JP2006130774A - Decorative sheet for molding and molding with decoration - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To keep high brightness in a decorative sheet for molding in which at least a decorative layer, a thin metal film layer, and an adhesive layer formed out of an adhesive are laminated on a substrate resin layer and in a molding with decoration decorated by using the decorative sheet. <P>SOLUTION: In the decorative sheet for molding in which at least the decorative layer, the thin metal layer, and the adhesive layer formed out of the adhesive are laminated on the substrate resin layer, a moisture curable reactive hot melt adhesive is used as the adhesive. The molding with decoration is decorated by using the decorative sheet. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative sheet for molding used for decorating the surface of a molded product and a molded article with decoration that is decorated using the sheet.

  Conventionally, a decorative sheet for molding is known which is used in combination with molding of the above molded product in order to enhance the design of the surface of the molded product such as a decorative panel for automobiles, a housing of home appliances or a mobile phone. . The decorative sheet for molding used in the film insert method includes a non-laminate type and a laminate type. Since the non-laminate type has only one base resin sheet, the cost can be reduced. However, since a variety of decorative layers are not used in the first place, and the ink used for the decorative layers cannot withstand the heat at the time of molding, it is impossible to obtain a high-quality molded article. For this reason, a laminated type decorative sheet for molding has been frequently used recently.

  The basic configuration of the laminated type decorative sheet for molding is a configuration in which the base resin sheet-1, the decorative layer, the adhesive layer, and the base resin sheet-2 are laminated in this order from one side of the sheet. Moreover, the basic composition of the molded object with decoration is {[base resin sheet-1 / decoration layer / adhesive layer / base resin sheet-2] / binder ink} from the surface side of the molding decorative sheet. / It is the structure which laminated | stacked in order of the molded object. Here, the binder ink is a binder for bonding the decorative sheet for molding and the molded body. In order to obtain a molded article with decoration, vacuum molding, pressure molding, pressure vacuum molding, or injection molding is performed in a state where a binder ink is applied to the decorative sheet for molding.

  Patent Document 1 discloses a technique in which a glittering decorative sheet is heated and softened using a heat source set at a temperature of 400 to 750 ° C. and then deformed by vacuum or pressure forming within 5 seconds. ing. Here, the reason why the heating temperature is set to 400 to 750 ° C. is to prevent the heating of the glittering layer due to thermal radiation particularly when heating from the glittering layer side. Further, the reason for deforming by vacuum or pressure forming within 5 seconds is that, if a too long time is taken, shrinkage of the glittering decorative sheet starts and microcracks are generated in the glittering layer. Here, the glittering layer refers to a metal thin film layer. The molded body thus obtained is trimmed with an unnecessary sheet using a die set or the like to become a final product.

  By the way, the adhesive for laminating conventionally used frequently for adhesion between the decorative layer and the base resin sheet includes an adhesive for dry laminating or a thermosensitive adhesive. For example, Patent Document 2 discloses a laminate material using a heat-sensitive adhesive as a laminating adhesive.

JP-A-2002-192649 (paragraph number 0008, etc.) JP 2001-098231 (abstract, etc.)

  However, the above-described conventional decorative sheet for molding has the following problems. A high temperature standing test in which a decorated molded body obtained using an aromatic polyester-based two-component solvent adhesive as an adhesive for dry lamination is allowed to stand at a temperature of 85 ° C. for 240 hours, a temperature of 60 ° C. and a humidity of 95% RH. Conventionally, it is used for the high temperature and high humidity test that is allowed to stand for 240 hours in the environment of the above and the thermal shock test that repeats the cycle that is left for 1 hour at 85 ° C. after being left for 1 hour at −40 ° C. Conventional adhesives have poor adhesive strength and heat resistance. For this reason, an adhesive layer and a decoration layer will peel, a micro crack or a wrinkle will enter into the metal thin film layer which forms a decoration layer, and a brightness | luminance will fall. In addition, even when a decorated molded body obtained using a thermosensitive adhesive as a laminating adhesive is subjected to the same environmental test as described above, the metal thin film layer forming the decorative layer has microcracks or wrinkles. Enters and brightness decreases.

  In view of such a problem, the present invention provides a decorative sheet for forming a laminate structure having at least a decorative layer, a metal thin film layer, and an adhesive layer formed of an adhesive on the base resin sheet. An object of the present invention is to maintain high luminance in a decorated molded body decorated with a sheet.

  As a result of intensive studies to solve the above problems, when the adhesive in the present invention is used, lamination can be performed while maintaining high luminance at a low temperature (50 ° C. or lower), and even at a high temperature (50 ° C. or higher). It was found to have adhesive strength. It has also been found that the occurrence of microcracks or wrinkles in the metal thin film layer can be suppressed even when vacuum forming, pressure forming, or pressure forming is performed. Moreover, foaming of an adhesive agent can also be suppressed by moisture absorption of the base resin sheet. For this reason, it is possible to suppress the occurrence of microcracks or wrinkles in the metal thin film layer, and to obtain an excellent decorative sheet for molding having a high-luminance metallic luster and a molded article with decoration. It came. In particular, the adhesive preferably has an adhesive layer with a 100% modulus of 3 to 9 MPa and an elongation of 30 to 1000%. In general, the elastic modulus is called modulus. Here, 100% modulus is the tensile elastic modulus when stretched to twice the initial value of the sample. A material having a large elastic modulus is hard to plastically deform, and thus tends to be hard and brittle. On the other hand, a material with a low elastic modulus is a material that is easily plastically deformed, soft, and sticky. The thickness of the adhesive layer is preferably in the range of 3 microns or more and 100 microns or less.

  According to the present invention, it is possible to obtain a decorative sheet for molding and a molded article with decoration that maintain high luminance.

  Hereinafter, embodiments of the present invention will be described in detail.

