JP2011140127A - Decorative article with partially transparent metallic thin coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative article with a metallic thin coating film, which does not have a clearly defined level difference formed between a pictorial pattern part and a pictorial pattern background part, as a decorative layer, and a method for manufacturing this decorative article in a simple operating way. <P>SOLUTION: This decorative article with the decorative layer is fixed to an object to be decorated. The decorative layer has a metallic thin coating film which includes a transparent part as a pictorial pattern background or a pictorial pattern. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an article decorated with a metallic luster pattern, and more particularly to an article decorated with a decoration layer having a partially transparent metal thin film.

  A method for protecting or decorating the surface of an article such as a plastic part or an exterior article using a decorative sheet has been known. For example, in Patent Document 1, a decorative sheet provided with a decorative layer on one side of a base sheet that is a support, and this decorative sheet is inserted into an injection mold, and in-mold injection molding is performed. And obtaining a decorated injection-molded body (simultaneous injection molding) is described.

  The decorative layer is generally a laminate in which a pattern, a colorant, an adhesive, and the like are laminated in layers. After being attached to the surface of the article, the decorative layer forms a coating having a decorative function or a protective function. Layers such as a pattern and a colorant are formed by sequentially printing or coating a printing ink such as gravure ink or a coating on a base sheet.

  In order to give a metallic luster appearance to the surface of an article as a kind of decoration, a metal thin film may be used for the decorative layer. In particular, when a metallic luster pattern is required, the metal thin film is formed in a pattern on a part of the sheet surface. That is, the metal thin film itself is formed in a planar manner, so that the metal thin film corresponding to the pattern background or the pattern is removed.

  In Patent Literature 2, a mask layer of a water-soluble resin is formed in advance on a background portion of a pattern, and after depositing a metal on the entire surface of the sheet surface, the mask layer and the metal thin film thereon are washed and removed. Thus, a method for forming a metal thin film into a shape corresponding to a pattern is described.

  However, the metal thin film has poor toughness, and may be damaged in the washing process or corroded by residual moisture. In addition, this method has many steps and is complicated in operation, and there is a limit to improving the accuracy of the pattern.

  In Patent Document 3, after depositing a metal on the outer surface of an article, the deposited metal layer is irradiated with laser light to be heated, decomposed, evaporated, sublimated, and partially removed to form a metal thin film. A method of forming a picture is described.

  However, heat transpiration using laser light tends to produce residues, and a process for removing them is required. Further, when the laser beam used in this method hits a layer or member other than the metal thin film, these are also removed, so that the degree of freedom of the irradiation mode is small and handling is difficult.

  In addition, when a part of the metal thin film is removed, a step is generated between the remaining portion and the base, and thus an air layer is easily generated when ink or the like is applied thereon. The air layer existing between the layers of the decorative sheet causes poor appearance such as pinholes or metal corrosion due to moisture intrusion.

  Furthermore, in order to decorate an article using a decorative sheet on which a pattern exists, the position of the decorative sheet is determined so that the pattern is arranged at a desired position of the object to be decorated in consideration of the position of the pattern. There is a need to. Therefore, the decoration work of the article is complicated, the yield is limited, and the use efficiency of the decorative sheet is lowered unless the interval between the patterns is conveniently matched with the dimension of the object to be decorated.

WO01 / 92006 JP-A-6-79997 JP2009-6673

  The present invention solves the above-mentioned conventional problems, and the object of the present invention is to decorate as a decorative layer a metal thin film in which no clear step is formed between the pattern portion and the pattern background portion. And providing a method for producing such a decorated article by a simple operation.

The present invention is a decorated article having a decorative layer fixed to an object to be decorated,
The decorative layer has a metal thin film, the metal thin film has a transparent portion as a pattern background or a pattern,
Provide decorated items.

  In one embodiment, the metal thin film is formed by a vacuum deposition method.

  In one embodiment, the metal thin film has a thickness of 20 to 70 nm.

  In one embodiment, the metal is at least one selected from the group consisting of tin, indium, aluminum, chromium, titanium, zinc, and nickel.

  In one embodiment, the transparent portion of the metal thin film is formed by irradiating the metal thin film with laser light.

  In one embodiment, the laser beam has a wavelength of 532 to 10600 nm and a Q switch frequency of 50 to 400 kHz.

  In one embodiment, the laser beam has a peak output of 10 to 150 kW.

