JP2005246891A - Metallic tone molded sheet and method for manufacturing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic tone molded sheet with a metallic tone hairline design which has both adhesiveness of a metal thin film layer and moldability, satisfies a reduction of lots and costs, and is suitable for a building material use with a design of calm feeling. <P>SOLUTION: The metallic tone molded sheet 10 is prepared by transferring (B) the metal thin film layer on a transparent thermoplastic resin sheet 4 through an adhesive layer 3 of a crosslinking curable resin, (A) from a transfer sheet S having a transfer layer in which the metal thin film layer 2 is the outermost surface on a hairline-like uneven releasing face of a releasing substrate 1, (C) providing a thin protective layer 5 comprising a protective sheet layer 5B with a thermoplastic resin sheet 5Bb or a crosslinking curable resin layer 5A through an adhesive resin layer 5Ba on the face of the metal thin film layer after transfer. When a light diffusing agent and a coloring agent are incorporated into the adhesive layer, the design of calm feeling can be obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a metal-like molded sheet that has a metallic hairline design and can be used for molding applications, and a method for producing the same.

  In order to give various designs to the uneven surface of an arbitrary base material, various techniques for laminating a moldable sheet made of a resin sheet on the uneven surface are known. However, when a metallic hairline design is imparted to the molded sheet, the biaxially stretched polyethylene terephthalate sheet that can form a stable hairline design on the resin sheet surface by hairline processing is poor in moldability as a molded sheet resin sheet. ,I can not use it. Therefore, as a molded sheet that solves the problem of moldability, (1) after performing a hair run on a thermoplastic resin sheet made of a moldable acrylic resin sheet, a metal thin film layer is further formed on the processed surface. In addition to the structure formed by aluminum vapor deposition, etc., and a structure in which a thermoplastic resin sheet is laminated on the surface of the metal thin film layer via an adhesive layer, a metal-like molded sheet expressing a metal-like hairline design has been proposed. (Patent Document 1).

(2) On the other hand, as a resin sheet for a molded sheet, an acrylic resin sheet having excellent moldability, transparency, weather resistance and the like can be expected to have moldability, but on the other hand, the surface of the resin sheet is higher than that of a biaxially stretched polyethylene terephthalate sheet. Since the undulation is large and the way of entering the hairline differs depending on the unevenness of the undulation, the design quality of the hairline is not stable and the finish is uneven (uneven). As a measure for achieving both formability and hairline design quality, there is a method in which a metallic hairline design is once provided as a transfer sheet, and the design is applied to the resin sheet by transfer from this transfer sheet. As a transfer sheet having a metal-like hairline design that can be used in such a method, for example, a protective layer made of a crosslinked resin or the like is provided on a releasable substrate, and the processed surface is subjected to hairline processing on the protective layer surface. A transfer sheet (see Patent Document 2, Patent Document 3, Patent Document 4, etc.), etc., in which a metal thin film layer is formed by aluminum vapor deposition, and a thermal adhesive layer is further provided thereon. According to the method of providing a metallic hairline design on a resin sheet indirectly from this transfer sheet, a thermoadhesive adhesive layer, a metal thin film layer, and a protective layer are laminated as a transfer layer on the thermoplastic resin sheet. Then, the interface between the metal thin film layer and the protective layer becomes a hairline-like uneven surface.

JP 2003-112399 A Japanese Patent Publication No.59-49919 Japanese Utility Model Publication No. 52-16803 Japanese Patent Publication No. 63-39436

The metal-like molded sheet according to (1) has already been described that the appearance quality of the hairline design is not stable due to the use of a moldable acrylic resin sheet or the like as the base material sheet. The adhesion between the processed surface and the metal thin film layer was poor, which was particularly problematic in forming applications because the sheet was stretched. In this respect, since the adhesive layer is interposed between the resin sheet and the metal thin film layer in the metal-molded sheet using the transfer sheet (2) at the time of manufacture, the adhesion problem is solved. However, on the other hand, as another problem, since a heat-adhesive adhesive is used, heat and pressure are indispensable when transferring the metal thin film layer. In addition, the transfer object is also a thermoplastic resin.
For this reason, the adhesive and the resin sheet flow due to heat and pressure during transfer, and the metal thin film layer is stretched and strained accordingly. In addition, during the forming process, the metal thin film layer is again subjected to heat and stress, and the adhesive layer also flows and deforms together. Therefore, there has been a problem that deterioration and deterioration such as cracking and whitening are likely to occur. Furthermore, as a production problem, the hairline processing surface is a protective layer surface once provided as a part of the transfer layer on the releasable substrate, so compared to the case where the hairline processing is directly performed on the releasable substrate itself. In addition, it is necessary to prepare a pre-formed layer up to the protective layer for hairline processing, and there is a problem that the degree of freedom in production planning is reduced and productivity is lowered.

  On the other hand, it cannot be said that the metallic luster of the hairline can be used at all depending on the use of building materials, but as it is, the design is too conspicuous and there is no calm feeling, so it cannot be used practically for building materials. . In this regard, in the above (1), it is disclosed that the thermoplastic resin sheet is fogged by addition of a filler or the like. In addition, since it is a resin sheet unit, it is difficult to make fine adjustments according to the design requirements.

  That is, the problem of the present invention is that the metal-formed sheet does not cause poor adhesion of the metal thin film layer, cracks, and whitening, achieves both formability and adhesion, and is compatible with small lots and reduced in cost. It is possible to provide a metal-formed sheet and a method for producing the same. Moreover, it is providing the metal-like hair Iran design of the calm feeling suitable for a building material use.

  In order to solve the above-described problems, the metal-molded sheet of the present invention is formed by sequentially laminating an adhesive layer made of a cross-linked cured resin and a metal thin film layer having a hairline-like uneven surface on one surface of a transparent thermoplastic resin sheet. Further, a thermoplastic resin sheet or a cross-linked cured resin layer via an adhesive resin layer is laminated thereon as a thin film protective layer.

