JP2007069354A - Metal-like decorative sheet and decorative metal sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal-like decorative sheet excellent in the adhesive to a metal and not peeled even by secondary processing such as punching, bending, deep drawing, etc. <P>SOLUTION: This metal-like decorative sheet A is constituted by integrally laminating a transparent film layer 2 on a modified polyolefinic resin layer 1 and the modified polyolefinic resin layer 1 contains a modified polyolefinic resin in an amount of at least 50 wt.% in total, which is obtained by modifying at least one polyolefinic resin, which is selected from the group consisting of a polyethylenic resin, a polypropylene resin and an ethylene/propylene rubber-based resin, with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative. A metal-like printing due to bright ink is applied to the surface opposed to the modified polyolefinic resin layer in the transparent film layer 2. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metallic decorative sheet used for imparting a metallic design to the surface of housing interior materials such as kitchen doors and storage doors, and home appliances such as a refrigerator, and a makeup using the metallic decorative sheet It relates to a metal plate.

  Conventionally, as surface materials for house interior materials such as kitchen doors and storage doors, and household appliances such as refrigerator doors, coated steel sheets coated with metal plates, polyvinyl chloride films filled with metal powder and polyester There is a decorative metal plate in which a decorative sheet obtained by laminating a film is attached to a steel plate via an adhesive.

  The coated steel sheet has a problem that the coating film is peeled off during processing, the coating film is cracked, and there is a problem in workability, or the coating film is easily damaged. In addition, a decorative sheet obtained by laminating a polyester film on a polyvinyl chloride film filled with metal powder has a problem in that it cannot sufficiently exhibit the target metallic design.

  In addition, as a metallic decorative sheet having a metallic design, for example, a decorative sheet in which a hairline process is applied to the back surface of a synthetic resin sheet that is an outermost layer, and a metal thin film and a synthetic resin layer are laminated. Is disclosed (Patent Document 1). In this decorative sheet, when the hairline processing is performed on the back surface of the synthetic resin sheet, there is a problem that the appearance quality is easily deteriorated because scratches are generated or dust is attached.

  Furthermore, the metallic layer printed matter which laminated | stacked the base material layer, the metal thin film layer, the printing layer, and the transparent film layer in this order, and provided the convex printing layer synchronized with the pattern of the said printing layer on the surface of the said transparent film layer. It is disclosed (Patent Document 2). This decorative sheet is used in various parts as a stainless steel-like design that is laminated on steel sheets used for the surface materials of various home appliances and AV equipment, but card paper and paperboard are used as the base layer. However, when applied to steel plates, there are problems such as poor workability such as bending and punching. Furthermore, it is necessary to use an adhesive when the decorative sheet is bonded to a steel plate or the like. For this reason, there is a problem in that the unevenness of the adhesive coating floats on the surface of the decorative sheet, which is not preferable in appearance.

  And the stainless steel foil laminated product of the structure where the sheet | seat by which a synthetic resin film is stuck on the single side | surface of stainless steel foil was laminated | stacked on the surface of the shaping | molding base | substrate was disclosed by making the synthetic resin film side inside (patent document) 3). This stainless steel foil laminate is used for store pillars, sashes and other applications as a stainless steel-like design. Polyvinyl chloride (PVC), polyethylene terephthalate (polyethylene terephthalate), polypropylene as a base layer (PP), acrylic resin, etc. are disclosed to be laminated by adhesion via an adhesive by a dry laminating method, and in the examples, PVC and polyethylene terephthalate are used, and during decorative sheet lamination, An adhesive must be used for adhesion to an adherend such as a steel plate. For this reason, it is inevitable that uneven coating due to the adhesive appears on the surface of the sheet, and there is an appearance defect that the appearance is similar to that of a real metal.

Japanese Patent Laid-Open No. 61-10415 JP 2000-153665 A JP-A-6-91804

  The present invention is a metal-like decorative sheet that is not damaged by the external pressing force, and is not peeled off from an adherend such as a metal plate by secondary processing such as punching, bending, and deep drawing. The present invention also provides a cosmetic metal plate having a beautiful appearance that does not flow out of the resin from the cut surface and does not drop off at the time of cutting or punching, and has no uneven pattern on the paste coating.

  As shown in FIG. 1, the metallic decorative sheet A of the present invention is formed by laminating and integrating a transparent film layer 2 on a modified polyolefin resin layer 1, and the modified polyolefin resin layer 1 is a polyethylene resin. A total of 50% by weight or more of modified polyolefin resins obtained by modifying one or more polyolefin resins selected from the group consisting of polypropylene resins and ethylene-propylene rubber resins with unsaturated carboxylic acids or unsaturated carboxylic acid derivatives In addition, the surface of the transparent film layer 2 facing the modified polyolefin resin layer 1 is subjected to metallic printing with glitter ink.

  The modified polyolefin resin constituting the modified polyolefin resin layer 1 is obtained by modifying each of a polyethylene resin, a polypropylene resin, or an ethylene-propylene rubber resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative. It will be. In addition, the modified polyolefin resin which comprises the modified polyolefin resin layer 1 may be used independently, or 2 or more types may be used together.