  The basic configuration of the molding decorative sheet according to the embodiment of the present invention is a configuration having at least a decorative layer, a metal thin film layer, and an adhesive layer between two base resin sheets.

[Base resin sheet]
Although the commercially available thermoplastic resin sheet can be used for the base resin sheet used, it is not specifically limited. For example, acrylic, polycarbonate, alloy made of polycarbonate and polyester resin, ABS, AS, polystyrene, polyolefin, vinyl chloride, and PET resin sheets can be used.

[Decoration layer]
As a decorative layer, for example, Gloss type NAN series, CG series, VAR series, or pearl ink VG series manufactured by Teikoku Ink Mfg. Co., Ltd., screen printing, offset printing, gravure printing, etc., designs, symbols, etc. The display portion can be formed. In order to easily perform more complicated and design-rich printing, it is preferable to use an electronic printing machine such as a melting type thermal transfer printer, a sublimation type thermal transfer printer, an ink jet printer, a toner transfer type printer, or the like. That is, by using at least one type of printer of sublimation type thermal transfer system, toner electronic system, electrostatic image system, laser exposure thermal development transfer system, ink jet system, thermal transfer system, and heat coloring system, for example, cyan (C), A display portion composed of light-transmitting colors, patterns, and symbols can be formed by using a plurality of micro dots such as magenta (M) and yellow (Y).

  The general thickness of the decorative layer is about 0.1 to 30 microns. When the decoration layer is 0.1 micron or less, the color of the decorated part is too thin, and a clean pattern or symbol cannot be expressed, which is not preferable. In addition, when the decorative layer is 30 microns or more, the decorative layer is too thick to be easily deformed into a three-dimensional shape when vacuum forming, pressure forming, pressure vacuum forming, or injection forming is performed. Microcracks or wrinkles are likely to enter the layer, which is not preferable. In addition, when forming a decoration layer, a metal thin film layer, and an adhesive bond layer on a base resin sheet, corona discharge treatment, plasma treatment, UV treatment, primer as a pretreatment for improving adhesiveness, if necessary. You may perform coating etc.

[Metal thin film layer]
In this embodiment, the metal thin film layer is formed so as to be in contact with the decorative layer. Examples of the material for the metal thin film layer include gold, silver, aluminum, chromium, nickel, indium, tin, and zinc. The method for producing the metal thin film layer includes a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method, but is not particularly limited. The metal thin film layer formed by vapor deposition is particularly called “metal vapor deposition layer”. Note that the metal thin film layer may be formed by a method other than the vapor deposition method. Here, the sputtering method is a method in which argon (Ar) ions generated by glow discharge in a low-pressure argon gas close to vacuum are accelerated and collided with a target to scatter the raw material and adhere to the product. Also, the ion plating method means that molecules and atoms of the deposition material deposited in a low-pressure Ar gas close to a vacuum are ionized and excited through the glow discharge region, and a negative high voltage together with neutral particles. It is a method to fold it into goods.

  As described above, as a method of forming the metal thin film layer on the base resin sheet, the metal is vapor-deposited in advance using a method of directly depositing metal on the base resin sheet, a sublimation thermal transfer printer or a thermal transfer printer. There is a method of printing by preparing an ink ribbon and hot stamping. Moreover, screen printing, offset printing, gravure printing, etc. can also be employ | adopted as a method of forming a metal thin film layer using SP mirror ink (product name) by Teikoku Ink Mfg. Co., Ltd.

[Thickness of metal thin film layer]
The thickness of the metal thin film layer is arbitrarily selected depending on the type of metal and appearance requirements, and is not particularly limited. For example, in the case of indium, the thickness of the metal thin film layer is set in the range of 100 angstroms to 1500 angstroms from the viewpoint of both high brightness with metallic luster (Gs = 130 or more) and microcracks and resistance to cracking. preferable. The thickness of the metal thin film layer is more preferably in the range of 200 angstroms to 100 angstroms, and still more preferably in the range of 300 angstroms to 700 angstroms. When the thickness of the metal thin film layer is less than 100 angstroms, it is not preferable because the metallic luster of indium with high brightness (Gs = 130 or more) cannot be obtained. Also, when the thickness of the metal thin film layer is thicker than 1500 angstroms, it is easy to form microcracks and wrinkles in the same film during vacuum forming and pressure forming, and has excellent high-brightness metallic luster (Gs = 130 or more). It is not preferable because a decorative sheet cannot be obtained.

[Moisture-curing reactive hot-melt adhesive used to form the adhesive layer]
The moisture-curable reactive hot melt adhesive for forming the adhesive layer in the present invention is preferably a polyurethane-based, polyurethane-polyester-based or polyurethane-polyether-based hot melt adhesive, but is not limited thereto. Is not to be done. The curing reaction mechanism of such an adhesive is a mechanism in which a urethane prepolymer having an isocyanate group at a molecular terminal is cured by reacting with moisture (water). When there is a urethane bond (—NHCOO) in the molecular chain, it reacts with an isocyanate group to form an allophanate bond and cure. When the molecular chain has a urea bond (-NHCONH), it reacts with an isocyanate group to form a biuret bond, and is cured while taking a three-dimensional crosslinked structure. For this reason, the cured product has high heat resistance and excellent adhesive strength. Generally, the curing time of a moisture curable reactive hot melt adhesive is about 1 to 5 days at a temperature of 25 ° C./humidity of 50% RH.