  By adopting such a configuration, the metal thin film layer is laminated on the transparent thermoplastic resin sheet via an adhesive layer composed of a cross-linked cured resin layer. Insufficient adhesion between the layer and the transparent thermoplastic resin sheet, cracking of the metal thin film layer, and whitening can be avoided. Accordingly, it is possible to prevent the appearance failure of the metallic hairline design due to the poor adhesion. In addition, since a specific thin film protective layer is provided on the metal thin film layer on the adherend side of the metal-like molded sheet, the metal-like molded sheet is applied to the adherend simultaneously with the injection molding of the adherend. When applied to molding applications to be laminated (for example, injection molding simultaneous painting method including insert molding method, etc.), it is possible to prevent the metal thin film layer from being broken due to hot pressure / flow of the injection resin.

Moreover, the metal-tone molded sheet of this invention set it as the structure in which an adhesive bond layer further contains a light-diffusion agent and / or a coloring agent with respect to one of the said structures.
By adopting such a configuration, the metallic hairline design exhibited by the side surface of the transparent thermoplastic resin sheet of the metal thin film layer is added to the adhesive layer located on the viewer side of the surface, a light diffusing agent, With the colorant, the light diffusing agent is cloudy, and the colorant is colored to reduce its spectral amount, thereby enabling a design suitable for a calm building material application.

  Further, in the method for producing a metal-like molded sheet of the present invention, (A) a transfer layer having a metal thin film layer as the outermost surface is formed on the release surface of the release substrate having hairline-like irregularities on the release surface. (B) The transfer sheet is laminated and bonded to the transparent thermoplastic resin sheet through an adhesive made of a cross-linked cured resin, and after that, only the release substrate is peeled off. The metal thin film layer is transferred to the transparent thermoplastic resin sheet through the adhesive layer by the adhesive by removing and leaving the transfer layer below the metal thin film layer on the transparent thermoplastic resin sheet substrate. (C) Further, a thin film protective layer made of a thermoplastic resin sheet or a cross-linked cured resin layer via an adhesive resin layer was laminated as a thin film protective layer on the surface of the transferred metal thin film layer.

By adopting a manufacturing method having such a configuration, the metallic hairline design is imparted to the transparent thermoplastic resin sheet by transfer, so the appearance quality of the hairline design is stable and uniform, and it is transparent to the metal thin film layer. The thermoplastic resin sheet is transferred and laminated through an adhesive layer composed of a cross-linked cured resin layer, so that it is likely to be a problem particularly in molding applications, and insufficient adhesion between the metal thin film layer and the transparent thermoplastic resin sheet and the metal thin film. The problem of layer cracking and whitening can also be avoided. Therefore, appearance failure of the metallic hairline design due to the poor adhesion can be prevented, and the stability of the metallic hairline design can be obtained. In addition, the surface of the metal thin film layer formed on the transfer sheet as the outermost surface layer can be quickly covered with an adhesive made of a cross-linked cured resin to protect it from surface oxidation. It is possible to avoid problems during manufacturing such that the appearance is deteriorated and the appearance is deteriorated.
Further, since a specific thin film protective layer is provided on the metal thin film layer on the adherend side of the metal-like molded sheet, the metal-like molded sheet is laminated on the adherend simultaneously with the injection molding of the adherend. When applied to a molding application (for example, an injection molding simultaneous painting method including an insert molding method, etc.), it is possible to produce a metal-like molded sheet that can prevent a failure of the metal thin film layer due to hot pressure / flow of the injection resin. Further, the surface of the metal thin film layer on the metal-molded sheet can be protected from oxidation.
In addition, the metal thin film layer once provided as the transfer layer of the transfer sheet is provided without any other layer such as a protective layer on the releasable substrate, so that it is easy to turn and can handle small lots and cost reduction. It becomes possible.

Moreover, the manufacturing method of the metal-like shaping | molding sheet | seat of this invention was made to use the adhesive agent which contains a light-diffusion agent and / or a coloring agent further as an adhesive agent in the structure of one of the said manufacturing methods.
By adopting such a production method, the metallic hair Iran design exhibited by the side surface of the transparent thermoplastic resin sheet of the metal thin film layer is a light diffusing agent, coloring in the adhesive layer located on the viewer side of the surface. With the agent, the light diffusing agent becomes cloudy, and with the colorant, the amount of light reflected from the metal thin film layer decreases due to coloring, and it is possible to produce a metal-like molded sheet with a design suitable for a calm building material application.

(1) According to the metal-molded sheet of the present invention, it is possible to avoid problems such as insufficient adhesion between the metal thin film layer and the transparent thermoplastic resin sheet and cracking / whitening of the metal thin film layer, which are likely to be a problem particularly in molding applications. Prevents appearance defects in metallic hairline designs. In addition, the appearance quality of the hairline design can be stable and uniform. Moreover, when the metal-like molded sheet is applied to a molding application (for example, an injection molding simultaneous painting method including an insert molding method) that is laminated on the adherend at the same time as injection molding of the adherend, This prevents the metal thin film layer from being damaged by hot pressure and flow.
(2) Furthermore, if the adhesive layer includes a light diffusing agent and a colorant, a design suitable for a building material application that feels calm as a metallic hairline design is possible.

(3) According to the method for producing a metal-like molded sheet of the present invention, the stability and uniformity of the appearance quality of the metal-like hairline design, and the metal thin film layer and the transparent thermoplastic resin sheet that are particularly problematic in molding applications. Both adhesion can be achieved. Moreover, although the metal thin film layer is the outermost surface layer of the transfer sheet and becomes the outermost surface layer after transfer, both the front and back surfaces can be protected from surface oxidation by the adhesive layer made of a cross-linked cured resin and the thin film protective layer. It is possible to avoid the problem that the metallic luster feeling is lowered during production and the appearance is poor. In addition, small lots can be handled and costs can be reduced.
(4) Furthermore, if an adhesive containing a light diffusing agent or a colorant is used as an adhesive, a metal-like molded sheet capable of a design suitable for a building material application with a calm feel as a metal-like hairline design can be produced.

  The best mode for carrying out the present invention will be described below with reference to the drawings.