The present invention also includes a step of fixing a decorative layer having a plain metal thin film on the surface of the article to be decorated; and a step of forming a transparent portion on the metal thin film as a pattern background or a pattern;
A method for producing a decorated article comprising:

Moreover, this invention provides the decorating sheet which has the decorating layer which has a plain metal thin film which can be fixed to a to-be-decorated object on the surface of a base sheet;
Feeding the decorative sheet into the molding die in such a direction that the outside faces the mold cavity surface;
Closing the mold and filling the mold resin with the molten resin so that the molten resin contacts the inner surface of the decorative sheet;
Cooling the resin, opening the mold and taking out the injection molded body; and partially transparentizing the metal thin film fixed on the surface of the injection molded body to form a pattern background or pattern;
A method for producing a decorated article comprising:

  In one embodiment, the metal thin film is formed by a vapor deposition method.

  In one embodiment, the transparent portion of the metal thin film is formed by irradiating the metal thin film with laser light.

  In one embodiment, the laser beam has a scanning speed of 1 mm / second to 12000 mm / second.

In this specification, the wording is used according to the definition described below.
“Fixed” refers to attaching so that it is substantially impossible to detach. The decoration layer may be directly fixed to the object to be decorated, or may be fixed by interposing an adhesive layer or a base sheet.
The “decorated object” refers to an independent article to be decorated using the decorative sheet of the present invention. For example, injection-molded bodies, injection-molded parts and the like correspond to objects to be decorated.
The “decorated article” refers to an article having the decoration layer of the present invention on the surface of an object to be decorated.

  The decorated article of the present invention is excellent in adhesion between layers because the metal thin film forming the metallic luster pattern does not have a clear step between the pattern part and the pattern background part, poor appearance or metal corrosion Is unlikely to occur. Moreover, since it can form a metallic luster pattern after fixing the decoration layer which has a metal layer to the surface of a to-be-decorated object, it is not necessary to align a decorating sheet in the stage which fixes a decorating layer to a to-be-decorated object Fine patterns can be formed with high accuracy.

It is sectional drawing which illustrates the structure of the decorated article | item which is embodiment of this invention. It is sectional drawing which illustrates the structure of the decorating sheet which has the decorating layer which has a plain metal thin film on the surface of a base sheet. It is sectional drawing which illustrates the form which irradiates a laser beam with respect to a metal thin film. It is a 200 times enlarged photograph which shows the external appearance of a tin vapor deposition layer surface. It is the spectrum obtained as a result of performing XPS analysis about a tin vapor deposition layer. It is a 200 times enlarged photograph which shows the external appearance of the tin vapor deposition layer surface after irradiating a laser beam. It is the spectrum obtained as a result of having performed the XPS analysis about the transparent part of a tin vapor deposition layer.

Decorated Article FIG. 1 is a cross-sectional view showing the structure of a decorated article according to an embodiment of the present invention. The decoration layer 2 is fixed to the surface of the article to be decorated 8.

  In FIG. 1 (a), the decoration layer 2 is composed of an anchor layer 3, a metal thin film 4, a pattern layer 5 and an adhesive layer 6, and the outermost side is a base sheet 1, which is used for simultaneous injection molding. It is an article formed when the base sheet is not peeled off after being performed.

  In FIG. 1 (b), the decorative layer 2 is composed of a hard coat layer 7, an anchor layer 3, a metal thin film 4, a pattern layer 5 and an adhesive layer 6, and the outermost side is a hard coat layer 7. It is an article formed when the base sheet is peeled after simultaneous injection molding.

  In FIG. 1 (c), the decorative layer 2 is composed of an anchor layer 3, a metal thin film 4 and a hard coat layer 7, and the decorative layer 2 is fixed to the object to be decorated 8 via the base sheet 1 and the adhesive layer 6. Goods.

  The metal thin film 4 is a metal layer that imparts a metallic luster pattern or appearance to the decorative layer. The metal thin film 4 has a transparent portion 41 as a pattern background or a pattern. The other part of the metal thin film 4 is a metallic luster part 42.

Manufacturing method of decorated article The metal thin film is first fixed to the surface of the object to be decorated, and then the pattern background or the part corresponding to the pattern is made transparent. Generally, a metal thin film is fixed to the surface of a to-be-decorated object using the decorating sheet which has the decorating layer which has a metal thin film at least on the surface of a base sheet.