[Rules for thickness of adhesive layer]
The thickness of the adhesive layer is more preferably 3 to 100 microns. A more preferred adhesive layer thickness is 5 to 80 microns. Furthermore, the more preferable thickness of the adhesive layer is 10 to 50 microns. When the thickness of the adhesive layer is 3 microns or more, thickness unevenness and streaks during coating are less likely to occur, so the risk of unevenness on the surface of the metal thin film layer is reduced. For this reason, high brightness (Gs = 130 or more) of the metal thin film layer is easily obtained. Moreover, when the thickness of the adhesive layer is 100 microns or less, the adhesive layer easily absorbs the difference in elongation rate of the metal thin film layer, and it is difficult for the adhesive layer and the metal thin film layer to be displaced. Cracks and wrinkles are unlikely to occur, and a high-brightness metallic luster (Gs = 130 or more) is easily obtained. Further, during the reaction, the adhesive layer is difficult to take in excessive moisture, and the generation of carbon dioxide gas (CO ₂ ) can be prevented, the microcracks and wrinkles of the metal thin film layer are reduced, and the high-brightness metallic luster (Gs = 130 or more) is easily obtained. When the thickness of the adhesive layer is 5 to 80 microns, and further 10 to 50 microns, it is possible to further reduce thickness unevenness during coating and more efficiently absorb the difference in elongation rate from the metal thin film layer. .

[Range of 100% modulus and tensile elongation at break]
An adhesive layer having a 100% modulus of 3 to 9 MPa and an elongation of 30 to 1000% is more adhesive than a layer of 100% modulus of less than 3 MPa and a tensile elongation at break of less than 30%. The layer has a moderately high hardness and a sufficient elongation. Thereby, the microcrack is hard to enter the metal thin film layer of the laminate film during sheet molding (preform), and the risk of the laminate film itself being cut can be further reduced. Therefore, the high brightness (Gs = 130 or more) of the metal thin film layer can be further sustained.

  In addition, the adhesive layer having a 100% modulus of 3 to 9 MPa and an elongation rate of 30 to 1000% is compared with the adhesive layer having a 100% modulus of less than 3 MPa and a tensile breaking elongation significantly exceeding 1000%. In addition, the adhesive layer has an appropriate hardness and can support the metal thin film layer more firmly during sheet molding (preform). Further, the metal spacing of the metal thin film layer is not excessively widened, and pseudo microcracks and wrinkles are less likely to occur. For this reason, high brightness (Gs = 130 or more) of the metal thin film layer is more easily obtained.

  In addition, the adhesive layer having a 100% modulus of 3 to 9 MPa and an elongation rate of 30 to 1000% is compared with that having a 100% modulus significantly exceeding 9 MPa and a tensile elongation at break of less than 30%. In addition, since the adhesive layer has a moderately soft and easy-to-extend property, it is difficult for microcracks to enter the metal thin film layer during sheet molding (preform), or the base sheet constituting the molding decorative sheet breaks or Wrinkles are less likely to occur due to the stretching. For this reason, high brightness (Gs = 130 or more) of the metal thin film layer is more easily obtained.

  An adhesive layer having a 100% modulus of 3 to 9 MPa and an elongation of 30 to 1000% has a 100% modulus greatly exceeding 9 MPa and a tensile breaking elongation exceeding 1000%. In contrast, the apparent intermolecular crosslink density of the base resin constituting the adhesive is not extremely dense and is difficult to stretch, so moisture in the air is absorbed during storage of the decorative sheet for molding. It becomes difficult. When the sheet is molded using the decorative sheet for molding in such a state, the moisture absorbed can be further reduced from foaming at the interface of the metal thin film layer, and the metal thin film layer may have microcracks or wrinkles. Can be further reduced. For this reason, high brightness (Gs = 130 or more) of the metal thin film layer is more easily obtained.

[Viscosity of moisture-curing reactive hot melt adhesive]
The viscosity of the reactive hot melt adhesive used for the adhesive layer (JIS K6862 test method for measuring melt viscosity of hot melt adhesive) is preferably 300 to 30,000 mPa · S. More preferably, the viscosity is 500 to 20,000 mPa · S. More preferably, the viscosity is 2000 to 10,000 mPa · S. However, the measurement temperature is 120 ° C. When the viscosity is 300 mPa · S or more, dripping or the like hardly occurs at the time of application, and workability is further improved. Further, when the viscosity is 30,000 mPa · S or less, it is difficult to form streaks or irregularities in the adhesive during application, and the risk of the laminated film hitting waves when laminated is reduced. As a result, high brightness (Gs = 130 or more) of the metal thin film layer is more easily obtained.

[Temperature during application of moisture-curing reactive hot melt adhesive]
The temperature when the moisture-curing reactive hot melt adhesive is applied to an adherend using an applicator is preferably in the range of 80 to 150 ° C. More preferably, the temperature is in the range of 90 to 140 ° C. More preferably, the temperature is in the range of 100 to 120 ° C. When the temperature is 80 ° C. or higher, the moisture-curing reactive hot melt adhesive is not too high in viscosity and is easy to apply by hand with an applicator. When the temperature is 150 ° C. or lower, the decomposition of isocyanate (—NCO) in the moisture-curing reactive hot melt adhesive hardly occurs during the operation, and the generation of carbon dioxide gas can be reduced. As a result, wrinkles are less likely to enter the metal thin film layer, and the high luminance (Gs = 130 or more) of the metal thin film layer is more easily obtained.

[Definition of position of adhesive layer]
The adhesive layer may be provided on or below the metal thin film layer or the decorative layer, or both, and can be arbitrarily set.

[Position of decorative layer and metal thin film layer]
The decorative layer may be above or below the metal thin film layer, or both, and can be arbitrarily set. Here, when a metal thin film layer is provided after providing a light-transmitting decorative layer as a decoration layer, various colors of metal thin film layers can be expressed. When a colored layer having high light shielding properties is provided after the metal thin film layer, the light shielding property of the metal thin film layer can be enhanced. Here, the colored layer having a high light hiding property refers to a layer made of highly concentrated colored ink or the like.