  First, FIG. 1 is a cross-sectional view for explaining a metal-molded sheet 10 and a method for producing the same according to the present invention. FIG. 1A shows a process of preparing a transfer sheet S in which a transfer layer having a metal thin film layer 2 as the outermost surface is formed on a release surface of a release substrate 1 having hairline-like irregularities on a release surface F. Indicates. FIG. 1 (B) shows a step of transferring the metal thin film layer 2 of the transfer sheet S to the transparent thermoplastic resin sheet 4 via an adhesive layer 3 made of a cross-linked cured resin. FIG. 1C shows a thin film protection comprising a thermoplastic resin sheet or a cross-linked cured resin layer via an adhesive resin layer on the surface of the metal thin film layer 2 transferred to the transparent thermoplastic resin sheet 4 after the transfer. The process of laminating | stacking the layer 5 and obtaining the desired metal-formation sheet | seat 10 is shown. FIG. 1 (D1) shows a mode in which the thin film protective layer 5 is formed of a cross-linked cured resin layer 5A in FIG. 1 (C), and FIG. 1 (D2) shows the thin film protective layer 5 in FIG. It is composed of a thermoplastic resin sheet 5Bb with an adhesive resin layer 5Ba interposed therebetween, and the protective sheet layer 5B of the adhesive resin layer 5Ba and the thermoplastic resin sheet 5Bb is a thin film protective layer 5. In addition, although the manufacturing method is not specifically limited as a metallic tone-forming sheet of the present invention, it can satisfy all of formability, adhesion of a metal thin film layer, and stability of a metallic tone hairline design. In view of the above, a method through the above-described steps is preferable.

  Hereinafter, the metal-tone molded sheet and the manufacturing method thereof according to the present invention will be described in order from the releasable substrate 1 for each layer.

[Transfer sheet]
As a method for producing a metal-molded sheet, the transfer sheet S used in the present invention is such that the release substrate 1 having a release surface F having hairline irregularities as shown in FIG. The metal thin film layer 2 is laminated directly on the mold surface as a transfer layer, and this metal thin film layer 2 is the outermost surface of the transfer layer (in the transfer sheet).

(Releasable substrate)
The releasable substrate 1 is a constituent layer of a transfer sheet used for forming the metal thin film layer 2 having hairline-like irregularities on the transparent thermoplastic resin sheet 4 that is a constituent layer of the metal-molded sheet 10 by transfer. is there. The releasable base material is not particularly limited as long as the release surface is a hair run-like uneven surface, and a conventionally known one can be used and may be appropriately selected. Moreover, the moldability is not necessary for this releasable substrate. Accordingly, it is possible to use one that takes into consideration suitability for hairline processing without considering formability. Among them, a typical one is a biaxially stretched polyester resin sheet made of polyethylene terephthalate, polyethylene naphthalate, or the like, and is typically a biaxially stretched polyethylene terephthalate sheet. Biaxially stretched polyethylene terephthalate sheet has less surface undulation (good flatness) and realizes hairline design with hairline-like irregularities formed on the substrate surface by hairline processing with stable and uniform (no unevenness) quality It is a preferable base material in terms of the capability and cost. In addition, the biaxially stretched polyethylene terephthalate sheet is a preferable base material in that it can be releasable from the metal thin film layer without providing an additional release layer in order to impart releasability to the base material surface. It is. In addition, the thickness of a releasable base material does not have a restriction | limiting in particular, For example, it is about 20-100 micrometers.

  The releasability is easily obtained even when the resin thin film layer is formed by vacuum deposition of a metal such as aluminum. However, if the releasability is insufficient and its improvement is necessary, it is appropriate. In addition, a known release layer made of a resin layer such as an acrylic resin, an alkyd resin, or a melamine resin may be formed as a releasable substrate by coating or the like.

In addition, what is necessary is just to give a well-known hairline process in order to make a mold release surface into a hairline-like uneven surface. In the case of a structure having a release layer, the surface irregularities shaped by hairline processing can be imparted to the metal thin film layer as it is by going to the surface of the release layer.
The hairline shape may be appropriately selected from known ones, and may be a straight line (parallel line segment group) or a curve group shape formed by so-called spin processing or the like. Moreover, the concave part width, convex part width, and concave part depth (convex part height) of the hairline are usually about 10 to 300 μm (however, the depth or height is less than the thickness of the releasable substrate). And).

[Metal thin film layer]
The metal thin film layer 2 is formed by a known thin film forming method such as vacuum vapor deposition, sputter vapor deposition, ion beam vapor deposition, plasma vapor deposition, or plating using a metal such as aluminum, chromium, indium, tin, gold, silver, or copper. Just do it. The metal thin film layer may be a combination of these materials and methods. The metal thin film layer is usually provided on the entire surface, but may be partially provided in a pattern. In addition, when applying a metal-formed sheet to an application where the elongation (squeezing) of the sheet is large, tin and indium are more ductile than the commonly used aluminum among the above various metals. The metal is a preferable metal in that it can improve a defect in which a fine crack enters the metal thin film layer at a portion where the elongation is large, resulting in poor appearance.

  Further, as a thin film forming method, in general, sputter deposition has better adhesion to the surface to be formed than vacuum deposition, but in the manufacturing method according to the present invention, a metal thin film layer is formed as a transfer sheet, and finally, In relation to transfer to a transparent transparent thermoplastic resin sheet, the adhesion of the metal thin film layer to the release surface (formation surface) of the release sheet of the transfer sheet may be as long as it does not hinder the transfer. unnecessary. Therefore, it can be said that the vacuum deposition method is a preferable method for forming a thin film. In addition, since the manufacturing method is not limited as the metal-tone molded sheet of the present invention, the metal thin film layer 2 may be formed directly on the surface of the transparent thermoplastic resin sheet 4 by a thin film forming method. become. However, in this case, the adhesion tends to be insufficient when forming by a vacuum vapor deposition method that can easily obtain a rich metallic luster. Therefore, even with the vacuum vapor deposition method, the problem of insufficient adhesion is solved by the method of forming the transparent thermoplastic resin sheet via the adhesive sheet of the cross-linked cured resin via the transfer sheet as described above.

  In addition, the thickness of the metal thin film layer should just be a thickness which can obtain a metallic luster feeling, and when too thick, the moldability (stretchability) of metal thin film layer itself will worsen. Further, the metal thin film layer is preferably formed by transfer from a transfer sheet. In the present invention, the back side of the transparent thermoplastic resin sheet (the surface far from the observer side) is used during transfer. In view of the lamination of the metal thin film layer, the observation surface of the metal thin film layer viewed by the observer is the metal thin film layer surface farther from the releasable substrate 1 on the transfer sheet S. Therefore, when the metal thin film layer is formed by the thin film forming method on the release surface of the releasable substrate that has become the hair-Iranian uneven surface, the larger the thickness, the more the hair-Iranian unevenness on the observation surface. If it is dull and extremely thick, it flattens. Therefore, the thickness of the metal thin film layer may be appropriately determined in consideration of these points and the like, but specifically, for example, about 100 to 2000 mm.

