US20040258945A1 - Laminate having color and metallic gloss, and method for production thereof - Google Patents

Laminate having color and metallic gloss, and method for production thereof Download PDF

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Publication number
US20040258945A1
US20040258945A1 US10/487,872 US48787204A US2004258945A1 US 20040258945 A1 US20040258945 A1 US 20040258945A1 US 48787204 A US48787204 A US 48787204A US 2004258945 A1 US2004258945 A1 US 2004258945A1
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United States
Prior art keywords
resin layer
dye
laminate
chromatic
metalescent
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Abandoned
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US10/487,872
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English (en)
Inventor
Yuuichi Kanayama
Hiroki Kashiwagi
Mitsuru Kawakita
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Techno UMG Co Ltd
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Individual
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Assigned to TECHNO POLYMER CO., LTD. reassignment TECHNO POLYMER CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KANAYAMA, YUUICHI, KASHIWAGI, HIROKI, KAWAKITA, MITSURU
Publication of US20040258945A1 publication Critical patent/US20040258945A1/en
Priority to US11/152,347 priority Critical patent/US20060151103A1/en
Priority to US11/350,281 priority patent/US20060172129A1/en
Priority to US12/591,529 priority patent/US20100071840A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/14—Metallic leaves or foils, e.g. gold leaf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to a laminate having chromatic color and a process for producing it. More particularly, it relates to a chromatic metalescent laminate having chromatic metalescence, or metallic luster, easily obtainable, capable of easy adjustment of coloration, and having excellent workability, and a method of producing such a laminate.
  • the chromatic metalescent laminate according to the present invention finds particularly useful application as various types of interior and exterior trims, containers and the like.
  • the laminates principally made of organic materials and having metal-like appearance have been used as a metal substitute as these laminates provide improvements of processability, workability and durability and are capable of a substantial weight reduction of the products.
  • An object of the present invention is to solve the above problems and to provide a chromatic metalescent laminate having desired chromatic metallic luster, easily obtainable and capable of easy working, and a method of producing such a laminate.
  • FIGS. 1 ( a ) and ( b ) are schematic sectional views of the examples of chromatic metalescent laminate according to the present invention.
  • An embodiment (I) of the chromatic metalescent laminate according to the present invention comprises a first resin layer and a metallic film which contains a dye.
  • Another embodiment (II) of the chromatic metalescent laminate of the present invention comprises, laminated in the said order, a first resin layer containing a dye, a metallic film and a second resin layer, in which the said second resin layer contains the dye which has migrated from the said first resin layer, and the laminate has chromatic metalescence at least on its second resin layer side.
  • Still another embodiment (III) of the chromatic metalescent laminate of the present invention comprises a dye-containing first resin layer and a metallic film, in which the said metallic film contains the dye which has migrated from the said first resin layer, and the laminate has chromatic metallic luster at least on its metallic film side.
  • the dye used in the present invention is not specifically designated; it is possible to use any type of dye as far as it has a color. It may be either chromatic or achromatic and may be lipophilic or soluble in water.
  • organic dyes As they are well dispersible in resins.
  • organic dyes include heterocyclic dyes (such as cyanine dyes, triazine dyes, pyrimidine dyes, quinoline dyes and quinoxaline dyes), anthraquinoline dyes, azo dyes (such as monoazo dyes, diazo dyes, bisazo dyes, trisazo dyes and stilbene dyes), indigoid dyes (such as indigo dyes and thioindigo dyes), naphthol dyes, triphenylmethane dyes, and indanthrene dyes.
  • These dyes may be direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes or fluorescent brightening dyes.
  • perinone dyes perylene dyes, heterocyclic dyes, anathraquinone dyes, azo dyes and indigoid dyes are preferred as they can migrate more easily to the second resin layer described later and are also well dispersible in this second resin layer.
  • dyes may be used either singly or as a combination of two or more.
  • the dye content in the first resin layer described later is not specifically defined as far as the obtained laminate can be confirmed to be chromatic on the second resin layer side.
  • the dye content is also variable depending on the type of the dye used, but usually it is 0.01 to 10 parts by mass (preferably 0.02 to 5 parts by mass, more preferably 0.03 to 3 parts by mass) based on 100 parts by mass of the whole first resin layer. (“Parts by mass” (weight) are hereinafter expressed simply as “parts” unless otherwise noted.) If the dye content is less than 0.01 part, the amount of the dye migrating to the second resin layer in the laminate producing process may prove insufficient, causing unsatisfactory coloration of the second resin layer. On the other hand, even if the dye is contained in excess of 10 parts, any further change of hue can hardly be expected.