  Here, as a method of modifying a polyolefin resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, for example, in the presence of an organic peroxide, crystalline polypropylene and an unsaturated carboxylic acid or unsaturated carboxylic acid derivative In a solvent or in the absence of a solvent, a heat treatment to a melting point or higher of crystalline polypropylene, or when polymerizing a polyethylene resin, a polypropylene resin or an ethylene-propylene rubber resin, an unsaturated carboxylic acid or Examples include copolymerizing an unsaturated carboxylic acid derivative.

  Examples of the polyethylene resin include polyethylene, a copolymer of ethylene containing 50% by weight or more of an ethylene component, and another monomer such as an α-olefin. Examples of the α-olefin include propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, neohexene, 1-heptene, 1-heptene, and the like. Examples include octene and 1-decene.

  Examples of the polypropylene resin include polypropylene, a copolymer of propylene containing 50% by weight of a propylene component and another monomer such as an α-olefin. As the α-olefin, for example, ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, neohexene, 1-heptene, 1- Examples include octene and 1-decene.

  The ethylene-propylene rubber-based resin is a copolymer mainly composed of ethylene and propylene, such as an ethylene-propylene copolymer or a copolymer of ethylene, propylene and a diene compound, and has a rubber elasticity. The thing which has. Examples of the diene compound include 1,4-hexadiene, dicyclopentadiene, norbornene, and the like.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and citraconic acid. Examples of the unsaturated carboxylic acid derivative include acid anhydrides, esters, amides, imides or metal salts of unsaturated carboxylic acids, and specifically include maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, and the like. Methyl acid, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monoethyl ester, fumaric acid Diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, fumaric acid monoamide Fumaric acid diamide, maleimide, N- butyl maleimide, N- phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, and the like can be illustrated potassium methacrylate, maleic anhydride is preferred.

  If the content of the unsaturated carboxylic acid or unsaturated carboxylic acid derivative in the modified polyolefin resin (hereinafter referred to as “modification rate”) is small, the adhesive strength of the modified polyolefin resin layer may decrease, but it is large. When the metallic decorative sheet is produced, there is a possibility of causing uneven extrusion or gelation, so 0.01 to 5% by weight is preferable, and 0.05 to 1% by weight is more preferable.

  In particular, the modification rate of the modified polyolefin resin constituting the first modified polyolefin resin layer 1 is preferably within the above range. If the modification rate is small, the adhesion of the metallic decorative sheet to the metal plate is reduced. This is because the metal-like decorative sheet may be peeled off from the metal plate during the next processing, whereas if it is large, the metal-like decorative sheet tends to cause blocking.

  As the modified polyolefin resin constituting the modified polyolefin resin layer 1, maleic acid-modified polypropylene having a modification rate of 0.05 to 1% by weight is used when the heat resistance of the metallic decorative sheet is important. Is preferred. The modified polyolefin resin constituting the modified polyolefin resin layer 1 is a maleic acid-modified ethylene-propylene having a modification rate of 0.1% by weight or more when the adhesive strength of the metallic decorative sheet to the metal plate is important. A rubber-based resin is preferable, and a maleic acid-modified ethylene-propylene rubber-based resin having a modification rate of 0.1 to 0.5% by weight is more preferable.

  And when the tensile stress at the time of 5% elongation in the modified polyolefin resin layer 1 is small, when a large number of metallic decorative sheets are laminated, the metallic decorative sheet curves in an arc shape, Since there is a possibility that delamination may occur when secondary processing such as punching, bending, and deep drawing is performed on the metallic decorative sheet, 25 to 500 MPa is preferable.

  In addition, the tensile stress at the time of 5% expansion | extension in the said modified polyolefin resin layer says what was measured in the following way. First, a test film having a thickness of 70 μm made of a modified polyolefin resin constituting the modified polyolefin resin layer is prepared. And the tensile stress at the time of 5% expansion | extension in this test film is measured based on JISK7127, and this measured value is made into the tensile stress at the time of 5% expansion | extension in a modified polyolefin resin layer.

  Other thermoplastic elastomers may be added to the modified polyolefin resin layer 1 as long as the effects of the present invention are not impaired. For example, ethylene-propylene rubber, ethylene-propylene-butadiene rubber, ethylene-1 -Butene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-butadiene rubber, poly (4-methyl 1-pentene), ethylene-vinyl acetate copolymer, styrene elastomer and the like.

  Further, the modified polyolefin resin layer 1 may contain a heat resistance stabilizer, a weather resistance stabilizer, a lubricant, a slip agent, a flame retardant, an antistatic agent, an inorganic filler, and the like as long as the function is not impaired. .