  In the stage where the decoration layer is fixed to the surface of the object to be decorated, the metal thin film is preferably plain. If the metal thin film is plain, the work of determining the position of the decorating sheet is unnecessary so that the pattern is arranged at a desired position of the object to be decorated. Therefore, it is possible to omit the interval that has been sent wastefully in order to align the position of the pattern with respect to the object to be decorated, and the use efficiency of the decorative sheet is also improved. The metal thin film is preferably formed over the entire surface of the object to be decorated, but may be formed in part.

  FIG. 2 is a cross-sectional view illustrating the structure of a decorative sheet having a decorative layer having a plain metal thin film on the surface of the base sheet. A decorative layer 2 having a plain metal thin film 4 is provided on one side of the base sheet 1. Specifically, the decorative layer 2 has an anchor layer 3, a metal thin film 4, and an adhesive layer 6 laminated on one side of the base sheet.

  The metal used for the metal thin film may be an alloy, compound, or the like of aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, zinc, etc. is there. The metal forming the metal thin film needs to be transparent by applying energy from the outside, and preferable ones are tin, indium, aluminum, chromium, titanium, zinc, and nickel.

  In one certain form, a metal thin film combines metal luster, insulation, radio wave permeability, and suitability for use adjacent to an electrostatic switch. The insulating metal thin film preferably has an island structure with an island size of 1 nm to 2 μm and an island interval of 2 nm to 500 nm. As the metal used for the insulating metal thin film, tin or indium is particularly preferable from the viewpoint of insulation.

  The metal thin film can be formed as a layer constituting the decorative layer 2 by a method similar to the conventional method. Specific examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. A preferred method for forming the metal thin film is a vacuum deposition method. The vacuum deposition method is preferable because it can form a metal thin film at a high speed, is excellent in cost and productivity, and can suppress damage to the decorative sheet substrate and the decorative layer.

  The thickness of the metal thin film is 10 to 300 nm, preferably 10 to 100 nm, more preferably 30 to 70 nm. If the thickness of the metal thin film is less than 10 nm, the metallic luster of the pattern formed becomes insufficient, and if it exceeds 300 nm, it becomes difficult to make the film transparent.

  In addition, the decoration layer 2 may include a release layer and a hard coat layer between the base sheet 1 and the metal thin film 4, and an additional anchor layer and an additional layer adjacent to the inner surface of the metal thin film 4, if necessary. There may be a pattern layer. In this specification, with respect to the layer structure of the decorative sheet, the side of the object to be decorated is referred to as the inside, and the viewer's side is referred to as the outside.

  For example, after performing simultaneous injection molding decoration, when the base sheet 1 is peeled off from the injection molded body leaving the decoration layer 2, the decoration layer 2 needs to have releasability from the base sheet 1. is there. In such a case, a release layer is formed between the base sheet 1 and the metal thin film 4 so as to be in contact with the base sheet 1.

  The method for fixing the decorative layer 2 having a plain metal thin film to the object to be decorated is not particularly limited, but is preferably a hot roll transfer method or an in-mold molding method. For example, in hot roll transfer, the decor sheet base is used by using a transfer machine such as a roll transfer machine or an up-down transfer machine with the inner surface (adhesive layer side) of the decorative sheet superimposed on the surface of the object to be decorated. Apply heat and pressure from the sheet side. By doing so, the decorative sheet adheres to the surface of the object to be decorated, and the surface of the article is decorated.

  In in-mold injection molding, first, a decorative sheet is fed into a molding die. At that time, the decorative sheet is oriented so that the outer side faces the mold cavity surface. Next, the mold is closed, so that the molten resin is in contact with the inner surface of the decorative sheet (that is, the adhesive layer side), that is, the decorative sheet is sandwiched between the molten resin and the mold cavity surface. Is filled into the mold cavity. As a result, the molten resin is molded, and at the same time, the decorative sheet is bonded to the surface of the injection molded body. When the resin is cooled, the mold is opened, and the injection molded body is taken out, the decorative layer is adhered to the surface of the injection molded body, and the surface of the injection molded body is decorated.

  When a release layer is formed between the base sheet and the decorative layer, the base sheet is finally peeled off.

  The metal thin film is made transparent by applying energy from the outside. The portion to which energy is applied is a portion corresponding to the pattern background of the metallic luster pattern. If this part of the metal thin film is made transparent, the part corresponding to the pattern is left with a metallic luster.