[Transfer process]
In the transfer sheet S as described above, since the outermost surface of the transfer layer is the metal thin film layer 2, the adhesive layer 3 is interposed between them in the step of bonding and transferring to the transparent thermoplastic resin sheet 4. Do it in the form. In addition, the surface to which the adhesive serving as the adhesive layer is applied may be either the metal thin film layer surface of the transfer sheet, the transparent thermoplastic resin sheet surface that is the transfer target, or both of these surfaces.

By the way, the surface of the metal thin film layer in the transfer sheet is exposed, and the exposed surface finally becomes an observation surface for displaying the metal-like hairline design in the metal-like molded sheet. In the meantime, it is preferable to bring the adhesive into contact with the surface of the metal thin film layer before the metal thin film layer is oxidized and the appearance of the metallic luster is changed. For this purpose, the transfer sheet is manufactured as a continuous belt-like roll whose metal thin film layer surface can be protected from oxidation by the sheet itself, and at the time of transfer, it is unwound as soon as possible after unwinding from this roll (for example, in-line bonding) If the adhesive is applied directly to the metal thin film layer surface of the transfer sheet, or the adhesive applied to the transparent thermoplastic resin sheet side is brought into contact with the metal thin film layer surface of the transfer sheet, etc. good.
The oxidation of the metal thin film layer may proceed as long as it does not lead to the deterioration of the metallic gloss on the observation side. In this sense, the contact of the adhesive with the metal thin film layer surface is substantially It is that it is not oxidized. This also applies to the oxidation of the exposed surface of the metal thin film layer after transfer.

  In addition, without directly contacting the adhesive to the transfer sheet (the metal thin film layer surface), a primer agent may be applied to the metal thin film layer surface of the transfer sheet to protect the metal thin film layer surface from oxidation. good. The adhesion of the adhesive can be enhanced by the primer agent. In addition, what is necessary is just to use well-known things, such as coupling agent systems, such as a silane coupling agent, and resin systems, such as a urethane resin type, as a primer agent.

  Further, it is preferable to consider the oxidation of the metal thin film layer even after the transfer is completed. That is, in the transfer sheet used in the present invention, the outermost surface after transfer is also the metal thin film layer surface itself, so that even if it is the back side to the observer, the thin metal thin film layer is oxidized by oxidation from the back side. This is because the appearance of the observation surface on the front side may be altered. For this reason, from the viewpoint of preventing oxidation of the metal thin film layer after transfer, it is preferable that a thin film protective layer described later is applied to the surface of the metal thin film layer as soon as possible after transfer (for example, in-line). Alternatively, as before the transfer, a primer agent may be applied before the thin film protective layer is formed.

[Adhesive / Adhesive layer]
As the adhesive used for the adhesive layer 3 for laminating and laminating the metal thin film layer 2 and the transparent thermoplastic resin sheet 4, those having transparency (more than the extent that the metal thin film layer can be seen through) and a desired adhesive strength are used. Choose. The adhesive can be bonded even with an adhesive made of a thermoplastic resin. However, in view of adhesion when using a metal-molded sheet, a cross-linked cured resin is preferable in terms of improving the adhesion. In addition, the completion of the cross-linking curing is performed after the metal thin film layer and the transparent thermoplastic resin sheet are both in contact with the adhesive layer (for example, after the transfer after the release of the releasable substrate). This is preferable.
As the cross-linked cured resin, a conventionally known resin such as a urethane resin or an acrylic resin may be appropriately selected. Moreover, as the cross-linked curable resin, there are a thermosetting type, a room temperature curable type, an ionizing radiation (electron beam, ultraviolet ray, etc.) curable type, etc. in the reaction temperature form, and a two-part curable type, one-part curable type in the resin mixed form. There are types and the like, but these may be appropriate. For example, a two-component curable adhesive at room temperature. In the case of a metal-like molded sheet, when the adhesive or the transparent thermoplastic resin sheet softens and flows by heating, the metal thin film layer cracks and whitens, and the transparent thermoplastic resin sheet is heated to impart formability. From the viewpoint of reaction temperature, the room temperature curing type is preferred from the viewpoint of reaction temperature. In addition, normal temperature here is 20 ° C. ± 15 ° C. (temperature range of 5 to 35 ° C. (JIS Z8703 “standard state of test place”)). Specific examples of such an adhesive include, for example, an adhesive made of a two-component curable urethane resin and a room temperature curable urethane resin.

  In the case of a two-component curable urethane resin, typically, for example, various polyols such as acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and urethane polyol are used as the main agent. Examples of the crosslinking agent include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tri-isocyanate. Polyisocyanates such as aliphatic (or alicyclic) isocyanates such as diisocyanates and hydrogenated diphenylmethane diisocyanates, or adducts or multimers of these polyisocyanates (for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers) Etc.) is used.

In the case of a one-component curable urethane resin, a prepolymer having a isocyanate group as a reactive group by reacting a diisocyanate or the like with the hydroxyl group of the various polyols is typically used. . This isocyanate group can be crosslinked and cured at room temperature by moisture in the air.
Alternatively, so-called blocked isocyanate obtained by blocking an isocyanate group of polyisocyanate as a crosslinking agent with alcohol or the like can be used, but in this case, heating is required for releasing the block and reacting the isocyanate.

Moreover, since the adhesive layer 3 is a layer on the observer side with respect to the surface of the metal thin film layer 2 that reveals the metallic hairline design, the adhesive layer 3 has a light diffusing property. An adhesive containing a colorant, a colorant, or both may be used. As a result, the metallic luster of the metallic hairline design can be pressed (by the light diffusing agent) or colored (by the colorant). As the light diffusing agent and the colorant, known ones may be appropriately selected and used. For example, as the light diffusing agent, inorganic fine particles such as silica, alumina, calcium carbonate, and barium carbonate, and resin bead particles such as acrylic resin, polystyrene, and urea resin are used. The average particle diameter of the light diffusing agent is usually about 1 to 10 μm. Examples of the colorant include titanium white, zinc white, carbon black, iron black, dial, cadmium red, ultramarine, cobalt blue, yellow lead, titanium yellow and other inorganic pigments, phthalocyanine blue, indanthrene blue, Organic pigments such as indolinone yellow, quinacridone red, perylene red, or dyes are used.
In addition, when light resistance is required for exterior applications, etc., known additives such as UV stabilizers, light stabilizers such as radical scavengers, antioxidants, etc. are appropriately included in the adhesive layer 3 as necessary. It is good to add.