  The transparent film layer 2 laminated and integrated on the modified polyolefin resin layer 1 is provided in order to have surface gloss and surface strength. Examples of the film constituting the transparent film layer 2 include a synthetic resin film. Examples of the synthetic resin constituting the synthetic resin film include polyvinyl chloride, polyvinylidene chloride, polypropylene, polyethylene, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon, polystyrene, ethylene-vinyl acetate copolymer, and ethylene. -A vinyl alcohol copolymer, an ionomer, etc. are mentioned, Polypropylene, polyethylene terephthalate, polybutylene terephthalate, and polyvinyl chloride with favorable transparency, smoothness, and glossiness are preferable. In addition, 10-200 micrometers is preferable and, as for the thickness of the transparent film layer 2, 12-35 micrometers is more preferable.

  The surface facing the modified polyolefin resin layer 1 in the transparent film layer 2 is subjected to metallic printing for the purpose of imparting metallic gloss. The surface of the transparent film layer 2 on which the metallic tone printing is applied is subjected to corona discharge treatment, polyethyleneimine, isocyanate compound, silane coupling agent, alkyl titanate, polyamide resin, etc. in order to stabilize ink adhesion. It is preferable that an easy adhesion treatment such as application of a primer is applied.

  Here, the metal is a substance having properties such as high conductivity, thermal conductivity, high strength, ductility, malleability, and relatively difficult to melt. A substance that does not have the above properties. However, these are roughly distinctions and are generally referred to as metals, including those that deviate somewhat from the above properties and those that have intermediate properties between metals and non-metals. Specifically, from atomic number 3 Li to 6 C, atomic number 11 Na to 15 P, atomic number 19 K to 34 Se, atomic number 37 Rb to 52 Up to Te, an element having an atomic number of 55 from Cs to 85 At and an atomic number of 87 or more. In the present invention, the metal includes a compound containing 50% by weight or more of one or more metal elements in addition to the simple substance of the metal.

  Metallic printing refers to printing in which a printed layer has a metallic luster exhibited by a metal surface or a luster imitating this metallic luster. In addition, pearl (pearl) luster etc. are mentioned as glossiness imitating metal luster.

  The metallic tone printing method may be either sheet-fed printing or winding printing, but winding printing is preferred from the viewpoint of easy winding. Examples of the winding printing include gravure rotary printing, flexographic rotary printing, and the like.

  In addition, when solid printing is performed on the surface of the transparent film layer 2 facing the modified polyolefin resin layer by the above printing method, the solid printing is performed partially even if it is performed on the entire surface of the transparent film layer 2. May be.

  A glittering ink is used for the metallic printing, and this glittering ink can be obtained by dispersing a glittering pigment in a vehicle obtained by dissolving a binder in a solvent.

  Examples of the solvent include water-soluble organic solvents such as alcohols such as isopropyl alcohol, cellosolves such as ethylene glycol monomethyl ether, and water. These may be used alone or in combination of two or more. Also good.

  And as a binder added to the said solvent, what is necessary is just to be suitably selected according to the kind of transparent film layer 2, for example, nitrified cotton / polyamide, polyurethane, polyester, vinyl chloride / vinyl acetate copolymer, acrylic resin, etc. Can be mentioned.

  As the glitter pigment used in the glitter ink, the printed layer obtained by using glitter ink (hereinafter sometimes referred to as “brilliant print layer”) has a metallic luster exhibited by the metal surface or the metal. What is necessary is just to be able to set it as the state which exhibited the glossiness imitating glossiness. In addition, pearl (pearl) luster etc. are mentioned as glossiness imitating metal luster.

  Specifically, examples of the glitter pigment that imparts a metallic luster to the glitter printing layer include a scale-like foil piece or fine powder of metal such as aluminum, copper, and brass, and a fragment of an aluminum vapor-deposited film. Since it has a vivid color and metallic tone, a piece of aluminum vapor deposited film is preferred.

  The aluminum vapor-deposited film is, for example, a biaxially stretched resin film having a thickness of 4 to 15 μm made of a synthetic resin such as polyester, and having a thickness of 50 to 2000 nm. It can be obtained by coloring the stretched film with a colorant. A fragment obtained by cutting the aluminum vapor-deposited film is used as a bright pigment.

  The colorant used for the aluminum vapor-deposited film may be either a pigment or a dye, but the pigment is chemically stable compared to the dye, and is excellent in weather resistance and chemical resistance. In the case where weather resistance and chemical resistance are important for the metallic decorative sheet, it is preferable to use a pigment as the colorant, while the dye is superior in transparency compared to the pigment, and the metallic decorative sheet When it is desired to impart transparency to the metallic luster exhibited or the luster imitating the metallic luster, it is preferable to use a dye as the colorant.

  Examples of the pigment include yellow pigments such as bench gin yellow, disazo yellow, chromophthal yellow, and isoindoline yellow, red pigments such as chromophthal red, dioxazine violet, quinacridone red, and perinone red, phthalocyanine blue, and indanthrone blue. Organic pigments such as blue pigments such as phthalocyanine green, and inorganic pigments such as chrome lead, chromium vermilion, and cobalt blue.

  Examples of the dye include natural dyes such as cochineal and synthetic dyes such as naphthol.