  On the other hand, when a transparent pattern is desired, energy may be applied to a portion corresponding to the pattern of the metal thin film.

  The mechanism by which the metal thin film becomes transparent is not clear. However, it is known that metals such as tin, indium and aluminum become transparent by oxidation. When these metal thin films are left in the air, the metallic luster gradually decreases. Therefore, there is a high possibility that the metal of the metal thin film reacts with an element such as oxygen contained in the thin film or entering from the surroundings, resulting in an oxidation reaction.

  The type of energy to be applied is not particularly limited as long as it realizes or accelerates the transparency of the metal thin film. For example, thermal energy or light energy is exemplified. The thermal energy can be partially applied using, for example, a thermal head. Considering the influence on the layers other than the metal thin film, the preferable energy is light energy. The light energy can be partially applied using, for example, a pattern mask.

  A particularly preferable energy among the light energies is laser light. It is because it is easy to irradiate correctly according to the pattern background or the shape of the pattern. For example, if a laser beam is used, it is possible to draw even a pattern with a submicron size. Laser light can be selected under irradiation conditions that do not affect the transparent material, and it is possible to irradiate a metal thin film while passing through a transparent layer such as a base sheet. The degree is great.

  Preferred laser light has a Q switch frequency of 50 to 400 kHz, preferably 100 to 400 kHz, and more preferably 300 to 400 KHz. If the Q switch frequency of the laser light is less than 50 kHz, the transparent layer may be damaged by a shock wave, and if it exceeds 400 kHz, it may be difficult to make the metal transparent.

  A preferable laser beam has a wavelength of 532 to 10600 nm, preferably 532 to 2000 nm, more preferably 532 to 1064 nm. If the wavelength of the laser beam is less than 532 nm, it will not be transparent because it is not the tin absorption range, and if it exceeds 10600 nm, it will be the absorption region of the transparent layer, so it is difficult to make tin transparent simply by engraving the transparent layer It becomes.

Specific examples of laser light that satisfies the above conditions include solid laser media such as Nd: YAG, Nd: YVO ₄ , Nd: YLF, semiconductor laser media such as GaAs, and gas laser media such as CO ₂ and He—Ne. And laser light obtained by exciting. Of these, the fundamental wave of Nd: YAG, Nd: YVO ₄ laser is preferable.

  The preferable laser light has a peak output of 10 kW to 150 kW, preferably 10 kW to 100 kW, more preferably 20 kW to 100 kW. If the output of the laser beam is less than 10 kW, it becomes difficult to make the metal transparent, and if it exceeds 100 kW, the design layer and the adhesive layer may be discolored and the design may be impaired.

  Furthermore, a preferable laser beam has a scanning speed of 1 mm / second to 12000 mm / second, preferably 2000 mm / second to 8000 mm / second, more preferably 3000 mm / second to 5000 mm / second. If the scanning speed of the laser beam is less than 1 mm / second, the sharpness of the transparent pattern is impaired, and if it exceeds 12,000 mm / second, the transparent layer may be scraped off.

  FIG. 3 is a cross-sectional view illustrating a mode in which laser light is irradiated onto a metal thin film. Irradiation with laser light may be performed through, for example, transparent layers such as the base sheet 1 and the anchor layer 3. The transparency of the metal thin film by laser light functions even if the metal layer is not exposed to the air.

Next, each layer other than the metal thin film, which constitutes the above decorative sheet preferable for producing the decorated article of the present invention, will be described.

  Of the layers constituting the decorative layer, each resin layer can be formed by the same method as before unless otherwise specified. Examples of conventional layer forming methods include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, and screen printing.

Substrate sheet The substrate sheet 1 is composed of a sheet material or a film material conventionally used for supporting a picture layer or a colored layer on a sheet. Film material refers to a sheet material made of synthetic resin. As the synthetic resin, polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, polyvinyl chloride resin and the like can be used. The base sheet is preferably light transmissive, and more preferably transparent.

  In some cases, the base sheet is peeled off from the decoration layer after performing the injection molding simultaneous decoration, and may remain after being subjected to the simultaneous injection molding decoration.

  In the case where the base sheet is peeled off from the injection-molded body leaving the decorative layer after the simultaneous injection molding, the base sheet is preferably thin and excellent in toughness. As the base sheet, for example, a stretched polyester resin film is preferable.