  In order to laminate the metal thin film layer by transfer from the transfer sheet to the transparent thermoplastic resin sheet using the adhesive as described above, for example, the transfer sheet and the transparent thermoplastic resin sheet are laminated by a so-called dry lamination method. Then, the release substrate of the transfer sheet may be peeled off. At that time, if it is necessary to dry the solvent of the adhesive and you do not want to apply the heat to the transparent thermoplastic resin sheet side, apply the adhesive to the transfer sheet side, dry the solvent, and laminate it. Heating can be avoided and deformation of the transparent thermoplastic resin sheet due to heat can be prevented.

[Transparent thermoplastic resin sheet]
The transparent thermoplastic resin sheet 4 is not particularly limited as long as it is a transparent and moldable resin sheet made of a thermoplastic resin, and may be appropriately selected from conventionally known ones according to the intended use. Examples of the thermoplastic resin of the transparent thermoplastic resin sheet include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, and olefin-based thermoplastic elastomer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid- Polyester resins such as isophthalic acid-ethylene glycol copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester-based thermal plastic elastomer, polyamide resin such as nylon 6, nylon 9, nylon 6,6 , Fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, poly (vinylidene fluoride), ethylene-tetrafluoroethylene copolymer, poly (tetrafluoroethylene), acrylic resin, polyvinyl chloride Polystyrene, polycarbonate resins.

  Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and ethyl (meth) acrylate-butyl. Resins such as a (meth) acrylate copolymer and a methyl (meth) acrylate-styrene copolymer (however, (meth) acrylate means acrylate or methacrylate) are used alone or in a mixture of two or more.

  The transparent thermoplastic resin sheet may be colored as long as it is transparent. Coloring may be performed using a known colorant as appropriate. Further, if it is transparent, it may be translucent. The translucent resin may be semi-transparent or a light diffusing agent may be added. However, in terms of cost and productivity, these are not added without adding a colorant or a light diffusing agent. When using the adhesive layer 3, it is preferable to use it for the adhesive layer 3 in terms of productivity because it is easy to deal with a small lot.

  In addition, an ink layer containing a light diffusing agent on the side opposite to the metal thin film layer 2 forming side of the transparent thermoplastic resin sheet 4 (the uppermost surface of the metal-like molded sheet 10 in FIGS. 1 and 2). Alternatively, a colored transparent ink layer containing a colorant may be formed. The light diffusing agent and the colorant can be selected from those similar to those exemplified for the adhesive layer. In addition, the binder resin of these inks may be selected from among known materials or in consideration of adhesion to a transparent thermoplastic resin sheet and printability. Typical examples include acrylic resins, vinyl chloride-vinyl acetate copolymers, chlorinated polyolefin resins, urethane resins, rubber resins, and the like. Moreover, the thickness of these ink layers shall be about 1-10 micrometers.

In addition, when light resistance is required for exterior use or the like, a known additive such as a UV stabilizer, a light stabilizer such as a radical scavenger, or an antioxidant is appropriately added to the adhesive layer 3 as necessary. It is good to add.
The thickness of the transparent thermoplastic resin sheet is not particularly limited and depends on the application, but is usually about 50 to 500 μm.

[Thin film protective layer]
The thin film protective layer 5 protects the non-observed surface side of the metal thin film layer from oxidation. In particular, when a metal-like molded sheet is applied to a molding application (for example, an injection molding simultaneous painting method including an insert molding method) simultaneously with injection molding of an article to be an adherend, and the like. In addition, it is provided to prevent a problem that the metal thin film layer is broken due to the thermal pressure and flow of the injection resin, for example, when the injection resin directly contacts the metal thin film layer. The place where the breakage is likely to appear is a portion where heat / pressure and flow are large, particularly in the vicinity of the gate portion where the resin flows into the mold.

  As described above, the thin film protective layer 5 is preferably provided as soon as possible (for example, provided inline) after the metal thin film layer is transferred to the transparent thermoplastic resin sheet for the purpose of preventing the oxidation of the metal thin film layer. In this respect, the thin film protective layer 5 is not particularly limited as long as it can cover the metal thin film layer, and may be a coating film of a thermoplastic resin. However, in order to protect from the injection resin at the time of molding of the metal-like molded sheet as described above, it is necessary to have something that can withstand the heat pressure and flow. When compared with a general resin sheet having a thickness of 100 μm or the like, the thin film protective layer is provided as a thin film protective layer). In this respect, it is preferable to provide a crosslinked cured resin layer made of a crosslinked cured resin.

As the cross-linked cured resin used for the cross-linked cured resin layer, in order to prevent cracking and whitening of the metal thin film layer, and to prevent the transparent thermoplastic resin sheet having moldability from being deformed by heat, a room-temperature curable resin is used. Also in the case of resin or heating and crosslinking and curing, a resin that is crosslinked at a temperature as low as possible is preferable. As such a resin, the resin used for the adhesive layer between the metal thin film layer and the transparent thermoplastic resin sheet can be used. That is, for example, a cross-linked cured resin such as a urethane resin or an acrylic resin.
Such a cross-linked cured resin layer may be formed by a known coating method such as gravure coating. The thickness of the cross-linked cured resin layer may be an appropriate thickness depending on the type of the injection resin. The thickness is usually about 10 to 40 μm.