  Further, examples of the glitter pigment for imparting pearl luster to the glitter printing layer include foil pieces or fine powder such as mica whose surface is coated with bismuth oxychloride or titanium dioxide, and two or more resins having different refractive indexes. Examples thereof include a cut piece of a resin laminated film having a thickness of several μm or less, which is formed by laminating films to produce an interference color.

  In addition, if the size of the glitter pigment contained in the glitter ink is small, the metallic layer of the printed layer obtained using the glitter ink may not be clear, while if large, the glitter ink is used. In some cases, the printed layer obtained may not be imparted with a metallic tone, and is preferably 0.1 to 100 μm, and more preferably 0.2 to 10 μm.

  The size of the glitter pigment refers to the diameter of the smallest true sphere that can surround the glitter pigment when the glitter pigment is in the form of particles. The glitter pigment is a fine piece such as a foil piece or a cut piece. When it is a piece, it means the diameter of the smallest perfect circle that can surround the glitter pigment.

  Further, if the amount of the glittering pigment added in the glittering ink is small, it may not be possible to impart a sufficient metallic tone to the metallic decorative sheet, whereas if it is large, the viscosity of the glittering ink becomes high. Since the printing quality may be deteriorated, the amount is preferably 50 to 600 parts by weight, more preferably 150 to 300 parts by weight with respect to 100 parts by weight of the binder.

  Furthermore, the glitter ink may be colored as long as the printed layer obtained using the glitter ink has a metallic gloss exhibited by the metal surface or a gloss imitating the metallic gloss. Examples of a method for coloring the glitter ink include a method of adding a pigment to the glitter ink. Note that the pigment added to the glitter ink is the same as the pigment used in producing the glitter pigment, and thus the description thereof is omitted.

  As described above, the metallic decorative sheet of the present invention is configured to exhibit a metallic tone by performing metallic printing with glittering ink on the surface of the transparent film layer facing the modified polyolefin resin layer.

  On the other hand, in a metal-like decorative sheet that has been produced with a metal foil that has been conventionally provided, when a pressing force is applied to the surface, the metal foil is irreversibly deformed, and with this deformation of the metal foil As a result, a concave portion is formed on the surface of the metallic decorative sheet, so that the surface property may be lowered or the metallic tone may be impaired.

  In this respect, the metallic tone decorative sheet of the present invention has a metallic tone texture due to the metallic tone printing formed on the transparent film layer as described above. Even if it is added, it is generally reversibly restored to its original state, and thus the metallic decorative sheet of the present invention can maintain its beautiful metallic tone over a long period of time.

  The vehicle may contain auxiliary agents such as a color stabilizer, a heat stabilizer, a weather stabilizer, a drying agent, a viscosity modifier, a lubricant, and an antifungal agent, as long as the function is not impaired. .

  In the above description, a case has been described in which printing is performed directly on the transparent film layer 2 using glitter ink, and the glitter ink may be colored as necessary, but instead of coloring glitter ink. It is preferable to print on the transparent film layer 2 using the colored transparent ink and the glitter ink in this order, that is, on the transparent film layer 2, a printing layer is formed by printing using the colored transparent ink. In addition, it is preferable that a printed layer formed by printing using glitter ink is formed on the printed layer in a superposed state. In addition, the printing method using colored transparent ink can use the well-known printing method mentioned above.

  This is due to the following reasons. When colored transparent ink is used, the color tone is adjusted separately by the printing layer using colored transparent ink, and the glossiness is adjusted separately by the printing layer using glittering ink. This is because they can be adjusted separately, and fine adjustment of the luster simulating the metallic luster or metallic luster can be performed with high accuracy.

  The colored transparent ink is obtained by adding a pigment excluding a bright pigment as a colorant to a vehicle obtained by dissolving a binder in a solvent. The colored transparent ink may be supplemented with an auxiliary agent within a range that does not impair its function, and the solvent, binder, and auxiliary agent used in the colored transparent ink are the same as in the case of glittering ink. Since it is the same, the description is omitted.

  And as a pigment used for colored transparent ink, the thing similar to the pigment used for manufacture of an aluminum vapor deposition film is used.

  In addition, the pigment used for the colored transparent ink may be used alone or may be used after blending two or more types to obtain a desired color tone, but the printed layer obtained using the colored transparent ink And it is necessary to adjust so that a glossy printed layer can be visually recognized through the transparent film layer 2.

  The color tone of the printed layer obtained by using the colored transparent ink (hereinafter sometimes referred to as “colored transparent printed layer”) is, for example, a metallic-like makeup by changing the colored transparent printed layer to a yellowish color tone. The sheet can have a golden or brass color, and the colored transparent printed layer can have a reddish brown color, so that the metallic decorative sheet can have a bronze color and is colored and transparent. By making the printing layer a blue color tone, the metallic tone decorative sheet can have a blue metallic color, and by making the colored transparent printing layer a green tone, the metallic tone decorative sheet is green. It becomes a metallic color.