  In the case of such a material, the thickness of the base sheet is preferably 10 to 100 μm, preferably 20 to 80 μm, more preferably about 30 to 70 μm. If the thickness of the base sheet is less than 10 μm, the strength is insufficient and may be damaged when performing simultaneous injection molding, and if it exceeds 100 μm, the followability to the three-dimensional shape of the decorative sheet may be reduced. .

  Even after the simultaneous injection molding, if the base sheet remains adhered to the decorative layer, the base sheet is preferably excellent in heat stretchability. This is because the followability to the three-dimensional shape of the decorative sheet is improved. As the base sheet, for example, an acrylic resin film, a polycarbonate resin film, a polycarbonate resin / polyester resin alloy film, and the like are preferable.

  In the case of such a material, the thickness of the base sheet is preferably 70 to 200 μm, preferably 80 to 160 μm, more preferably about 90 to 140 μm. If the thickness of the base sheet is less than 70 μm, the strength is insufficient, and there is a risk of damage when performing simultaneous injection molding, and if it exceeds 200 μm, the heat of the injection resin will not easily escape to the mold and ink flow will occur. It becomes easy.

Release layer The release layer may be separated from the decorative layer together with the base sheet during transfer, or may be separated from the base sheet to form the outermost surface of the decorative layer. . As the material of the release layer, melamine resin, silicone resin, fluorine resin, cellulose derivative, urea resin, polyolefin resin, paraffin resin, and composites thereof can be used.

The hard coat layer 7 is a layer that becomes the outermost side of the transfer layer 2 after fixing the decorative layer to the object to be decorated. The hard coat layer has a certain hardness to protect the ornament.

  As the hard coat layer, an energy crosslinkable resin that crosslinks or cures when energy such as heat, ultraviolet rays, or an electron beam is applied is used. Examples of the material of the hard coat layer include ionizing radiation curable resins such as cyanoacrylate and urethane acrylate, and thermosetting resins such as acrylic and urethane, but are not particularly limited. Preferably, the energy crosslinkable resin is an active energy ray crosslinkable resin that is crosslinked by applying an ultraviolet ray or an electron beam. This is because the active energy ray resin can easily adjust the degree of crosslinking by increasing or decreasing the amount of energy applied.

Anchor layer The anchor layer 3 is a resin layer that adheres the metal foil film 4 to the transfer layer. The anchor layer 3 is formed on the entire sheet surface. After the transfer layer is transferred to the article, the anchor layer 3 serves to protect the metal thin film 4 from scratches and the like together with the hard coat layer and improve the corrosion resistance.

  The resin used for the anchor layer includes two-component cured urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, epoxy resin, Examples include vinyl copolymer resins.

The pattern layer The pattern layer 5 is a layer for decorating the object to be decorated. The picture layer here includes a colored layer having no picture in addition to a layer for forming a character or a picture.

  The pattern layer is formed, for example, by spreading a color ink or paint containing a synthetic resin as a binder and a colorant on the surface of a layer adjacent to the pattern layer such as the metal thin film 4. Examples of methods for spreading ink or paint include, for example, printing methods such as gravure printing, flexographic printing, and screen printing; and gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss Coating methods such as a touch coater, a kiss touch reverse coater, a comma coater, a comma reverse coater, and a micro gravure coater can be used.

  Synthetic resins that serve as binders in the pattern layer include polyvinyl resins, polyamide resins, polyester resins, acrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and chlorides. At least selected from the group consisting of vinyl vinyl acetate copolymer resins, thermoplastic urethane resins, methacrylic resins, acrylic ester resins, chlorinated rubber resins, polyethylene chloride resins, and chlorinated polypropylene resins One synthetic resin is preferred.

  Specific examples of preferable colorants include (1) plant pigments such as indigo, alizarin, carsamine, anthocyanins, flavonoids, shikonin, (2) food pigments such as azo, xanthene, triphenylmethane, (3) loess, green soil, etc. Natural inorganic pigments, (4) inorganic pigments such as acrylic and urethane, and (5) calcium carbonate, titanium oxide, aluminum lake, mudder lake, and cochineal lake.