  • the “first resin layer” referred to herein is a layer whose main component (usually not less than 80 mass % of the whole first resin layer) is a polymer (which may be a homopolymer and a copolymer).
  • the polymer constituting this resin layer is not specifically defined; the layer may be formed from a thermoplastic polymer, thermosetting polymer, elastomer, rubber or the like, or a mixture thereof.
  • thermoplastic polymers usable for the first resin layer include, but are not limited to, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-ethylene-propylene-styrene copolymer, thermoplastic polyurethane polymers, poly(meth)acrylate polymers, polyacrylic acid polymers, polyolefinic polymers, polyester polymers, polyalkene terephthalate polymers (such as polyethylene terephthalate and polybutylene terephthalate), ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polystyrene polymers, vinyl chloride polymers, polycarbonate polymers, polyacetal polymers, polyamide polymers, and fluoropolymers.
  • acrylonitrile-butadiene-styrene copolymer acrylonitrile-styrene copolymer
  • thermosetting resins usable for the first resin layer include, but are not limited to, phenol polymers, epoxy polymers, unsaturated polyester polymers, polyurethane polymers, urethane-urea copolymer, urea polymers, and silicon polymers.
  • the elastomers usable for the first resin layer include, but are not limited to, styrene-based thermoplastic elastomers (such as styrene-butadiene-styrene block copolymer and its hydrogenated product), thermoplastic polyolefin elastomers, thermoplastic polyurethane elastomers, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, thermoplastic 1,2-polybutadiene elastomers, silicone resin elastomers, and fluorine resin elastomers.
  • styrene-based thermoplastic elastomers such as styrene-butadiene-styrene block copolymer and its hydrogenated product
  • thermoplastic polyolefin elastomers such as styrene-butadiene-styrene block copolymer and its hydrogenated product
  • thermoplastic polyolefin elastomers such as st
  • styrene-butadiene rubber styrene-butadiene rubber, isobutylene-isoprene rubber, acrylonitrile-butadiene rubber and ethylene-propylene-diene rubber can be mentioned as examples, but the rubbers usable for the above purpose are not limited to those mentioned above.
  • thermoplastic polymer a mixture thereof with rubber, a thermoplastic elastomer or a mixture of a thermoplastic polymer and a thermoplastic elastomer.
  • thermoplastic polymer it is particularly preferable to use an acrylonitrile-butadiene-styrene copolymer, a polycarbonate polymer, a mixture of an acrylonitrile-butadiene-styrene copolymer and a polycarbonate polymer, or an acrylonitrile-styrene copolymer.
  • the size and shape of the first resin layer can be optionally chosen. Its thickness is also free to choose in accordance with the purpose of use of the laminate, but usually it is in the range of 300 ⁇ m to 15 mm. In order to secure appropriate moldability, the layer thickness is preferably selected from the range of 0.5 to 10 mm (more preferably 0.5 to 7 mm).
  • This first resin layer can be obtained by any method available. For instance, it can be obtained by kneading and thereafter molding a polymer or a mixture of polymers such as mentioned above.
  • the kneading method can be optionally selected; for instance, kneading can be effected by using various types of extruder and mixing machine such as Banbury mixer, kneader, roll mill, feeder ruder etc., singly or in combination (kneading can be effected at one time or by adding the polymer in portions).
  • the dye may be mixed with a predetermined polymer before kneaded or may be mixed in the course of kneading.
  • the molding method is also not restricted; for instance, molding can be effected by using known molding techniques such as injection molding, extrusion molding, vacuum molding, profile molding, foam molding, injection press molding, press molding, and blow molding.
  • the “metallic film” is provided to afford metallic luster to the laminate of the present invention.
  • the type of metal used for forming this layer is not specified; it is possible to use, for instance, chromium, aluminum, gold, platinum, silver, rhodium, palladium, indium, titanium, iron, nickel, copper, zinc, tin and silicon. A mixture of two or more of these materials may be used.
  • This metallic film may be of a single layer or may consist of two or more sublayers. In case where it consists of two or more sublayers, these sublayers may differ from each other in type of metal used therefor.
  • This metallic film also has gaps between the metal particles composing the film, said gaps being of a degree that allows dispersion of the dye.
  • this metallic layer (total thickness in case where the layer consists of two or more sublayers) is not specifically defined as far as it is sufficient to maintain metallic luster, but usually it is around 10 to 200 nm (preferably 10 to 150 nm, more preferably 10 to 100 nm). Its shape is also an option. Further, this metallic film may be formed in whatever manner conceivable; for instance, it may be formed by such method as vapor deposition, ion plating, sputtering, CVD or plating.