  Furthermore, it is preferable to print on the transparent film layer 2 using colored transparent ink, colorless transparent ink and glitter ink in this order, that is, printing using the colored transparent ink on the transparent film layer 2. In addition to forming a printing layer by the above method, a printing layer by printing using a colorless and transparent ink (hereinafter sometimes referred to as “colorless and transparent printing layer”) is formed on the colored and transparent printing layer. It is preferable that a print layer (bright print layer) is formed by printing using the bright ink.

  The colorless and transparent ink refers to a vehicle in which a colorant such as a pigment or a dye is not added to a vehicle obtained by dissolving a binder in a solvent. And it is necessary to adjust so that a glittering printing layer can be visually recognized through a colorless transparent printing layer, a colored transparent printing layer, and the transparent film layer 2. FIG. Further, the colorless transparent ink may be supplemented with an auxiliary agent as long as the function is not impaired. Since the solvent, binder, and auxiliary agent used in the colorless and transparent ink are the same as in the case of the glitter ink, the description thereof is omitted.

  As a printing method using a colorless and transparent ink, when the thickness of the colorless and transparent printing layer is relatively thin, such as 1 to 10 μm, a method such as gravure rotary printing, gravure coating, and roll coating is preferable. In the case where the thickness of the layer exceeds 10 μm and is relatively thick such as 200 μm or less, methods such as comma coating, knife coating, curtain flow coating, and die coating are preferable.

  If the colorless transparent printing layer is thin, the distance between the colored transparent printing layer and the glittering printing layer is too short, and the colored metallic luster may not be clear. Since there is a possibility that the color tone of the printing layer may appear to float from the glittering printing layer and become unnatural, 1 to 200 μm is preferable.

  Also, the colorless and transparent printing layer, instead of printing using the colorless and transparent ink, supplies the binder used for the colorless and transparent ink to the extruder, melts and kneads it, and then the colored transparent printing of the transparent film layer 2 from the extruder. It may be formed by extrusion lamination onto the layer.

  Furthermore, it is preferable that the surface facing the modified polyolefin resin layer 1 in the transparent film layer 2 is embossed to improve the design of the metallic decorative sheet A, and the hairline processing is performed. More preferably.

  In order to impart further surface gloss and surface strength to the metallic tone decorative sheet A, as shown in FIG. 2, the surface protective layer 3 may be laminated and integrated on the surface of the transparent film layer 2. The surface protective layer 3 is preferably a three-dimensional cross-linking type cured resin layer for the purpose, and the cured resin constituting the cured resin layer may be a thermosetting resin or an ionizing radiation curable resin. Also good.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, Examples include melamine-urea cocondensation resin, silicon resin, polysiloxane resin, and the like. A curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator may be added to the resin as necessary. For example, an isocyanate or an organic sulfonate as a curing agent is added to an unsaturated polyester resin or polyurethane resin, an organic amine or the like as a curing agent is added to an epoxy resin, and a peroxide such as methyl ethyl ketone peroxide or an azo compound. Isobutyronitrile or the like is added to the unsaturated polyester as a polymerization initiator.

  Specific examples of the ionizing radiation curable resin include a composition curable by ionizing radiation in which a prepolymer, an oligomer, or a monomer having a polymerizable unsaturated bond or an epoxy group is appropriately mixed in the molecule. It is done. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and includes ultraviolet rays and electron beams.

  Examples of the above prepolymers and oligomers include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylates, polyether methacrylates, polyol methacrylates, methacrylates such as melamine methacrylates, polyester acrylates and epoxy acrylates. Acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

  Examples of monomers used in ionizing radiation curable resins include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate , Methacrylate esters such as methoxybutyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate , 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) methyl acrylate, acrylic acid- 2- (N, -Substituted amino alcohol esters of unsaturated acid such as diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide, methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, In addition to polyfunctional compounds such as 1,6-hexanediol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, two or more in the molecule Polythiol compounds having a thiol group such as trimethylolpropane trithioglycolate, trimethylolpropane tri Examples thereof include thiopropionate and pentaerythritol tetrathioglycol. Usually, one or two or more of the above compounds are used as necessary, but in order to impart ordinary coating suitability to the ionizing radiation curable resin, the prepolymer or polythiol is contained in an amount of 5% by weight or more. The monomer or polythiol is preferably 95% by weight or less.

  When irradiating with ultraviolet rays to cure the ionizing radiation curable resin, a photopolymerization initiator or a photopolymerization accelerator (sensitizer) may be added to the ionizing radiation curable resin. Examples of the initiator include acetophenones, benzophenones, Michler benzoyl benzoate, α-amino oxime ester, tetramethyl thiuram monosulfide, thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes and the like. Furthermore, examples of the photopolymerization accelerator (sensitizer) include n-butylamine, triethylamine, and tri-n-butylphosphine.

  Spherical particles may be added to the three-dimensional crosslinking type cured resin. By adding spherical particles, it is possible to give the surface protective layer 3 a matte feeling, and it is possible to suppress the reflection of the surface by design and to expect an improvement in the scratch properties of the surface protective layer 3. Can do.