  In order to form a picture layer, a high-brightness ink layer made of an ink having a mirror-like metallic luster (hereinafter referred to as a high-brightness ink) in which metal thin film strips are dispersed in a binder resin may be used. It is preferable that content with respect to the non volatile matter in the ink of a metal thin film piece is the range of 3-60 mass%. High brightness ink using metal thin film strips as a pigment, when the ink is printed or applied, the metal thin film strips are oriented in a direction parallel to the surface of the object, resulting in a high-brightness mirror-like metallic luster. can get.

The adhesive layer adhesive layer 6 is a layer for adhering the decorative layer and the injection molded body at the time of simultaneous injection molding. As the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for an injection-molded product is appropriately used. For example, when the material of the injection molded body is an acrylic resin, an acrylic resin may be used.
And formed on a portion of the inner surface of the transfer sheet that is desired to be adhered to the decorative article. That is, when it is desired to bond the entire inner surface to the article to be decorated, an adhesive layer is formed on the entire surface. Moreover, when it is desired to adhere a part of the inner surface to the article to be decorated, an adhesive layer is formed on a part thereof.

  The constituent material of the adhesive layer is not particularly limited as long as sufficient adhesiveness to the article to be decorated can be obtained. When the adhesive layer is thermocompression bonded to the article to be decorated, a synthetic resin having heat sensitivity and pressure sensitivity may be appropriately selected as a constituent material of the adhesive layer.

  For example, when the constituent material of the surface portion of the article to be decorated is a polyacrylic resin, it is preferable to use a polyacrylic resin as the constituent material of the adhesive layer. For example, when the constituent material of the surface portion of the article to be decorated is a polyphenylene oxide copolymer, a polystyrene copolymer resin, a polycarbonate resin, a styrene resin, or a polystyrene blend resin, The polyacrylic resin, polystyrene resin, polyamide resin and the like having an affinity for these resins may be appropriately selected and employed.

  Further, for example, when the constituent material of the surface portion of the article to be decorated is a polypropylene resin, the constituent materials of the adhesive layer are chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone Indene resin can be used.

  The present invention will be specifically described by the following examples, but the present invention is not limited thereto. In addition, unless otherwise indicated, the quantity represented by "part" or "%" in an Example is represented on the basis of mass.

Reference Example It was investigated how the physical properties of the irradiated area change when the tin deposition layer is irradiated with laser light.

  Using a vapor deposition method, a tin vapor deposition layer having a thickness of 70 nm was formed on the surface of the polyethylene terephthalate film. FIG. 4 is a 200 × magnified photograph showing the appearance of the surface of the tin vapor deposition layer. Although the central portion is bright and the peripheral portion is dark due to reflection of illumination, the surface of the tin vapor deposition layer is actually uniform over the entire surface. That is, the tin vapor deposition layer is not yet irradiated with laser light, and there is no transparent portion.

  X-ray photoelectron spectroscopic analysis (XPS analysis) was performed on the tin vapor deposition layer. Specifically, first, the oxide layer on the surface of the tin deposition layer was removed by performing sputtering for 2 minutes at a voltage of 3 kV using argon.

  Next, an MgKα ray was obtained by irradiating magnesium with an electron beam at an output of 400 W, and this MgKα ray was irradiated on the surface of the tin vapor deposition layer from which the oxide layer was removed at an output of 58.7 eV and an irradiation angle of 45 degrees. As a result, photoelectrons were emitted from the tin vapor deposition layer, and the kinetic energy of the photoelectrons was measured. The kinetic energy of the photoelectron has a value specific to the atom from which the photoelectron is emitted, and information on the chemical bonding state of the element can be obtained from the measured value.

  FIG. 5 is a spectrum obtained as a result of XPS analysis of the tin vapor deposition layer. In the spectrum, the peak at 485 eV means the presence of tin, and the shoulder at 486 to 487 eV means the presence of tin oxide.

  Subsequently, the exposed surface of this tin vapor deposition layer was irradiated with laser light so as to form a grid having a width of about 10 mm. Irradiation conditions are as follows.

[Table 1]

  FIG. 6 is a 200 × magnified photograph showing the appearance of the surface of the tin vapor deposition layer after irradiation with laser light. The tin vapor deposition layer has a transparent portion corresponding to the portion irradiated with the laser beam.

  XPS analysis was performed on the transparent portion of the tin vapor deposition layer in the same manner as described above except that the transparent portion of the tin vapor deposition layer was irradiated with MgKα rays. FIG. 7 is a spectrum obtained as a result of XPS analysis of the transparent portion of the tin vapor deposition layer.

