 10 and B layer 20)
A biaxially stretched polyethylene terephthalate resin film (Tetron DuPont Films, Tetron SG-2, thickness 75 μm) is used as the A layer 10, and the B layer 20 shown in Table 1 continuously using a die coater for the A layer 10. At the same time as applying the adhesive composition, the surface of the A layer 10 is continuously supplied so that the surface of the A layer 10 coated with the adhesive composition overlaps the C layer 30 side of the metal plate prepared above. The embossed convex portion of the C layer 30 is interposed between the B layer 20 having a thickness that does not directly contact the A layer 10 by passing between a pair of silicone rubber rolls capable of appropriately adjusting the roll gap. The A layer 10 was laminated and integrated, and the B layer 20 was cured by an ultraviolet irradiation device disposed immediately thereafter to produce a designable laminated sheet-coated metal plate 200. Note that the irradiation intensity of the ultraviolet irradiation apparatus was the same in all examples and comparative examples, and curing was performed at a cumulative irradiation amount of 340 mJ / cm ² using a high-pressure mercury lamp.

  The types of solventless adhesives and acrylate oligomer / acrylate monomers in Table 1 are shown below.

<Solvent-free adhesive>
[1]: Takei Mitsui Chemicals, Takenate A663 / Takelac A18 = 100/65
[2]: Dainippon Ink & Chemicals, Dick Dry 2K-SF-350A / HA-550B = 3/1
[3]: Dainippon Ink & Chemicals, Dick Dry 2K-SF-900A / HA-900B = 2/1

<Acrylate oligomer / acrylate monomer>
A: New Frontier R1213 (urethane acrylate / acryloylmorpholine = 50/50) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
B: manufactured by Negami Kogyo Co., Ltd., Art Resin NPC18 (urethane acrylate) / Daiichi Kogyo Seiyaku Co., Ltd., New Frontier IBA (isobornyl acrylate) = 30/70
C: Art resin NPC18 (urethane acrylate) / Daiichi Kogyo Seiyaku Co., Ltd., New Frontier PHE (phenoxy acrylate) = 50/50
D: manufactured by Negami Kogyo Co., Ltd., Art Resin NPC18 (urethane acrylate) / manufactured by Kojin Co., Ltd., diethylacrylamide DEAA = 60/40
E: manufactured by Negami Kogyo Co., Ltd., Art Resin NPC25 (urethane acrylate) / manufactured by Kojin Co., Ltd., dimethylacrylamide DMAA = 60/40
F: manufactured by Negami Kogyo Co., Ltd., Art Resin NPC18 (urethane acrylate) / manufactured by Kojin Co., Ltd., diisopropylacrylamide = 70/30

Table 1 revealed the following.
(1) The adhesive using only the solvent-free adhesive as the adhesive for the B layer 20 has a good appearance but is inferior in the state immediately after lamination, the boiling water resistance test, and the elixir processability (Comparative Example). 1).
(2) As an adhesive for the B layer 20, a solvent-less adhesive 90 mass% / acrylate oligomer / acrylate monomer 10 mass% is improved in the state immediately after lamination, but the boiling water resistance test, The Eriksen processability was inferior (Comparative Example 2).
(3) However, in the case of adding a predetermined acrylate oligomer / acrylate monomer within the scope of the present invention to the solventless adhesive, the state immediately after lamination, the appearance, and the bending workability at 0 ° C. In addition, the boiling water resistance test and the Erichsen workability were satisfied (Examples 1 to 6).
(4) About the type of acrylate monomer outside the scope of the present invention, the state immediately after lamination and the appearance were good, but the boiling water resistance test and the Erichsen workability were poor (Comparative Example 3). ).
(5) In addition, when the addition amount of the acrylate oligomer / acrylate monomer exceeds the range of the present invention with respect to the solventless adhesive, the appearance was inferior (Comparative Examples 4 and 5). .

  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 laminate sheet and the design laminate sheet-coated metal plate with 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 of the designable lamination sheet of this invention. It is explanatory drawing which shows the outline | summary of the screw bending test apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Designable laminated sheet 200 Designable laminated sheet coated metal plate 10 Transparent stretched polyester resin layer (A layer)
20 Adhesive layer (B layer)
30 Thermoplastic resin layer (C layer)
32 C1 layer containing high-brightness pigment 34 C2 layer containing colored pigment 40 Printing layer (D layer)
50 Adhesive layer 60 Metal plate

Claims (10)

A laminated sheet comprising a transparent stretched polyester resin layer (A layer), an adhesive layer (B layer), and a thermoplastic resin layer (C layer) as a base material layer from the surface side,
The C layer is a layer that has an uneven design by embossing on the surface on the side laminated with the B layer, and includes a pigment having a thickness of 100 μm or more and 300 μm or less,
The B layer has a thickness that exceeds the thickness at which the embossed convex portion of the C layer is completely filled, and a solvent-free adhesive composed of a terminal isocyanate group-containing urethane prepolymer and a polyol, and an acryloyl group or becomes a methacryloyl group and an acrylate-based oligomers and acrylate monomers 60 to 20 wt% having in the molecule, the acrylate monomer is acryloyl morpholine, dimethylacrylamide, diethylacrylamide, diisopropylacrylamide, and selected from isobornyl acrylate 1 or more types of acrylate-type monomers. The designable lamination sheet characterized by the above-mentioned. In the B layer, the content ratio of the solvent-free adhesive comprising the terminal isocyanate group-containing urethane prepolymer and the polyol is 50 to 80% by mass, and the acrylate oligomer having the acryloyl group or methacryloyl group in the molecule The designable laminated sheet according to claim 1, wherein the content ratio of the acrylate monomer is 50 to 20% by mass. The designable laminated sheet according to claim 1 or 2 , wherein a printed layer (D layer) is provided between the B layer and the C layer. The printing layer (D layer) includes at least two layers, that is, a D1 layer formed with a printing ink containing a bright pigment and a D2 layer formed with a printing ink containing a general coloring pigment. The designable laminated sheet according to claim 3 , wherein The C layer includes at least two layers, a C1 layer facing the B layer side and containing a bright pigment, and a C2 layer located on the opposite side to the B layer side and containing a coloring pigment having a hiding power. The designable laminated sheet according to any one of claims 1 to 4 , which is a layer to be formed. The designable laminated sheet according to claim 5 , 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 design laminated sheet covering metal plate which has the designable lamination sheet and metal plate in any one of Claims 1-6 , and the surface by the side of the said C layer of the said design lamination sheet is laminated | stacked on the metal plate. . A unit bath wall material, a unit bath ceiling material, and other unit bath members 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 . Building interior materials, such as a partition material and a general wall material, using the designable laminated sheet-coated metal plate according to claim 7 .

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