  Examples of the spherical particles include spherical inorganic particles made of an inorganic material such as alumina and silica, and spherical organic particles made of an organic material such as a silicon resin and a crosslinked acrylic resin. Inorganic particles may be treated with an organic acid, a surfactant, a silane coupling agent or the like in order to improve dispersibility. The particle diameter of the spherical particles is not particularly limited, and usually spherical particles having an average particle diameter of 3 to 50 μm are used. Moreover, the addition amount of a spherical particle is not specifically limited, Usually, 3-30 weight part is added with respect to 100 weight part of resin components.

Addition of coloring agents such as dyes and pigments, other fillers such as fine powder of CaCO ₃ , BaSO ₄ , nylon resin, antifoaming agent, leveling agent, thixotropic agent, etc. May be. For the three-dimensional cross-linking type cured resin, in order to adjust the viscosity, a solvent capable of dissolving the resin component and having a boiling point of 70 to 150 ° C. at normal pressure is used in the composition within a range of 50% by weight or less. be able to. When the amount of the solvent added is in the range of 50% by weight or less, the drying is smooth and the production speed is not greatly reduced.

  As the solvent, those commonly used for paints, inks and the like can be used. Specific examples include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ethyl acetate. , Acetates such as isopropyl acetate and amyl acetate, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as dioxane, tetrahydrofuran and diisopropyl ether, and mixtures of two or more thereof. As a method of forming a three-dimensional crosslinked type cured resin layer, a direct coating method in which a coating composition is directly applied, or a three-dimensional crosslinked type cured resin layer is formed in advance on the surface of a releasable substrate. Then, a transfer coating method or the like for transferring the cured resin layer is used.

  The direct coating methods include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, silk screen solid coat, wire bar coat, flow coat, comma coat Flow-through coating, brush coating, spray coating, and the like can be used, and gravure coating is preferred.

  As an ionizing radiation irradiator used to cure ionizing radiation curable resins, light sources such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, black light lamp, metal halide lamp are used when irradiating ultraviolet rays. In addition, when irradiating an electron beam, various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. It is done.

The electron beam is usually irradiated with electrons having an energy of 100 to 1000 keV, preferably 100 to 300 keV at an irradiation amount of about 0.1 to 30 Mrad. If the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and if the irradiation amount exceeds 30 Mrad, the cured coating film or substrate may be damaged. Moreover, the irradiation amount in the case of hardening with ultraviolet rays is preferably 50 to 1000 mJ / cm ² . If the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , curing may be insufficient, and if the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film may be yellowed.

  And when the light transmittance of the surface protective layer 3 is low, the transparent film layer 2 cannot be visually recognized through the surface protective layer, and the metallic tone of the metallic decorative sheet may be lowered, so 70% or more is preferable. .

  In addition, the light transmittance of the surface protective layer 3 means what was measured in the following way. First, a test sheet made of a synthetic resin constituting the surface protective layer and having the same thickness as the surface protective layer is prepared.

  Next, using an ultraviolet / visible / near infrared spectrophotometer, the wavelength is continuously increased from 380 nm to 800 nm in the wavelength region of 380 to 800 nm, and the light transmission of the test sheet in the wavelength region of 380 to 800 nm. The rate was measured continuously. And let the minimum light transmittance in the wavelength range of 380-800 nm be the light transmittance of a surface protective layer.

  As shown in FIG. 3, the metallic decorative sheet A is laminated and integrated on the metal plate M so that the first modified polyolefin resin layer 1 of the metallic decorative sheet A faces the metallic plate M. The decorative metal plate B is formed.

  Examples of the metal plate M include a plate made of a metal such as iron, steel, aluminum, copper, zinc, tin, nickel, titanium, and an alloy containing one or more of these as a main component. A steel plate is preferred. Also, the surface of the metal plate is often plated, and examples of such plating include hot dip galvanizing and electrolytic galvanizing. The thickness of the metal plate is preferably 0.05 to 2 mm, more preferably 0.15 to 1.0 mm.

  And as the method of laminating and integrating the metallic decorative sheet A on the metal plate M, in addition to the method of thermally laminating the metallic decorative sheet A on the metal plate M, the modified polyolefin resin on the metallic plate M Examples include a method of extruding and laminating a layer, and then thermally laminating the transparent film layer on the modified polyolefin resin layer so that the surface of the transparent film layer that has been subjected to metallic printing is opposed to the modified polyolefin resin layer.

  And the obtained decorative metal plate B has high designability, and can be suitably used for surface materials such as house interiors, refrigerator doors, kitchen doors, posters, labels, packages, displays, and the like.

  The metallic decorative sheet of the present invention is formed by laminating and integrating a transparent film layer on a modified polyolefin resin layer, and the modified polyolefin resin layer is made of a polyethylene resin, a polypropylene resin, and an ethylene-propylene rubber resin. In addition to containing a total of 50% by weight or more of modified polyolefin resins obtained by modifying one or more polyolefin resins selected from the group with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, the above in the transparent film layer The surface facing the modified polyolefin resin layer is characterized by metallic printing with glitter ink, so it can be laminated and integrated on a metal plate without using an adhesive, and beautiful metal In addition, from the top of the metal plate by secondary processing such as punching, bending, cutting, deep drawing, etc. It is not to be away.