  Further, in order to protect the metal thin film layer against the thermal pressure and flow of the injection resin, even if it is a thermoplastic resin layer, if it is as thick as 0.5 mm, 1 mm, etc., the thermoplastic resin layer Even if the film is deformed to some extent, it can prevent the metal thin film layer from being destroyed. In order to prevent the transparent thermoplastic resin sheet from being heated and deformed, such a thick thermoplastic resin layer is formed by avoiding the melt coating method and laminating the formed thermoplastic resin sheet with an adhesive. preferable. The adhesive (adhesive resin layer) used at this time may be either a cross-linked cured resin or a thermoplastic resin. However, since the thermoplastic resin sheet is protected from the injection resin, the heat resistance may be low. In terms of not adversely affecting the moldability, thermoplastic resins are more advantageous than cross-linked cured resins. On the other hand, the cross-linked cured resin tends to be more advantageous in terms of adhesion. Here, FIG. 1 (D2) shows a configuration in which a thermoplastic resin sheet 5Bb is laminated on the surface of the metal thin film layer 2 as a thin film protective layer 5 via an adhesive resin layer 5Ba. The adhesive resin layer 5Ba and the thermoplastic resin sheet 5Bb form the thin film protective layer 5 as the protective sheet layer 5B.

  The thermoplastic resin sheet 5Bb is not particularly limited as long as it has moldability and can withstand the heat pressure and flow according to the type of the injection resin, and the one according to the application should be used. It ’s fine. Further, since the thermoplastic resin sheet 5Bb is not on the observer side like the transparent thermoplastic resin sheet 4, transparency is not essential. Examples of the resin of the thermoplastic resin sheet 5Bb include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, and olefin-based thermoplastic elastomer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid. -Polyester resins such as isophthalic acid-ethylene glycol copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester-based thermal plastic elastomer, polyamides such as nylon 6, nylon 9, nylon 6,6, etc. Resin, polyvinyl fluoride, polyvinylidene fluoride, polytrivinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, and other fluorine-based resins, acrylic resin, polyvinyl chloride , Polystyrene, polycarbonate resin, ABS (acrylonitrile - butadiene - styrene copolymer) resins, and the like.

Further, the thermoplastic resin resin sheet 5Bb may be concealing or may be colored. For example, if it is concealing, such as black, white, etc., the appearance color of the adherend of the metal-like molded sheet is concealed, and even if a fine crack occurs in the portion where the metal thin film layer is particularly elongated, This prevents the appearance color of the adherend from being mixed with the metallic luster. This is because, if the color is dark such as black, the light from the metal-like molded sheet is mainly reflected light from the metal thin film layer.
In addition, although the thickness of thermoplastic resin sheet 5Bb depends on a use, it is about 50-500 micrometers normally.

The protective sheet layer may be laminated with the thermoplastic resin sheet 5Bb on the surface of the metal thin film layer 2 on the transparent thermoplastic resin sheet 3 through an adhesive made of a thermoplastic resin or a cross-linked cured resin.
As the adhesive, in the case of a thermoplastic resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, an acrylic resin, a thermoplastic polyester resin, a thermoplastic urethane resin, a polyamide resin, etc., and a cross-linked cured resin In this case, conventionally known adhesives such as acrylic resins and urethane resins are appropriately used.

  Moreover, when the back surface exposed surface of the thermoplastic resin sheet 5Bb is poor in adhesiveness with the injection resin, known means such as primer layer formation and back surface adhesive layer formation may be applied to the back surface. For the back surface adhesive layer, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer, chlorinated polyolefin resin, urethane resin, rubber resin, or the like is used.

[Uses of metal-like molded sheets]
The use of the metal-formed sheet according to the present invention is an application in which the metal-formed sheet is preferably stretched, and even if it is not stretched, it is laminated on the adherend simultaneously with the molding of the adherend. It is. As a specific example of such an application, a so-called injection molding simultaneous painting method (see Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc.) is typically mentioned. In addition, as a method for simultaneous painting with injection molding, a method in which a (metal-like) molded sheet is stretched (molded) and laminated on the surface of a molded article, which is an adherend, is representative in that form. A form of insert molding method in which a molded sheet is loaded into an injection mold, and the molded sheet is not stretched, and is laminated on the surface of the molded product simultaneously with the molding of the resin molded product as an adherend. Is also included.
Alternatively, it may be used in a vacuum forming / laminating method, or a vacuum forming method (including vacuum / pressure forming) in which a molded sheet itself formed without being laminated on an adherend is the final object. In addition, as described in Japanese Patent Publication No. 56-45768 (overlay method), Japanese Patent Publication No. 60-58014 (vacuum press method), etc., a vacuum forming lamination method is used for a three-dimensional substrate such as a molded product. This is a method in which a molded sheet is opposed to or placed on the surface, and the molded sheet is laminated on the surface of the base material by a pressure difference due to the combined use of at least vacuum suction from the base material side and further appropriate pressure-pressing from the molded sheet side.
Among these uses, the use that can remarkably enjoy the protective effect of the thin film protective layer provided on the back surface side of the metal thin film layer as the effect of the metallic tone forming sheet according to the present invention is the simultaneous injection molding method.

In addition, in the injection molding simultaneous painting method, there are various sheet molding modes of the molded sheet to be used. All of these are applicable to the metal-molded sheet of the present invention. That is, (A) a form with sheet molding and (B) a form without sheet molding. In the former form (A) with sheet molding, (A1) offline preforming form in which the sheet molding is preformed outside the injection mold, (A2) sheet molding, vacuum molding mold (including the injection mold) In-line pre-molding form that is pre-molded in the mold prior to resin injection and also used as vacuum / pneumatic molding) (A3) Pre-molding is not performed, but sheet molding is performed using the injection mold as the molding mold. It is a form molded by the hot pressure of the injection resin. In addition, in the forms (A1) and (A2), an incomplete molded shape in detail may be finally molded by (A3). Also, so-called insert molding corresponds to (A3) and (B).
In addition, among these sheet molding forms, the effect of improving the adhesion of the metal thin film layer to the transparent thermoplastic resin sheet can be remarkably enjoyed as the effect of the metal-like molded sheet of the present invention. It is a form.

  Here, the so-called injection molding simultaneous painting method will be outlined with reference to the conceptual diagram of FIG. In addition, the form demonstrated here is a case where a metal-like decorative sheet is applied to the form of the in-line preforming which performs the vacuum forming process on the injection mold for the sheet forming of (A2).

