JP5339700B2 - Radio wave transmitting transfer material and manufacturing method thereof - Google Patents

Description

  The present invention relates to a radio wave transmissive transfer material having a radio wave permeable metal thin film excellent in durability and a method for producing the same.

  In a communication device such as a mobile phone, an information device inside a car, a home appliance, and the like, there is a method in which a transfer material is used to decorate the surface of a plastic molded product in order to express a metallic luster that transmits radio waves.

  There is a transfer method as a method for decorating the surface of the transfer object. The transfer method uses a transfer material in which a transfer layer composed of a release layer, a design layer, an adhesive layer, etc. is formed on a substrate sheet, and heat-presses the transfer layer to adhere to the transfer object, This is a method of performing decoration by peeling and transferring only the transfer layer to the surface of the transfer object. In addition, when the material to be transferred is a resin molded product, there is a simultaneous molding transfer method as a method for performing the transfer method more rationally. The molding simultaneous transfer method is a method in which a transfer material is sandwiched in a molding die, a resin is injected and filled in the die, and cooled to obtain a resin molded product. In this method, the substrate sheet is peeled off and the transfer layer is transferred to the surface of the transfer object to decorate.

  As a transfer material provided with a metallic luster having radio wave transmission used in such a method, there is one in which a radio wave transparent metal thin film made of a metal such as tin is formed in an island structure (for example, see Patent Document 1). As the radio wave permeable metal thin film, tin is generally used because it is harmless and easy to deposit. However, the tin film thus formed in the island-like structure has a large surface area, so that the rate of adhesion of oxygen, water, chlorine, etc. is high, and the corrosion rate is high. In addition, since tin becomes transparent when oxidized, there is a problem that, for example, the metallic luster fades with time and becomes transparent.

  In order to solve such a problem, for example, a water-soluble paint is partially applied to the surface of the substrate by printing or the like, and a radio wave permeable metal thin film is formed on the entire surface thereof. Applying a water-insoluble paint with a thickness of 0.05-1.0μm from the top of the thin film, and then washing the resulting product with water to dissolve and remove the water-soluble paint. A method of partially applying a radio wave permeable metal thin film characterized by removing the permeable metal thin film and the water insoluble paint, and leaving the water permeable metal thin film and the water insoluble paint in a portion where no water soluble paint exists. (For example, refer to Patent Document 1).

JP-A-62-174189 Japanese Patent Publication No. 7-37111

  However, the method for producing the transfer material described above can improve the corrosion resistance to the radio wave permeable metal thin film made of tin at the time of washing with water, but a water-soluble paint layer must be formed, leading to an increase in the number of processes. There was a problem.

  Therefore, an object of the present invention is to provide a radio wave transmissive transfer material having a radio wave permeable metal thin film having excellent durability, and a method for producing the same, which solve the above problems.

  In order to achieve the above object, the radio wave transmission transfer material of the present invention is configured as follows.

  That is, in the method for producing a radio wave transmissive transfer material according to the first aspect of the present invention, a release layer is entirely formed on a substrate sheet having peelability, and then a water-soluble pattern layer is partially formed thereon. Then, a fine island-shaped radio wave-transmitting metallic gloss layer made of an alloy of tin and a metal having a higher ionization tendency than tin is formed on the entire surface, and then washed with water to perform a water-soluble pattern layer. And the radio wave transmitting metallic luster layer formed thereon are peeled and removed, and then the adhesive layer is formed entirely or partially.

  In addition, as a second aspect of the invention, the radio wave transmitting transfer material manufacturing method of the first aspect may be configured such that the radio wave transmitting metallic luster layer is made of an alloy of tin and aluminum.

  In addition, as a third aspect of the invention, the radio wave transmitting transfer material manufacturing method according to the first aspect has an atomic concentration (Al) of the outermost layer of the radio wave transmitting metallic glossy layer measured with a fluorescent X-ray measuring device of Al. /Sn=0.01-2.0 can also be configured.

  Further, as a fourth aspect of the invention, the radio wave transmitting transfer material manufacturing method according to the first aspect has an atomic concentration (Al) of the outermost layer of the radio wave transmitting metallic glossy layer measured with a fluorescent X-ray measuring device of Al. It is also possible to configure so that /Sn=0.15 to 1.5.