  The metallic decorative sheet of the present invention is configured to exhibit a metallic tone by performing metallic-tone printing with glittering ink on the surface of the transparent film layer that faces the modified polyolefin resin layer. The tone printing layer is almost reversibly restored to its original state even when a pressing force is applied from the outside, and therefore the metal tone decorative sheet of the present invention can maintain its beautiful metal tone for a long period of time. it can.

  Furthermore, the decorative metal plate in which the above-mentioned metallic decorative sheet is laminated and integrated on the metal plate is excellent in secondary workability such as cutting, punching, bending, deep drawing, and the cut surface during cutting or punching. The resin does not run out or drops off, and there is no appearance defect of the uneven paste coating pattern, resulting in excellent durability and adhesion.

  The decorative metal plate is configured to exhibit a metallic tone by performing metallic printing with glittering ink on the surface of the transparent film layer facing the modified polyolefin resin layer, and the metallic printing layer is Even when a pressing force is applied from the outside, the original state is reversibly restored, and thus the metallic decorative sheet of the present invention can maintain its beautiful metallic tone for a long period of time.

  Furthermore, the design of a metallic decorative sheet can be further improved by embossing the transparent film layer.

Example 1
100 parts by weight of aluminum scaly foil pieces containing 85% by weight of aluminum scaly foil pieces having a thickness of 0.25 μm and a foil area of 20 to 2000 μm ² , 40 parts by weight of polyester resin, and 800 weights of ester solvent. A glittering ink (trade name “mirror ink”, manufactured by Teikoku Ink Manufacturing Co., Ltd., viscosity: 80 cps) was prepared by uniformly mixing 500 parts by weight of a ketone solvent.

  Next, hairline processing was performed on one side of a 25 μm thick polyethylene terephthalate film (Toyobo Co., Ltd.). On the film surface subjected to the hairline processing, glitter printing was performed by solid printing by gravure rotary printing using the glitter ink, thereby forming a glitter printing layer.

  Subsequently, maleic acid-modified polypropylene modified with maleic anhydride (modification rate: 0.8% by weight) was extrusion laminated on the glittering printing layer of the polyethylene terephthalate film, and the thickness was increased on the polyethylene terephthalate film. A 20 μm maleic acid-modified polypropylene layer was laminated and integrated to obtain a metallic decorative sheet. In the obtained metallic decorative sheet, the tensile stress at 5% elongation of the maleic acid-modified polypropylene layer was 250 MPa.

  Further, an ionizing radiation curable resin paint having the following composition was applied on a polyethylene terephthalate film of a metallic tone decorative sheet using a reverse coater and dried with a dryer to form a coating film having a thickness of 10 μm. This coating film was irradiated with an electron beam for 7 Mrad under the conditions of 175 keV and oxygen concentration of 200 ppm or less using an electron beam emission device, and the coating film was cured, and a surface protective layer was laminated and integrated on the polyethylene terephthalate film. In the metallic decorative sheet, the glittering printed layer could be visually recognized through the surface protective layer and the polyethylene terephthalate film.

  Next, an electrolytic galvanized steel sheet is prepared, and after the electrolytic galvanized steel sheet is heated to 200 ° C., the above-mentioned metal-like decorative sheet is placed on the electrolytic galvanized steel sheet and the maleic acid-modified polypropylene layer faces the electrolytic galvanized steel sheet. The decorative steel sheet was obtained by stacking and integrating a metallic decorative sheet on the electrolytic galvanized steel sheet.

(Composition of ionizing radiation curable resin paint)
Urethane acrylate oligomer: 50 parts by weight Bifunctional acrylate monomer: 40 parts by weight Trifunctional acrylate monomer: 10 parts by weight Silicone acrylate: 3 parts by weight Spherical alumina: 25 parts by weight Ethyl acetate ... 100 parts by weight

(Example 2)
Hairline processing is performed on one side of a 25 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.), and transparent blue colored transparent ink (trade name “PC Series” manufactured by Toyo Ink Manufacturing Co., Ltd.) is applied on the surface of the film subjected to this hairline processing. The colored transparent printing layer was formed by performing solid printing by gravure rotary printing using “)”.

  Next, on the colored transparent printing layer of the polyethylene terephthalate film, a thickness of 1.5 μm is obtained by solid printing by gravure rotary printing using a colorless transparent ink (trade name “PC series” manufactured by Toyo Ink Manufacturing Co., Ltd.). A colorless and transparent printing layer was formed.

  Subsequently, on the colorless and transparent printing layer of the polyethylene terephthalate film, glitter printing was performed by performing solid printing by gravure rotary printing using the glitter ink used in Example 1 to form a glitter printing layer. . The glitter print layer could be visually recognized through the polyethylene terephthalate film, the colored transparent print layer and the colorless transparent print layer.