  First, as shown in FIG. 2 (A), as an injection mold, a metal Ma molded sheet having a mold Ma having a runner communicating with an injection nozzle and a gate and a suction hole 41 on the cavity surface. A pair of molds of a mold Mb that also serves as a preforming mold for the vacuum forming process is used. These molds are made of metal such as iron or ceramics. In the mold open state, the metallic tone forming sheet 10 is supplied between the two molds Ma and Mb, and the metallic tone forming sheet 10 is fixed to the die Mb by pressing it with a sheet clamp 42 having a frame shape in plan view. At this time, of course, the back surface side of the (metal-like) molded sheet on which the thin film protective layer is provided on the metal thin film layer side (relative to the transparent thermoplastic resin sheet) is the injection resin side on the right side of the drawing. . Next, as shown in FIG. 2B, the heater 43 that has been retracted at the retracted position outside the mold (in the drawing, above the mold) is appropriately moved and inserted between both molds. Soften by heating. The heating is, for example, non-contact radiation heating, but may be conduction heating by contact. And it sucks from a suction hole and vacuum-forms, A metal tone-forming sheet | seat is preformed along the cavity surface of type | mold Mb. Next, the heater is retracted from between both molds, and both molds are clamped as shown in FIG. 2C, and a cavity formed by both molds is filled with a resin in a fluid state such as a heat-melted state. And after resin solidifies by cooling etc., a mold is opened and a molding is taken out. Then, if the unnecessary part of the metal-like molded sheet is appropriately trimmed, the metal-like molded sheet is laminated on the surface of the resin molded product, and a molded product with a picture with a metal-like hairline design is obtained.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the adhesion evaluation of the metal thin film layer was evaluated by visually observing the metallic luster of the molded product with a metallic hairline design after applying the metallic molded sheet to the injection molding simultaneous painting method. Those that are not recognized as good. In addition, the formability was good if the metal-like molded sheet sufficiently followed the surface shape of the molded product. Also, the presence or absence of damage to the metallic luster of the gate portion was visually observed, and it was satisfactory if there was no damage.

[Example 1]
A single-sided, biaxially stretched polyethylene terephthalate sheet having a thickness of 25 μm is subjected to hairline processing, and a sheet having the processed surface as a release surface is used as a releasable substrate 1 directly to the release surface. Then, a metal thin film layer 2 having a thickness of 450 mm was formed by vacuum evaporation of tin, and a transfer sheet S wound up on a roll was prepared [see FIG. 1 (A)].

  Next, the transfer sheet S was unwound from the roll, and 10 parts by mass of a hexamethylene diisocyanate-based cross-linking agent was blended on the surface of the metal thin film layer as a cross-linked cured resin with respect to 100 parts by mass of the polyester polyol main component. After applying an adhesive using a liquid curing type room temperature curing type urethane resin, on one side of the transparent thermoplastic resin sheet 4 made of a continuous belt-shaped acrylic resin sheet with a thickness of 125 μm unwound from another roll, After laminating and bonding by the dry lamination method through the adhesive layer 3 by the adhesive, the release base material of the transfer sheet is peeled off in-line, and the transparent thermoplastic resin sheet 4 / adhesive layer 3 / metal The laminated sheet consisting of the thin film layer 2 was once wound up into a roll [see FIG. 1 (B)]. The thickness of the adhesive layer 3 is 5 μm.

  Next, the laminated sheet was unwound from a roll, and 10 parts by mass of a hexamethylene diisocyanate-based crosslinking agent was blended on the surface of the metal thin film layer as the thin film protective layer 5 with respect to 100 parts by mass of the main component of polyester polyol. A liquid-curable and room-temperature-curing type urethane resin is applied to form a 5 μm-thick cross-linked cured resin layer 5A, on which a vinyl chloride-vinyl acetate copolymer and an acrylic resin are formed. After coating a coating solution made of a mixed resin having a weight ratio of 1: 1, a back adhesive layer (not shown) having a thickness of 3 μm was coated and formed, and then wound into a roll. Thereafter, curing was performed at room temperature (30 ° C.) for 1 week to complete the curing of the cross-linked cured resin of the adhesive layer and the cross-linked cured resin layer, thereby obtaining a desired metal-molded sheet 10 [FIG. 1 (D1) reference〕.

Next, the molded article simultaneously with the molding of the resin molded article made of the ABS resin by the injection molding simultaneous painting method in a form in which the metal-like molded sheet obtained above is preformed (vacuum molding) in an injection mold. A three-dimensional surface was laminated to obtain a molded article with a picture. The molding conditions are a sheet heating temperature of 120 ° C., an injection resin temperature of 240 ° C., and an injection mold temperature of 60 ° C.
When the metal-like hairline design of the obtained molded article was visually observed, no whitening of the metallic luster and cracks in the metal thin film layer were observed even in the sheet-formed part, and the moldability and adhesion were good. . Also, no metallic luster damage was observed at the gate portion.

[Example 2]
In Example 1, instead of the cross-linked cured resin layer 5A used as the thin film protective layer 5, as a protective sheet layer 5B, a thermoplastic resin sheet 5Bb made of a black ABS resin sheet having a thickness of 300 μm is added to a polyester polyol main ingredient 100. A coating liquid composed of a two-component curable urethane resin containing 10 parts by mass of hexamethylene diisocyanate-based crosslinking agent in mass parts is applied, and a metal thin film is formed through the adhesive resin layer 5Ba by the coating liquid. A metal-molded sheet was produced in the same manner as in Example 1 except that the layer 2 was laminated on the back surface.

And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The resulting molded article with picture did not show any whitening of metallic luster or cracks in the metal thin film layer even in the sheet-molded part, and was excellent in moldability and adhesion. Also, no metallic luster damage was observed at the gate portion.

Example 3
In Example 1, except that 10 parts by mass of acrylic resin beads having an average particle size of 3 μm as a light diffusing agent was added to the resin of the adhesive layer 3 made of a cross-linked cured resin with respect to 100 parts by mass of the resin. In the same manner as in Example 1, a metal-like molded sheet was produced.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The resulting molded article with picture did not show any whitening of metallic luster or cracks in the metal thin film layer even in the sheet-molded part, and was excellent in moldability and adhesion. Also, no metallic luster damage was observed at the gate portion. In addition, the metallic luster was slightly weakened and calmed, making it more suitable for building materials.

Example 4
In Example 1, 0.5 parts by mass of phthalocyanine blue as a colorant with respect to 100 parts by mass of the resin was added to the resin of the adhesive layer 3 made of a cross-linked cured resin, so that the adhesive layer was thin. A metal-molded sheet was prepared in the same manner as in Example 1 except that it was colored blue.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The resulting molded article with picture did not show any whitening of metallic luster or cracks in the metal thin film layer even in the sheet-molded part, and was excellent in moldability and adhesion. Also, no metallic luster damage was observed at the gate portion. In addition, the metallic luster was bluish and calm, making it more suitable for building materials.