  The radio wave transmitting transfer material according to the fifth aspect of the present invention has a release layer and a fine island-like shape made of an alloy of metal and tin, which has a higher ionization tendency than tin, on a base sheet having peelability. A patterned radio wave transmitting metallic luster layer and an adhesive layer may be formed at least.

  Further, as a sixth aspect of the invention, the radio wave transmitting transfer material of the fifth aspect can be configured such that the radio wave transmitting metallic luster layer is made of an alloy of tin and aluminum.

  In addition, as a sixth aspect of the invention, the radio wave transmitting transfer material according to the fifth aspect has an atomic concentration of the outermost layer of the radio wave transmitting metallic glossy layer measured by a fluorescent X-ray measuring apparatus, wherein Al / Sn = It can also comprise so that it may be 0.01-2.0.

  In addition, as a sixth aspect of the invention, the radio wave transmitting transfer material according to the fifth aspect has an atomic concentration of the outermost layer of the radio wave transmitting metallic glossy layer measured by a fluorescent X-ray measuring apparatus, wherein Al / Sn = It can also comprise so that it may be 0.15-1.5.

  In the method for producing a radio wave transmitting transfer material of the present invention, a release layer is entirely formed on a peelable substrate sheet, and then a water-soluble pattern layer is partially formed thereon, and then on the release layer. In addition, a fine island-shaped radio wave transparent metallic luster layer made of an alloy of tin and a metal that has a higher ionization tendency than tin is formed on the entire surface, and then washed with water to form a water-soluble pattern layer and the water-soluble pattern layer. The radio wave permeable metallic luster layer is peeled and removed, and then the adhesive layer is entirely or partially formed. Can be obtained.

  In the radio wave transmitting transfer material of the present invention, a release layer is entirely formed on a peelable substrate sheet, and then a water-soluble pattern layer is partially formed on the release layer. A fine island-shaped radio wave permeable metallic luster layer made of an alloy of tin and a metal having a higher ionization tendency than tin was formed on the entire surface, and then washed with water to form a water-soluble pattern layer and the water-soluble pattern layer. It is a radio wave permeable transfer material having a radio wave permeable metal thin film with excellent durability because the radio wave permeable metallic luster layer is peeled off and then the adhesive layer is formed entirely or partially. .

  Embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an embodiment of a method for producing a radio wave transmitting transfer material of the present invention. FIG. 2 is a sectional view showing an embodiment of the radio wave transmitting transfer material of the present invention. In the figure, 1 is a radio wave transmitting transfer material, 2 is a base sheet, 3 is a release layer, 4 is a water-soluble pattern layer, 5 is a radio wave transmitting metallic gloss layer, 6 is an adhesive layer, 7 is a pattern layer, and 8 is a front layer. An anchor layer 9 is a rear anchor layer. In addition, the same code | symbol is attached | subjected about the same component in each figure.

  In the method for producing a radio wave transmissive transfer material 1 according to the first embodiment of the present invention, a release layer 3 is entirely formed on a substrate sheet 2 having peelability, and then a water-soluble pattern layer is formed thereon. 4 is then partially formed, and then a finely island-shaped radio wave-transmitting metallic gloss layer 5 made of an alloy of tin and a metal having a higher ionization tendency than tin is formed on the entire surface, and then washed with water. The water-soluble pattern layer 4 and the radio wave transmissive metallic luster layer 5 formed thereon are peeled and removed, and then the adhesive layer 6 is entirely or partially formed (see FIG. 1). ).

  As the base sheet 2 having releasability, it is used as a base sheet for ordinary transfer materials, such as resin sheets such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, and polyvinyl chloride resin. Things can be used. Moreover, when the surface of the base sheet 2 has fine irregularities, the irregularities are copied onto the transfer layer, and surface shapes such as matte and hairline can be expressed.

  In order to improve the peelability of the transfer layer from the base sheet 2, a release layer may be formed on the entire surface (not shown) before the transfer layer is provided on the base sheet 2. The release layer is released from the transfer layer together with the base sheet 2 when the base sheet 2 is peeled off after transfer or after simultaneous molding transfer. As the material of the release layer, melamine resin release agent, silicone resin release agent, fluororesin release agent, cellulose derivative release agent, urea resin release agent, polyolefin resin release agent, Paraffin-type release agents and composite release agents thereof can be used. As a method for forming the release layer, there are a coating method such as a roll coating method and a spray coating method, a printing method such as a gravure printing method and a screen printing method.