  A maleic acid-modified polypropylene layer is laminated and integrated on the glittering printed layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a metallic decorative sheet, and this metallic decorative sheet has the same procedure as in Example 1. The surface protective layer was laminated and integrated. In the metallic decorative sheet, the glittering printed layer could be visually recognized through the surface protective layer, the polyethylene terephthalate film, the colored transparent printed layer and the colorless transparent printed layer.

  Then, the obtained metallic decorative sheet was laminated and integrated on the electrolytic galvanized steel sheet in the same manner as in Example 1 to obtain a decorative steel sheet.

(Comparative Example 1)
A metallic decorative sheet and a decorative steel sheet were obtained in the same manner as in Example 1 except that unmodified polypropylene was used instead of maleic acid-modified polypropylene.

(Comparative Example 2)
Maleic acid-modified polypropylene modified with maleic anhydride (modification rate: 0.8% by weight) was supplied to an extruder and melt-kneaded, and then a maleic acid-modified polypropylene film having a thickness of 40 μm was extruded from the extruder. .

  Next, the surface of the maleic acid-modified polypropylene film is subjected to corona discharge treatment under conditions of 6 KW and a processing speed of 20 m / min so that the surface tension of the maleic acid-modified polypropylene film surface is 45 dyne / cm or more. It was adjusted.

  On the other hand, an aluminum foil having a thickness of 50 μm was prepared, and the surface of the aluminum foil was subjected to hairline processing. Next, the aluminum foil was dry-laminated on the corona discharge-treated surface of the maleic acid-modified polypropylene film so that the hairline processed surface was on the outside.

  Subsequently, printing was performed on the hairline processed surface of the aluminum foil by gravure printing using a light black transparent urethane resin-based ink to form a printed layer.

  Thereafter, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm is dry laminated on the printed layer of the aluminum foil using a polyester-based adhesive (trade name “Seika Bond E295” manufactured by Dainichi Seika Kogyo Co., Ltd.). To obtain a metallic decorative sheet.

  A surface protective layer was laminated and integrated on the polyethylene terephthalate film of the metallic decorative sheet in the same manner as in Example 1, and a decorative steel sheet was obtained in the same manner as in Example 1.

(Performance evaluation)
The performance of each decorative steel sheet obtained above was evaluated by the following method. The results were as shown in Table 1.
1) Erichsen test After making cuts in the cut surface at intervals of 3 mm on the surface of each decorative steel plate, the Ericksen test is performed on the crosscut part to measure the push-in distance until the decorative sheet peels off, The state of peeling of the sheet was visually observed.
2) Appearance The metal-like decorative sheet surface of each decorative steel sheet was visually observed to determine the presence or absence of stainless steel, and the presence or absence of glue was evaluated based on the following criteria.
[After glue]
There is paste. ・ The surface of the metal-like decorative sheet was uneven.
No pasting or unevenness due to pasting on the surface of the metallic decorative sheet.

3) Surface pressing test The tip of a pencil lead having a hardness of 4H was pressed into the surface of the metallic decorative sheet of each decorative steel plate with a weight of 1000 g. Thereafter, the presence or absence of a press mark on the surface of the metallic decorative sheet was observed by visual observation and evaluated based on the following criteria.
[Press mark]
There was a pressing mark. The surface of the metal-like decorative sheet was uneven.
There was no pressing mark. No irregularities were generated by pressing on the surface of the metallic decorative sheet.

It is the longitudinal cross-sectional view which showed the metal-like decorative sheet of this invention. It is the longitudinal cross-sectional view which showed the metal-like decorative sheet of this invention. It is the longitudinal cross-sectional view which showed the decorative metal plate of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Modified polyolefin resin layer 2 Transparent film layer 3 Surface protective layer A Metal-tone decorative sheet B Cosmetic metal plate

Claims (5)

A transparent film layer is laminated and integrated on the modified polyolefin resin layer, and the modified polyolefin resin layer is one or more selected from the group consisting of polyethylene resins, polypropylene resins, and ethylene-propylene rubber resins. The surface of the transparent film layer facing the modified polyolefin resin layer and containing a total of 50% by weight or more of a modified polyolefin resin obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative A metallic-tone decorative sheet characterized in that a metallic-tone printing with glittering ink is applied to the surface. 2. The metallic decorative sheet according to claim 1, wherein a surface of the transparent film layer facing the modified polyolefin resin layer is embossed. 3. The metallic decorative sheet according to claim 1, wherein colored transparent printing and metallic printing are performed in this order on a surface of the transparent film layer facing the modified polyolefin resin layer. 3. The metallic tone according to claim 1, wherein colored transparent printing, colorless transparent printing, and metallic tone printing are performed in this order on a surface of the transparent film layer facing the modified polyolefin resin layer. Makeup sheet. 5. The metal decorative sheet according to any one of claims 1 to 4 is laminated and integrated on a metal plate in a state where the modified polyolefin resin layer faces the metal plate. Decorative metal plate.

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