Hereinafter, the basic configuration of a suitable decorative sheet for molding will be described. 1 to 5 show the basic configuration of the following five types of decorative sheets for molding. Here, a metal thin film layer formed by vapor deposition (metal vapor deposition layer) is shown.
Part 1
Base resin sheet-1 / decorative layer-A / metal deposition layer-a / adhesive layer / base resin sheet-2
Part 2
Base resin sheet-1 / metal deposition layer-a / decorative layer-A / adhesive layer / base resin sheet-2
Part 3
Base resin sheet-1 / decoration layer-A / metal vapor deposition layer-a / decoration layer-B / adhesive layer / base resin sheet-2
4
Substrate resin sheet-1 / metal deposition layer-a / decorative layer / metal deposition layer-b / adhesive layer / substrate resin sheet-2
Part 5
Decorative layer-A / Base resin sheet-1 / Metal vapor deposition layer-a / Decorative layer-B / Adhesive layer / Base resin sheet-2

[Binder ink]
The binder ink is a binder used for bonding a decorative sheet for molding to a molded product used for vacuum molding, pressure molding or pressure vacuum molding, or an injection molding resin. The layer made of the binder ink is not an essential layer. When the base resin sheet constituting the decorative sheet for molding is an acrylic resin and the molded article or injection molding resin as an adherend is an acrylic resin, the acrylic or vinyl chloride-vinyl acetate copolymer system is used. It is desirable to use a binder ink. Further, when the base resin sheet is a polycarbonate resin and the molded article or the injection molding resin as the adherend is a polycarbonate resin, it is desirable to use a polycarbonate binder ink. The binder ink can be formed by screen printing, gravure printing or the like, but is not particularly limited to such a forming method. The thickness of the binder ink is generally about 5 to 20 microns.

[Receptive layer]
In particular, in a sublimation type thermal transfer printer, when a display unit composed of colors, designs, and symbols is formed, a receiving layer for receiving three colors of cyan (C), magenta (M), and yellow (Y) is formed. The receiving layer is generally formed from a vinyl chloride / vinyl acetate copolymer. As a method of forming this receiving layer, it may be formed by printing using an ink ribbon dedicated to the receiving layer, or may be formed in advance by screen printing or gravure printing. The forming method can be arbitrarily determined.

[Protective layer]
In particular, when forming a display unit consisting of colors, designs, and symbols using a melt-type thermal transfer printer, sublimation-type thermal transfer printer, etc., protection is provided for the purpose of improving the weather resistance, abrasion resistance, and solvent resistance of the display unit. Layers can be employed. Resin that can be used as the protective layer includes polyester-based, acrylic-based, and polycarbonate-based resins in consideration that transparency is a requirement. These resins may be used alone or in combination of two or more, but it is more preferable to use a polyester-based resin film. As a method for forming the protective layer, similarly to the method for forming the receiving layer, the protective layer may be formed by printing using an ink ribbon dedicated to the protective layer, or may be formed in advance by screen printing or gravure printing. The forming method can be arbitrarily determined. Moreover, in order to improve weather resistance, abrasion resistance, and solvent resistance, an ultraviolet absorber, an antioxidant, a filler, and various additives can be arbitrarily added.

  Next, the molded body used will be described.

[Molded body used for vacuum forming, pressure forming, pressure forming, and resin that can be used for injection molding]
In the present invention, a thermoplastic resin or a thermosetting resin can be used. Examples of the thermoplastic resin include ABS, AS, styrene, vinyl chloride, acrylic, polycarbonate, or polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, Examples thereof include polyolefin resins such as ethylene-propylene-butene copolymers and olefin thermoplastic elastomers. Examples of the thermosetting resin include a urethane resin, an unsaturated polyester resin, an epoxy resin, and a phenol resin, which are two-part curable resins.

  Next, a molding method and an evaluation method will be described.

[Vacuum forming]
In the vacuum forming adopted here, a transfer sheet is placed on or opposite to the surface of a three-dimensional product such as a molded product, as appropriate, with an adhesive interposed between them, and the pressure difference due to vacuum suction of the three-dimensional product. This is a transfer method using a so-called vacuum forming lamination method in which a transfer layer of a transfer sheet is transferred to the surface of a three-dimensional article.

[Pneumatic forming]
In the air pressure molding, the decorative sheet for molding is heated and softened once, and it is brought into close contact with the mold by compressed air of 294,198 Pa (3 kg / cm ² ) to 490,330 Pa (5 kg / cm ² ) A method for obtaining a shape. A deep-drawn molded article having a higher molding pressure and superior mold reproducibility compared to vacuum molding can be obtained.

[Pneumatic vacuum forming]
The pneumatic vacuum forming is a method in which the decorative sheet for molding is molded along a mold by using the above vacuum and compressed air together.

[Method of simultaneous injection molding]
The injection molding simultaneous decorating method is a method in which a decorative sheet for molding is placed between both male and female molds for injection molding, and then a resin in a fluid state is injected and filled into the mold, simultaneously with the molding of the resin molding. This is a method of laminating sheets for simultaneous injection molding and decorating a resin molded product by lamination or transfer to obtain a decorative molded product.

[Measurement of 100% modulus and tensile elongation at break of adhesive layer]
Applicator (Nordson Co., Ltd.) a moisture-curable reactive hot-melt adhesive (manufactured by Hitachi Chemical Co., Ltd., product name: Hibon 4830) on a Teflon (registered trademark) sheet (thickness: 1 mm, size: A4) manufactured by NICHIYASU ), Product name: MX4424), and heated to 110 ° C. to a thickness of 100 microns. A Teflon (registered trademark) sheet is placed on the applied adhesive to form a sandwich, and one pass is performed using the above laminator. The adhesive is left in a room at a temperature of 23 ° C./humidity of 50% RH for 3 days. Harden. This is designated as Adhesive-A.

  Next, in order to measure the 100% modulus and the tensile elongation at break, the adhesive-A cured using the dumbbell 1B was punched out, and the Teflon (registered trademark) sheets above and below the adhesive layer were peeled off. -1. The test standard is JIS K7127, and the pulling speed is 50 mm / min. The measurement is performed in a room at a temperature of 23 ° C./humidity of 50% RH using a strograph VES5D (product name) manufactured by Toyo Seiki Seisakusho.