  Next, the release layer 3 is formed over the entire surface (see FIG. 1A). The release layer 3 is a layer that peels from the base sheet 2 or the release layer and becomes the outermost surface of the transfer object when the base sheet 2 is peeled after transfer or after simultaneous molding transfer. The release layer 3 can be made of acrylic resin, polyester resin, polyvinyl chloride resin, cellulose resin, rubber resin, polyurethane resin, polyvinyl acetate resin, or vinyl chloride-vinyl acetate copolymer. Copolymers such as system resins and ethylene-vinyl acetate copolymer resins may be used. When the release layer 3 requires hardness, a photo-curing resin such as an ultraviolet curable resin, a radiation curable resin such as an electron beam curable resin, or a thermosetting resin may be selected and used. The release layer 3 may be colored or uncolored. Examples of the method for forming the release layer 3 include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

  Next, a water-soluble pattern layer 4 is partially formed thereon (see FIG. 1 (a)). A radio wave-transmitting metallic luster layer 5 is entirely formed on the partially formed water-soluble pattern layer 4, and the water-soluble pattern layer 4 is removed by washing with water, so that the water-soluble pattern layer 4 is not formed. A radio wave transmissive pattern having a metallic luster is formed in the region. The water-soluble pattern layer 4 is formed by using a printing method such as a gravure printing method, a flexographic printing method, or a screen printing method using an ink having a water-soluble resin typified by polyvinyl alcohol, starch, algide, epoxy, polyurethane, or the like as a binder. It is good to form.

  Next, a radio-transmitting metallic gloss layer 5 having a fine island shape made of an alloy of tin and a metal having a higher ionization tendency than tin is formed on the entire surface (see FIG. 1A). The radio wave permeable metallic luster layer 5 is for expressing metallic luster, and is formed by an alloy of tin and a metal that has a higher ionization tendency than tin by a vacuum deposition method, a sputtering method, an ion plating method, or the like. It is formed into a shape. Examples of metals having a greater ionization tendency than tin include aluminum, zinc, and indium. By configuring the radio wave permeable metallic luster layer in this way, it is possible to dramatically slow the corrosion rate, and with excellent corrosion resistance, it is possible to suppress discoloration over time to a practical level. It becomes. In addition, the adhesiveness to other layers is excellent, and physical scratches are hardly caused. Further, since it is an alloy, it is possible to adjust the color of the metallic luster.

  Among these, when aluminum is used, it is excellent in terms of controlling the alloy composition ratio in the vacuum deposition method. Further, it is preferable that the atomic concentration (Atomic Concentration) of the outermost layer of the radio wave transmitting metallic luster layer measured with a fluorescent X-ray measuring apparatus is Al / Sn = 0.01 to 2.0. When it is within the above range, the metallic luster and the corrosion resistance are excellent. If it is less than the above range, there is a problem of poor contribution to corrosion resistance. Moreover, when it exceeds the above range, there is a problem that the fine island-like shape of the metallic luster layer is not formed and the radio wave transmission is hindered. In particular, the atomic concentration is more preferably Al / Sn = 0.15 to 1.5.

  Next, washing with water is performed (see FIG. 1B), and the water-soluble pattern layer 4 and the radio wave transmitting metallic luster layer 5 formed thereon are peeled and removed (see FIG. 1C). In order to perform the water washing treatment, the surface on which the radio wave permeable metallic luster layer 5 is formed is softened while the sheet on which the water-soluble pattern layer 4 is formed is immersed in cold water or a hot water tank, or cold water or warm water shower water is discharged. The water-soluble pattern layer 4 may be completely removed together with the radio wave permeable metallic luster layer 5 formed on the water-soluble pattern layer 4 by friction cleaning with a simple brush. Next, water adhering to the sheet is removed by hot air drying.