  Compared with the spectrum of FIG. 6, in the spectrum of FIG. 7, the peak of 485 eV corresponding to tin decreases, and the peak of 486 to 487 eV corresponding to tin oxide grows.

  From these results, it was shown that the irradiated portion was made transparent by irradiating the tin vapor deposition layer with laser light, and that tin oxide was formed in the transparent portion.

Example A polyethylene terephthalate film having a thickness of 38 μm was prepared as a base sheet. On this base sheet, a release layer was formed by applying and drying a melamine resin release agent. Thereafter, a paint containing a melamine resin was applied and dried to form a hard coat layer. On the hard coat layer, a paint containing a urethane resin was applied to form a front anchor layer.

  A vacuum deposition method was performed to form a 15-nm-thick tin deposition layer having an island-like structure and insulation on the surface of the front anchor layer.

  A paint for forming an anchor layer was prepared by dissolving a polyurethane polyol having a number average molecular weight (Mn) of 70000, a softening point of 45 ° C. and a hydroxyl value of 1.7 in methyl ethyl ketone as a solvent.

  On the surface of the tin vapor deposition layer, the obtained paint was applied and dried to form a post anchor layer having a thickness of 1.0 μm from the surface of the tin vapor deposition layer. Furthermore, a coating film containing an acrylic resin was applied and dried to form an adhesive layer to obtain a transfer film. In the above process, all the resin layers were formed by a gravure coating method.

  The obtained transfer film was put into a mold and PMMA resin was in-mold molded to obtain a 2.0 mm thick PMMA resin plate having a metallic appearance.

  A part of the surface of the PMMA resin plate was irradiated with laser light in a 10 mm × 10 mm square shape from the base sheet side. Irradiation conditions were as follows.

[Table 2]

  As a result, a 10 mm × 10 mm transparent portion was formed in the tin vapor-deposited layer, and a PMMA resin plate having a partially transparent metal thin film was obtained.

  The present invention is used to decorate the appearance of injection molded articles and industrial products whose parts are injection molded articles.

1 ... Base sheet,
2 ... decorative layer,
3 ... Anchor layer,
4 ... metal thin film,
5 ... Pattern layer,
6 ... adhesive layer,
7 ... Hard coat layer,
8 ... Decoration.

Claims (12)

A decorated article having a decorative layer fixed to an object to be decorated,
The decorative layer has a metal thin film, the metal thin film has a transparent portion as a pattern background or a pattern,
Decorated article.   The decorated article according to claim 1, wherein the metal thin film is formed by a vacuum deposition method.   The decorated article according to claim 1 or 2, wherein the metal thin film has a thickness of 10 to 300 nm.   The decorated article according to any one of claims 1 to 3, wherein the metal is at least one selected from the group consisting of tin, indium, aluminum, chromium, titanium, zinc, and nickel.   The decorated article according to any one of claims 1 to 4, wherein the transparent portion of the metal thin film is formed by irradiating the metal thin film with laser light.   The decorated article according to any one of claims 1 to 5, wherein the laser light has a wavelength of 532 to 10600 nm and a Q switch frequency of 50 to 400 kHz.   The decorated article according to claim 1, wherein the laser light has a peak output of 10 kW to 150 kW. Fixing a decorative layer having a plain metal thin film on the surface of the article to be decorated; and forming a transparent portion on the metal thin film as a pattern background or pattern;
A method for producing a decorated article comprising: Providing a decorative sheet having a decorative layer having a plain metal thin film that can be fixed to the object to be decorated on the surface of the base sheet;
Feeding the decorative sheet into the molding die in such a direction that the outside faces the mold cavity surface;
Closing the mold and filling the mold resin with the molten resin so that the molten resin contacts the inner surface of the decorative sheet;
Cooling the resin, opening the mold and taking out the injection molded body; and partially transparentizing the metal thin film fixed on the surface of the injection molded body to form a pattern background or pattern;
A method for producing a decorated article comprising:   The method for producing a decorated article according to claim 8 or 9, wherein the metal thin film is formed by a vapor deposition method.   The method for producing a decorated article according to claim 8, wherein the transparent portion of the metal thin film is formed by irradiating the metal thin film with laser light.   The method for producing a decorated article according to any one of claims 8 to 11, wherein the laser beam has a scanning speed of 1 mm / second to 12000 mm / second.

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