[Method for measuring thickness of metal thin film layer]
Measurement is performed in a temperature 23 ° C./humidity 50% RH environment using a Nanostep 3000 model (product name) manufactured by Rank Thera Hobson.

[Environmental testing]
The environmental test employs three types of tests: a high temperature storage test, a high temperature and high humidity test, and a thermal shock test. The equipment used for the high temperature storage test is ETAC HT210 type (product name) manufactured by Enomoto Kasei Co., Ltd. The equipment used for the high temperature and high humidity test is ETAC NT510 type (product name) made by Enomoto Kasei Co., Ltd. The apparatus used for the impact test is ETAC FH20C (product name) manufactured by Enomoto Kasei Co., Ltd. The conditions for the high temperature standing test are to stand at a temperature of 85 ° C. for 240 hours. The high temperature and high humidity test is performed at a temperature of 60 ° C./humidity of 95% RH for 240 hours. In the thermal shock test, a cycle of leaving at a temperature of −40 ° C. for 1 hour and then leaving at a temperature of 85 ° C. for 1 hour is repeated 100 times.

  The acceptance criteria for the environmental test are (1) no peeling between the adhesive layer and the decorative layer in each of the three types of tests, (2) the metal thin film layer is visually free of microcracks or wrinkles, (3) Gs is 130 or more.

[Method for confirming microcracks and wrinkles in metal thin film layer]
After the decorative sheet for molding is vacuum-formed, pressure-formed, or vacuum-pressure-formed, NSZF-44FT (product name), a stereomicroscope manufactured by Carlton Co., Ltd., is used in an environment where the measurement temperature is 23 ° C./humidity 50% RH. And visually determined at a magnification of 10 times.

[Brightness measurement method]
The luminance is measured by a specular glossiness-measuring method defined in JIS Z-8741. In this measurement, the luminance is quantitatively evaluated by the gloss value (Gs) at 60 °. In this embodiment, Gs is 130 or more as a high luminance condition. As a measuring device, a digital variable gloss meter UGV-5D type (product name) manufactured by Suga Test Instruments Co., Ltd. is used. The measurement is performed in an environment of temperature 23 ° C./humidity 50% RH.

  Next, examples of the present invention will be described. In the following examples and comparative examples, the metal thin film layer will be described as an example of a metal vapor deposition layer that is one form thereof.

Table 1 shows the properties of the adhesives used in Examples and Comparative Examples described below and the adhesive layers formed by the same adhesives.

In Table 2, the result of the characteristic evaluation of the molded object with a decoration in each Example and each comparative example demonstrated below is shown collectively.

[Example 1]
The basic configuration of the decorative sheet for molding was the configuration described above. As a result, the structure of the molded article with decoration is: base resin sheet-1 / decoration layer-A / metal vapor deposition layer-a / adhesive layer / base resin sheet-2 / binder ink / molded body. It was.

  As the base resin sheet-1, a polycarbonate resin sheet having a thickness of 125 microns (Mitsubishi Engineer Plastics, product name: Ipylon, size: A4) is a sublimation thermal transfer printer (manufactured by Victor Co., Ltd., product name). : Color printer Trueprint 3500). Next, the receiving layer (manufactured by Victor Co., Ltd., vinyl chloride resin, trade name: JP-D304F) was set on the printer and printed. Next, a sublimation color ink ribbon (manufactured by Victor Co., Ltd., trade name: JP-D304I) was set, and characters, pictures, and symbols were printed on demand to form a decorative layer. Next, in order to form a metal vapor deposition layer, an ink ribbon on which aluminum was vapor deposited to a thickness of 300 angstroms was set in the same printer, and letters and symbols were printed on demand. Next, a moisture curing type reactive hot melt adhesive (manufactured by Hitachi Chemical Co., Ltd., product name: Hibon 4830) was heated to 110 ° C. using an applicator (manufactured by Nordson Co., Ltd., product name: MX4424). However, it was applied to a thickness of 10 microns to form an adhesive layer. Finally, the same resin sheet as the base resin sheet-1 is used as the base resin sheet-2, and this is laminated on the adhesive layer, and then laminated at 60 ° C. using a laminator manufactured by Fuji PLA Co., Ltd. went. Thereafter, the adhesive was cured by leaving it in a room at 23 ° C./50% RH for 3 days to obtain a decorative sheet for molding.

  Next, in order to form a binder ink layer on the back surface of the base resin sheet-2 of the decorative sheet for molding, binder ink IMB-009 (product name) manufactured by Teikoku Mfg. Co., Ltd. was used as a 200 mesh screen. Was used to print to a thickness of 20 microns after drying (80 ° C./1 hour) to form a binder ink layer.

  First, a molding (made by Mitsubishi Rayon, product name: Acrypet VH) made of an acrylic resin shaped like a mobile phone casing is cooled with a cooling mold (hereinafter referred to as “vacuum mold”). Was set in a vacuum forming machine adjusted to 30 ° C. Next, the decorative sheet for molding was heated by an infrared heater at 350 ° C. for 10 seconds, and then inserted between vacuum molding dies. Next, the pressure was reduced from the vacuum air hole of the lower mold, and vacuum molding was performed. After cooling for 3 seconds, the vacuum molding mold was opened to obtain a molded body. Finally, using a die set, an unnecessary sheet was punched out from the molded body to obtain a decorated molded body.

Next, an environmental test of the molded article with decoration obtained in this way was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, and the aluminum vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, free from microcracks and wrinkles, and was excellent in high luminance (Gs = 140). In addition, as a vacuum forming machine, Seiko Sangyo Co., Ltd. product name: 300X was used.
[Example 2]

The adhesive used in Example 1 was applied using the applicator used in Example 1 so that the thickness was 30 microns. Other conditions were the same as in Example 1. An environmental test of the decorative molded body thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, and the aluminum vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, free from microcracks and wrinkles, and was excellent in high luminance (Gs = 143).
[Example 3]

  The adhesive used in Example 1 was applied using the applicator used in Example 1 so that the thickness was 50 microns. Other conditions were the same as in Example 1. An environmental test of the decorative molded body thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, and the aluminum vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, free from microcracks and wrinkles, and was excellent in high luminance (Gs = 148).