  Next, the adhesive layer 6 is formed entirely or partially (see FIG. 1D) to obtain the radio wave transmissive transfer material 1. The adhesive layer 6 adheres each of the above layers to the surface of the transfer object. The adhesive layer 6 is formed on a portion to be bonded. That is, when the part to be bonded is the entire surface, the adhesive layer 6 is formed on the entire surface. If the part to be bonded is partial, the adhesive layer 6 is partially formed. As the adhesive layer 6, a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer object is appropriately used. For example, when the material of the transfer object is an acrylic resin, an acrylic resin may be used. In addition, when the material of the material to be transferred is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, acrylic resin, polystyrene resin, polyamide having affinity with these resins A series resin or the like may be used. Further, when the material of the transfer object is a polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used. Examples of the method for forming the adhesive layer 6 include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, a printing method such as a gravure printing method, and a screen printing method.

  The configuration of the transfer layer is not limited to the above-described embodiment. For example, in addition to the metallic luster pattern by the radio wave permeable metallic luster layer 5, the pattern layer 7 is used to decorate various patterns and characters. You may form (refer FIG. 2). As the material of the pattern layer 7, a resin such as a polyvinyl resin, a polyamide resin, a polyester resin, an acrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin is used as a binder. And a color ink containing an appropriate color pigment or dye as a colorant may be used. As a method for forming the printing layer, a normal printing method such as a gravure printing method, a screen printing method, or an offset printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, or a comma coating method may be employed. The symbol layer 7 may be provided in an arbitrary pattern according to the symbol to be expressed.

  Further, when the radio wave transmitting metallic gloss layer 5 is provided, the front anchor layer 8 and the rear anchor layer 9 may be provided in order to improve the adhesion between the other transfer layer and the radio wave transmitting metallic gloss layer 5. (See FIG. 2). As materials of the front anchor layer 8 and the rear anchor layer 9, two-component cured urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin Epoxy resins and vinyl copolymer resins may be used. Examples of methods for forming the front anchor layer and the rear anchor layer include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, and screen printing.

  The radio wave transmitting transfer material 1 configured as described above can be used to decorate an object to be transferred by using as follows.

  As the material to be transferred, those made of various materials such as a resin molded product can be used. The transfer object may be transparent, translucent, or opaque. Further, the transfer object may be colored or not colored. Examples of the resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate-modified polyphenylene ether resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, polysulfone resins, polyphenylene sulfide resins Super engineering resins such as polyphenylene oxide resins, polyarylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat-resistant resins can also be used. Furthermore, composite resins to which reinforcing materials such as glass fibers and inorganic fillers are added can also be used.

  A method of decorating the surface of the transfer object using the transfer method using the radio wave transmitting transfer material having the above-described layer structure will be described. First, the adhesive layer side of the radio wave transmitting transfer material is brought into close contact with the surface of the transfer object. Next, using a transfer machine such as a roll transfer machine or an up-down transfer machine equipped with a heat-resistant rubber-like elastic body such as silicon rubber, a heat-resistant rubber-like condition set at a temperature of about 80 to 260 ° C. and a pressure of about 490 to 1960 Pa. Heat and pressure are applied from the base sheet side of the radio wave transmitting transfer material through the elastic body. By doing so, the adhesive layer adheres to the surface of the transfer object. Finally, when the base sheet is peeled off after cooling, peeling occurs at the interface between the base sheet and the release layer, and the transfer is completed.

  Next, a method for decorating the surface of a resin molded product, which is a transfer object, using the above-described radio wave transmitting transfer material and utilizing a molding simultaneous transfer method by injection molding will be described. First, a radio wave transmitting transfer material is fed into a molding die composed of a movable die and a fixed die. At this time, the sheet-like radio wave transmission material may be fed one by one, or a necessary part of the long radio wave transmission material may be intermittently fed. In the case of using a long radio wave transmissive transfer material, it is preferable to use a feeding device having a positioning mechanism so that the register of the radio wave transmissive transfer material pattern coincides with the molding die. In addition, when the radio wave transmission material is intermittently fed, if the radio wave transmission material is fixed between the movable type and the fixed type after the position of the radio wave transmission material is detected by the sensor, it is always the same. This is convenient because the radio wave transmitting transfer material can be fixed at the position, and the pattern is not displaced. After the molding die is closed, the molten resin is injected and filled from the gate into the die, and at the same time as the transfer object is formed, the radio wave transmitting transfer material is adhered to the surface. After the resin molded product, which is the transfer target, is cooled, the molding die is opened and the resin molded product is taken out. Finally, the transfer is completed by removing the base sheet.