Example 5
In Example 1, 10 parts by mass of acrylic resin beads having an average particle diameter of 3 μm as a light diffusing agent are added to the resin of the adhesive layer 3 made of a cross-linked cured resin with respect to 100 parts by mass of the resin, and are colored. A metal-like molded sheet was prepared in the same manner as in Example 1 except that 0.5 parts by mass of phthalocyanine blue as an agent was added to 100 parts by mass of the resin and the adhesive layer was colored light blue.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The resulting molded article with picture did not show any whitening of metallic luster or cracks in the metal thin film layer even in the sheet-molded part, and was excellent in moldability and adhesion. Also, no metallic luster damage was observed at the gate portion. In addition, the metallic luster was slightly weakened and bluish, and became calm and suitable for building materials.

Example 6
In Example 2, instead of the black ABS resin sheet having a thickness of 300 μm used for the thermoplastic resin sheet 5Bb, a polyester resin sheet having a three-layer structure having a white thickness of 200 μm was used. In the same manner, a metal-like molded sheet was produced. The polyester resin sheet is made of a low crystalline polyester resin having a center layer of 150 μm and made of a mixture of polyethylene terephthalate and polybutylene terephthalate. The front and back of the polyester resin sheet are made of terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer. A resin sheet having a structure sandwiched between 25 μm-thick surface resin layers and laminated simultaneously by a three-layer coextrusion method.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The resulting molded article with picture did not show any whitening of metallic luster or cracks in the metal thin film layer even in the sheet-molded part, and was excellent in moldability and adhesion. Also, no metallic luster damage was observed at the gate portion.

Example 7
The metal-like molded sheet itself is the same as in Example 2, but for application to the molding method, it is loaded at a position where the sheet is not molded in the injection mold and a position where it hits the gate portion, and in a form without sheet molding. By a simultaneous injection molding method (so-called insert molding), a resin molded product made of ABS resin was molded and laminated on the flat surface of the molded product to obtain a picture molded product. The molding conditions are an injection resin temperature of 240 ° C. and an injection mold temperature of 60 ° C.
The resulting molded article with a picture had good adhesion without whitening of metallic luster or cracking of the metal thin film layer even in the portion corresponding to the gate portion. Also, no metallic luster damage was observed at the gate portion.

[Comparative Example 1]
In Example 1, instead of the cross-linked cured resin layer 5A used as the thin film protective layer 5, a coating solution made of a mixed resin of 1: 1 weight ratio of vinyl chloride-vinyl acetate copolymer and acrylic resin was applied. Then, a metal-molded sheet was prepared in the same manner as in Example 1 except that a 5 μm-thick thermoplastic resin coating layer was formed and the back surface adhesive layer was omitted.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The obtained molded article with a picture had a white portion of metallic luster and cracks in the metal thin film layer in the sheet-formed portion, and had good formability but poor adhesion. Moreover, the metallic luster damage was seen in the gate part.

[Comparative Example 2]
In Example 1, a 1: 1 weight ratio mixed resin of vinyl chloride-vinyl acetate copolymer and acrylic resin is used as the resin of the adhesive layer 3 to which the cross-linked cured resin is to be used to form the thin film protective layer 5. Instead of the cross-linked cured resin layer 5A, a 5 μm-thick thermoplastic resin coating layer made of a 1: 1 weight ratio mixed resin of vinyl chloride-vinyl acetate copolymer and acrylic resin is formed. A metal-molded sheet was prepared in the same manner as in Example 1 except that the curing of the crosslinked cured resin was omitted and the curing of the crosslinked cured resin was omitted.
And this metal-tone molded sheet was applied to the form of the injection-molding simultaneous painting method similar to Example 1, and the painting molded article was produced.
The obtained molded article with a picture had a white portion of metallic luster and cracks in the metal thin film layer in the sheet-formed portion, and had good formability but poor adhesion. Moreover, the metallic luster damage was seen in the gate part.

Sectional drawing explaining the metal tone-forming sheet | seat and its manufacturing method by this invention. The conceptual diagram explaining the injection molding simultaneous painting method by the one form.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Releasable base material 2 Metal thin film layer 3 Adhesive layer 4 Transparent thermoplastic resin sheet 5 Thin film protective layer 5A Cross-linked cured resin layer 5B Protective sheet layer 5Ba Adhesive resin layer 5Bb Thermoplastic resin sheet 10 Metal tone molding sheet 41 Suction hole 42 Sheet Clamp 43 Heater F Mold Release Surface Ma Injection Mold (Male)
Mb injection mold (female)
S transfer sheet

Claims (4)

On one surface of the transparent thermoplastic resin sheet, an adhesive layer composed of a cross-linked cured resin and a metal thin film layer having a hairline-like uneven surface are sequentially laminated, and further, a thin film protective layer is provided thereon via an adhesive resin layer. A metal-like molded sheet on which a thermoplastic resin sheet or a cross-linked cured resin layer is laminated. The metal tone-formed sheet according to claim 1, wherein the adhesive layer contains a light diffusing agent and / or a colorant. (A) Prepare a transfer sheet on which a transfer layer having a metal thin film layer as the outermost surface is formed on the release surface of the releasable substrate having hairline-like irregularities on the release surface,
(B) The transfer sheet is laminated and bonded to a transparent thermoplastic resin sheet via an adhesive made of a cross-linked cured resin, and after that, only the releasable base material is peeled and removed to form a metal thin film layer. By transferring the following transfer layer on the transparent thermoplastic resin sheet substrate, the metal thin film layer is transferred to the transparent thermoplastic resin sheet via the adhesive layer by the adhesive,
(C) Furthermore, a metal-molded sheet manufactured by laminating a thin film protective layer made of a thermoplastic resin sheet or a cross-linked cured resin layer via an adhesive resin layer as a thin film protective layer on the surface of the transferred metal thin film layer. Method. The manufacturing method of the metal-form molding sheet | seat of Claim 3 using the adhesive agent containing a light-diffusion agent and / or a coloring agent as an adhesive agent.

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