[Example 4]
The basic configuration of the decorative sheet for molding was the basic configuration 2 described above. As a result, the configuration of the molded article with decoration is: base resin sheet-1 / metal deposition layer-a / decoration layer-A / adhesive layer / base resin sheet-2 / binder ink / molded body. It was.

  As the base resin sheet-1, an acrylic resin sheet (manufactured by Sumitomo Chemical Co., Ltd., product name: Technoloy S001, size A4) having a thickness of 75 microns was set in the same printer used in Example 1. Subsequently, an ink ribbon on which indium was vapor-deposited to a thickness of 670 angstroms was set in the printer, characters and symbols were printed, and a metal vapor-deposited layer was formed. Next, FM ink 3101 white (trade name) manufactured by Jujo Chemical Co., Ltd. was screened using a 200-mesh screen so that the thickness of the heat-cured (80 ° C./20 minutes) coating film would be 7 microns. Printed to form a decorative layer. The constant temperature dryer used for heat drying was ETAC HT210 type (product name) manufactured by Enomoto Kasei Co., Ltd. Next, a moisture-curing reactive hot melt adhesive (manufactured by Hitachi Chemical Polymer Co., Ltd., product name: Hibon 4820) was heated to 110 ° C. using the same applicator as in Example 1 to a thickness of 13 microns. This was applied to form an adhesive layer. Finally, as the base resin sheet-2, using the same acrylic resin sheet as the base resin sheet-1, it is superimposed on this adhesive layer, and using a laminator manufactured by Fuji PLA Co., Ltd. Lamination was performed at 60 ° C. However, the thickness of the base resin sheet-2 was 200 microns. Thereafter, the adhesive was cured by leaving it in a room at a temperature of 23 ° C./humidity of 50% RH for 3 days to obtain a decorative sheet for molding.

  Next, the binder ink used in Example 1 was printed on the back surface of the base resin sheet-2 of the decorative sheet for molding so as to have a thickness of 12 microns to form a binder ink layer. . The drying conditions and printing conditions were the same as in Example 1. The molded product used in Example 1 was set in a compressed air molding machine in which the temperature of a cooling compressed air mold (hereinafter referred to as “compressed air mold”) was adjusted to 50 ° C. Next, the decorative sheet for molding was heated at 370 ° C. for 10 seconds with an infrared heater, and then inserted between compressed air molds. Next, pressure forming was performed by applying an air pressure of 0.5 MPa from the pressure air hole of the upper mold, and after cooling for 5 seconds, the pressure forming mold was opened to obtain a molded body. Finally, using a die set, an unnecessary sheet was punched out from the molded body to obtain a decorated molded body.

  Next, an environmental test of the molded article with decoration obtained in this way was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the indium vapor-deposited layer, which was a metal vapor-deposited layer, was uniformly stretched, free from microcracks and wrinkles, and excellent in high brightness (Gs = 152). As a pressure forming machine, a vacuum forming machine and pressure forming machine FM160 / 1 manufactured by Minos Co., Ltd. was used.

[Example 5]
The adhesive used in Example 4 was applied using the applicator used in Example 1 so that the thickness was 20 microns. Other conditions were the same as in Example 4. An environmental test of the decorative molded body thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the indium vapor-deposited layer, which was a metal vapor-deposited layer, was uniformly stretched, free from microcracks and wrinkles, and excellent in high brightness (Gs = 168).

[Example 6]
The adhesive used in Example 4 was applied using the applicator used in Example 1 so that the thickness was 45 microns. Other conditions were the same as in Example 4. An environmental test of the decorative molded body thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the indium vapor-deposited layer, which was a metal vapor-deposited layer, was uniformly stretched, free from microcracks and wrinkles, and excellent in high brightness (Gs = 165).

[Example 7]
The basic configuration of the decorative sheet for molding was the basic configuration No. 5 described above. As a result, the structure of the molded article with decoration is as follows: decoration layer-A / base resin sheet-1 / metal deposition layer-a / decoration layer-B / adhesive layer / base resin sheet-2 / binder ink / Molded body.

  As the base resin sheet-1, the acrylic resin sheet used in Example 4 was used. This resin sheet was set in a pigment-based thermal transfer printer (manufactured by ALPS, product name: Micro Dod Printer MD5000). Next, a pigment-based ink ribbon (manufactured by ALPS, product name: MDC-FLCM yellow, cyan, magenta, black) is set in the printer, and characters and symbols are printed on demand to form a decorative layer-A. did. Subsequently, in order to form the metal vapor deposition layer-a on the opposite surface on which the decorative layer-A was formed, an ink ribbon in which tin was vapor deposited to a thickness of 500 angstroms was set in the printer used in Example 1, and on demand. Printing was done. Furthermore, EG POS 852 (product name) manufactured by Teikoku Ink Co., Ltd. was used for the coating film after heat curing (80 ° C./60 minutes) with the constant temperature dryer used in Example 4 using a 300 mesh screen. Screen-printing was performed so that the thickness was 3 microns, and decorative layer-B was formed. Next, a moisture curable reactive hot melt adhesive (product name: Bond 7 manufactured by Nippon SC Co., Ltd.) was applied using the applicator used in Example 1 to a thickness of 47 microns. . As the base resin sheet-2, an ABS resin sheet having a thickness of 500 microns and a size A4 (product name: ABS sheet, manufactured by Sekisui Molding Industry Co., Ltd.) was used and placed on the adhesive layer. Thereafter, the adhesive was cured by leaving it in a room at a temperature of 23 ° C./humidity of 50% RH for 5 days to obtain a decorative sheet for molding.