  A 38 μm-thick polyethylene terephthalate film having a release layer is used as a base sheet, and a photocurable resin is first formed on the entire surface as a release layer by a coater printing method at a thickness of 5 μm. A water-soluble resin made of an acrylate copolymer was formed by gravure printing as a water-soluble pattern layer having a thickness of 1 μm.

  Next, using a resistance heating type vacuum vapor deposition apparatus, Sn and AL were mixed in the vapor deposition crucible to form a radio wave transmitting metallic gloss layer with a thickness of 200 mm on the entire surface.

  In the above vapor deposition step, the mixing ratio (weight ratio) of Al / Sn is four types: (1) 0.01, (2) 0.02, (3) 0.05, (4) 0.1. went.

  Next, the film was passed through a washing machine at a traveling speed of 10 m / min, and the water-soluble pattern layer and the radio wave permeable metal vapor deposition layer formed thereon were peeled and removed (water washing treatment).

  Next, a vinyl chloride resin was used as an adhesive layer, and the entire surface was formed by gravure printing so as to have a thickness of 1 μm (film thickness when dried) to obtain a radio wave transmissive transfer material.

  The radio wave transmission transfer material thus obtained was subjected to a moisture resistance acceleration test in a constant temperature and humidity layer at a temperature of 60 ° C. and a humidity of 95% for 96 hours. The total light transmittance was 40 before the test. After the test, (1) 46%, (2) 43%, (3) 42%, and (4) 41% all showed excellent corrosion resistance.

  In addition, as a comparative example, only the point that the radio wave permeable metallic luster layer was formed only from Sn was changed from the above process, and the radio wave transmissible transfer material was obtained in the same manner as in the above example. The total light transmittance was 40%, 70% after the test, and the corrosion resistance was inferior.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for decoration of various molded products such as communication devices such as mobile phones, information devices inside automobiles, and home appliances, and is industrially useful.

It is sectional drawing which shows one Example of the manufacturing method of the radio wave transmission transcription | transfer material of this invention. It is sectional drawing which shows one Example of the radio wave transmission transcription | transfer material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Radio wave transmission transfer material 2 Base sheet 3 Release layer 4 Water-soluble pattern layer 5 Radio wave transmission metallic luster layer 6 Adhesive layer 7 Pattern layer 8 Front anchor layer 9 Rear anchor layer

Claims (8)

A release layer is entirely formed on a substrate sheet having peelability, and then a water-soluble pattern layer is partially formed thereon, and then a metal and tin having a higher ionization tendency than tin are formed thereon. Forming a fine island-shaped radio wave-transmitting metallic luster layer made of an alloy entirely, then performing a water washing treatment to peel and remove the water-soluble pattern layer and the radio wave transmitting metallic luster layer formed thereon, Next, a method for producing a radio wave transmitting transfer material, wherein the adhesive layer is formed entirely or partially. 2. The method for producing a radio wave permeable transfer material according to claim 1, wherein the radio wave permeable metallic luster layer is made of an alloy of tin and aluminum. 3. The production of a radio wave transmissive transfer material according to claim 2, wherein the atomic concentration of the outermost layer of the radio wave permeable metallic luster layer (Atomic Concentration) measured with a fluorescent X-ray measuring device is Al / Sn = 0.01-2.0. Method. 3. The production of a radio wave transmitting transfer material according to claim 2, wherein the atomic concentration of the outermost layer of the radio wave transmitting metallic luster layer measured with a fluorescent X-ray measuring device is Al / Sn = 0.15 to 1.5. Method. A release layer, a patterned radio wave-transmitting metallic gloss layer made of a fine island-like shape made of an alloy of metal and tin, which has a higher ionization tendency than tin, and an adhesive layer on a base sheet having peelability A radio wave transmitting transfer material characterized by being formed at least. 6. The radio wave transmitting transfer material according to claim 5, wherein the radio wave transmitting metallic luster layer is made of an alloy of tin and aluminum. The radio wave transmitting transfer material according to claim 6, wherein the atomic concentration of the outermost layer of the radio wave transmitting metallic luster layer measured with a fluorescent X-ray measuring device is Al / Sn = 0.01-2.0. The radio wave transmitting transfer material according to claim 6, wherein the atomic concentration of the outermost layer of the radio wave transmitting metallic luster layer measured with a fluorescent X-ray measuring device is Al / Sn = 0.15 to 1.5.

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