  Next, in order to form a binder ink layer on the back surface of the base resin sheet-2 of the decorative sheet for molding, B-2 (product name) manufactured by Jujo Chemical Co., Ltd. and a standard product are used as a binder ink. (Diluted solvent product name) was blended so that B-2 / standard product = 100/20, and screen-printed so that the thickness after drying (80 ° C./1 hour) would be 8 microns. Went. The same dryer and screen printer as those used in Example 1 were used.

  First, a molded product made of polycarbonate resin in the shape of a mouse for a personal computer (manufactured by Teijin Chemicals Ltd., product name: Panlite L-1250Z100) was prepared, and a compressed air vacuum mold for cooling (hereinafter referred to as “compressed vacuum vacuum mold” The temperature of the “mold” was set in a compressed air vacuum forming machine adjusted to 50 ° C. Next, the decorative sheet for molding was heated at 350 ° C. for 12 seconds with an infrared heater, and then inserted between compressed air vacuum molding dies. Next, the pressure air vacuum forming is performed by simultaneously applying the air pressure of 0.5 MPa from the pressure air hole of the upper mold and the pressure reduction from the vacuum air hole of the lower mold, and after cooling for 5 seconds, the pressure air vacuum forming mold is opened, A molded body was obtained. Finally, using a die set, an unnecessary sheet was punched out from the molded body to obtain a decorated molded body.

  Next, an environmental test of the molded article with decoration obtained in this way was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the tin vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, had no microcracks and wrinkles, and was excellent in high luminance (Gs = 175). As a compressed air vacuum forming machine, FKS-0631-20 manufactured by Asano Laboratory Co., Ltd. was used.

[Example 8]
The adhesive used in Example 7 was applied using the applicator used in Example 1 so that the thickness was 15 microns. Other conditions were the same as in Example 7. An environmental test of the molded body with decoration thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the tin vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, had no microcracks and wrinkles, and was excellent in high luminance (Gs = 182).

[Example 9]
The adhesive used in Example 7 was applied using the applicator used in Example 1 so that the thickness was 33 microns. Other conditions were the same as in Example 7. An environmental test of the decorative molded body thus obtained was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the tin vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, had no microcracks and wrinkles, and was excellent in high luminance (Gs = 190).

[Example 10]
Using the applicator used in Example 1, the adhesive layer of Example 7 was changed to a moisture-curing reactive hot melt adhesive (product name: Bond 234-9014, manufactured by Nippon SC Co., Ltd.) The coating was applied to a thickness of 95 microns. As the base resin sheet-2, the same base resin sheet-2 used in Example 7 was used. On the back surface of the base resin sheet-2 of this decorative sheet for molding, the binder ink used in Example 7 was printed so as to have a thickness of 15 microns to form a binder ink layer. Other conditions were the same as in Example 7. Thereafter, the adhesive was cured by leaving it in a room at a temperature of 23 ° C./humidity of 50% RH for 4 days to obtain a decorative sheet for molding.

  Next, the base resin sheet -1 of the decorative sheet for molding is set so as to be in direct contact with the injection molding mold in which the casing of the digital camera is molded. As a thermoplastic resin for injection molding, ) Parapet GR 01270 (product name) manufactured by Kuraray Co., Ltd. was used. And as injection molding conditions, injection molding was performed at a cylinder temperature of 240 ° C., an injection pressure of 120 MPa, a screw rotation speed of 70 rpm, and a mold temperature of 80 ° C. Next, the injection mold was opened, the molded body was taken out, and unnecessary sheets were punched out using a die set to obtain a molded body with decoration.

  Next, an environmental test of the molded article with decoration obtained in this way was performed. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the tin vapor deposition layer, which was a metal vapor deposition layer, was uniformly stretched, had no microcracks and wrinkles, and was excellent in high luminance (Gs = 170). As an injection molding machine, HS40-5A manufactured by Nissei Plastic Industry Co., Ltd. was used.

[Example 11]
The basic configuration of the decorative sheet for molding was the above-described basic configuration No. 4. As a result, the configuration of the molded article with decoration is as follows: base resin sheet-1 / metal vapor deposition layer-a / decoration layer / metal vapor deposition layer-b / adhesive layer / base resin sheet-2 / binder ink / molding The body became.

  Base resin sheet-1 was a 125 micron thick polycarbonate resin sheet (manufactured by Bayer, product name: Byhole A4), and was set in the sublimation type thermal transfer printer used in Example 1. Subsequently, an ink ribbon on which indium was vapor-deposited to a thickness of 150 angstroms was set in the same printer, characters and symbols were printed, and a metal vapor-deposited layer-a was formed. Next, letters and symbols were printed by the thermal transfer printer used in Example 7 to form a decorative layer. Next, the thickness of the coating film after drying (90/1 hour) by gravure printing using SP mirror ink (product name) silver (provided for PC) manufactured by Teikoku Ink Co., Ltd. is 0. Metal vapor deposition layer-b was formed so that it might be set to 5 microns. Next, the thickness of the moisture-curing reactive hot melt adhesive (manufactured by Nitta Gelatin Co., Ltd., product name: ARX-1252) was heated to 120 ° C. using the applicator used in Example 1. Was applied to a thickness of 28 microns to form an adhesive layer. The base resin sheet-2 was the same resin sheet (size A4) as the base resin sheet-1, covered with the previous adhesive layer, and laminated at 80 ° C. using the laminator used in Example 1. . Thereafter, the adhesive was cured by leaving it in a room at a temperature of 23 ° C./humidity of 50% RH for 3 days to obtain a decorative sheet for molding.

Next, in order to form a plurality of pushbutton portions of a predetermined shape on the decorative sheet for molding, a heating mold having a shape corresponding to the key top projection surface of the pushbutton switch and engraved 5 mm in the depth direction with the same area and Then, a pressured vacuum forming die for cooling (hereinafter referred to as “pressured vacuum forming die”) for forming the key top into a convex shape was used. The upper resin sheet is arranged so that the acrylic sheet is on the upper mold side and the polyester sheet is on the lower mold side, and the temperature of the heating mold is adjusted to 190 ° C. and the temperature of the pressure vacuum molding mold is adjusted to 30 ° C. The upper resin sheet is heated with a heating mold for 1 second, and after 1 second, the heated upper resin sheet is inserted between the compressed air vacuum forming molds, and is 5 kg / cm ² from the compressed air hole of the upper mold. The air pressure and the vacuum pressure of 80 Torr were simultaneously applied to form a compressed air vacuum. Next, after cooling for 3 seconds, the compressed air vacuum forming mold was opened to obtain a pushbutton switch sheet (hereinafter referred to as a shaped sheet) shaped into a convex shape. Next, the shaped sheet is placed on the jig so that the convex part is on the bottom, and UV curable resin (manufactured by Nogawa Chemical Co., Ltd .: trade name UV130L) is aired inside the key top convex part with a height of 3 mm. It was filled by filling with a dispenser with a dispenser, and cured by ultraviolet irradiation with a high-pressure mercury lamp (120 W / m, irradiation distance 15 cm, irradiation time 15 seconds). Since the concave portion cured in this manner is concaved by 0.5 mm due to the curing shrinkage, a key top member for a pushbutton switch was obtained by further curing by irradiation with ultraviolet rays at an irradiation distance of 15 cm and an irradiation time of 5 seconds. . Then, the unnecessary sheet | seat was punched out using the die set and the molded object with a decoration was obtained.

  Next, an environmental test was performed on the decorated molded body (key top) thus obtained. As a result of the environmental test, there was no peeling between the adhesive layer and the decorative layer, the indium vapor-deposited layer, which was a metal vapor-deposited layer, was uniformly stretched, free from microcracks and wrinkles, and excellent in high brightness (Gs = 200).

[Comparative Example 1]
Except that the adhesive used in Example 1 was changed to a dry laminate type adhesive (manufactured by Dainippon Ink & Chemicals, Inc., product name: Dick Dry LX-901), all conditions were the same as in Example 1. did. As a result of conducting an environmental test on the decorative molded body thus obtained, a high temperature storage test (after 85 ° C./240 hours) and a thermal shock test (−40 ° C./1 hour + 85 ° C./1 hour, 100 cycles) ), Peeling occurred at the interface between the adhesive layer and the metal vapor-deposited layer-a, and microcracks and wrinkles entered the aluminum vapor-deposited layer, which was the metal vapor-deposited layer, and the high luminance was lost (Gs = 80).

[Comparative Example 2]
All conditions were the same as in Example 4 except that the adhesive used in Example 4 was changed to a thermoplastic hot melt adhesive (product name: Diabond DA3130, manufactured by Nogawa Chemical Co., Ltd.). As a result of conducting an environmental test of the molded article with decoration thus obtained, in the high-temperature and high-humidity test (after 60 ° C./95% RH / 240 hours), the interface between the decorative layer-A and the adhesive layer And peeling occurred, and microcracks and wrinkles were formed in the indium vapor-deposited layer, which was a metal vapor-deposited layer, and high luminance was lost (Gs = 43).

[Comparative Example 3]
Except that the adhesive layer used in Example 7 was changed to a heat-sensitive adhesive (manufactured by Hitachi Chemical Polymer Co., Ltd., product name: Hibon 11-803), and a decorative sheet for molding was created using a laminator, All conditions were the same as in Example 7. As a result of conducting an environmental test of the decorative molded body thus obtained, a high temperature standing test (after 85 ° C./240 hours) and a high temperature and high humidity test (temperature 60 ° C./humidity 95% RH / after 240 hours) , Peeling occurs at each interface between the adhesive layer, the decorative layer-B, and the base resin sheet-2, and a tin vapor deposition layer that is a metal vapor deposition layer has microcracks, and a part of the shaped sheet is It broke. Also, the high luminance disappeared (Gs = 25).

  INDUSTRIAL APPLICABILITY The present invention can be used in an industry for manufacturing a decorative molded body and an industry for implementing the molded body, and in particular, manufactures or uses a molded product such as a decorative panel for automobiles, a housing for home appliances, or a mobile phone. It can be suitably used in the industrial field.

It is a figure which shows the basic composition (the 1) of the decorating sheet for shaping | molding of this invention. It is a figure which shows the basic composition (the 2) of the decoration sheet for shaping | molding of this invention different from the structure shown in FIG. It is a figure which shows the basic composition (the 3) of the decoration sheet for shaping | molding of this invention different from the structure shown in FIG. 1 and FIG. It is a figure which shows the basic composition (the 4) of the decoration sheet for shaping | molding of this invention different from the structure shown in FIG.1, FIG.2 and FIG.3. It is a figure which shows the basic composition (the 5) of the decoration sheet for shaping | molding of this invention different from the structure shown in FIG.1, FIG.2, FIG.3 and FIG.

Claims (4)

  In the decorative sheet for forming a laminate structure having at least a decorative layer, a metal thin film layer, and an adhesive layer formed of an adhesive on the base resin sheet, the adhesive layer is used as the adhesive. A decorative sheet for molding, which is a layer formed using a moisture-curable reactive hot melt adhesive.   2. The molding according to claim 1, wherein a 100% modulus of the adhesive layer is in a range of 3 MPa or more and 9 MPa or less, and an elongation percentage of the adhesive layer is in a range of 30% or more and 1000% or less. Decorative sheet.   The decorative sheet for molding according to claim 1 or 2, wherein a thickness of the adhesive layer is in a range of 3 microns or more and 100 microns or less.   A molded article with decoration, which is decorated with the decorative sheet for molding according to claim 1, 2 or 3.

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