  • this metallic film can be formed by applying a paste of fine metal particles formed by turning a large amount of fine metal particles into a paste with a small quantity of resin binder and solvent, and then removing the solvent.
  • a metallic film is formed as the other layer.
  • the other layer is not specified and can be formed from various materials. It is possible to apply the same polymer as used for the said first resin layer and the later-described second resin layer, and preferably a metallic film is formed on at least one side of the first resin layer and/or the second resin layer.
  • the second resin layer mainly comprises a polymer (usually not less than 80 mass % of the whole second resin layer is constituted by a polymer).
  • the polymer forming this second resin layer is not specifically defined, and those applicable to the first resin layer can be used.
  • the first and second resin layers may be formed with a same polymer.
  • This second resin layer contains the “dye which has migrated from the first resin layer.” A part or whole of the dye contained in the second resin layer is the one which has migrated from the first resin layer during production of the chromatic metalescent laminate of the present invention.
  • this dye is let migrate to the second resin layer, but in case where two or more types of dye are contained in the first resin layer, either only one type of dye or all types of dye contained in the first resin layer may be allowed to migrate to the second resin layer.
  • These dyes may be contained in the polymer forming the second resin layer or may be concurrently contained between the metal particles composing the metallic film.
  • this second resin layer in addition to the dye which has migrated from the first resin layer, there may also originally be contained other dye. Such originally contained dye may be of the same type of dye as used for the first resin layer.
  • the amount of the dye allowed to migrate to the second resin layer is not specifically defined, but usually it is set to be about 0.001 to 0.02 part based on 100 parts of the whole dye contained in the first resin layer.
  • the second resin layer preferably undergoes a color difference of not less than 0.8 (preferably not less than 1) after migration of the dye from the first resin layer.
  • This color difference can be determined by the method described in the Examples given later.
  • the second resin layer can be formed in the same way as the first resin layer.
  • the said first resin layer, metallic film and second resin layer are laminated in that order. (See FIG. 1( a )). It is possible to provide one or more other layers between the said respective layers, on the side of the first resin layer not facing the second resin layer, and on the side of the second resin layer not facing the first resin layer. In case where such other layer(s) is provided between the first and second resin layers, such other layer(s) preferably does not obstruct the migration of the dye from the first to the second resin layer.
  • the “other layer” may be for instance a protective layer which is provided for the purpose of protecting the underside of the essential layers and which can be separated in use. Or it may be an adhesive layer designed to assist cementing of the respective layers or a metallic film of the other type than the above-mentioned.
  • the material of the protective layer is not specifically restricted; it is possible, for instance, to use the polymers exemplified before as resin for forming the first and second resin layers.
  • Thickness of the protective layer is also not defined, but usually it is set to be in the range of 5 to 1,000 ⁇ m (preferably 10 to 750 ⁇ m, more preferably 10 to 500 ⁇ m). If the thickness is less than 5 ⁇ m, the protective layer may not be able to perform its anticipated function, while if the thickness exceeds 1,000 ⁇ m, molding of the layer may become difficult.
  • the chromatic metalescent laminate according to the present invention has chromatic metallic luster at least on its second resin layer side.
  • This metallic luster derives from the said metallic film. Therefore, in case where the metallic film is an internal layer, the layers positioned closer to the surface than the metallic film may be required to be “colorless and transparent” or “colored and transparent” within limits not affecting metallic luster.
  • the first and second resin layers according to the present invention may contain, beside the dye such as mentioned above, other additives such as pigment as required.
  • pigment it is possible to use inorganic pigments such as mica-like iron oxide, black iron oxide, zinc carbonate, dilead tetroxide, lead chromate, zinc sulfide, mercury sulfide, barium sulfate, ultramarine, Prussian blue, cobalt oxide, titanium dioxide, chromium oxide, strontium chromate, zinc chromate, lead molybdenate, calcium molybdenate, calcium-zinc molybdenate, copper acetoarsenite, and cadmium sulfide, and organic pigments such as azo pigments (soluble azo pigments, insoluble azo pigments and condensed azo pigments), phthalocyanin blue, isoindolinone, quinacridone, dioxazine violet, perinone pigments, and perylene pigments.
  • inorganic pigments such as mica-like iron oxide, black iron oxide, zinc carbonate, dilead tetroxide, lead chromate
  • additives it is possible to add carbon fiber, metallic fiber, glass fiber, mild fiber, zinc oxide whisker, potassium titanate whisker, organic fibers, etc. which are used for the purpose of improving mechanical strength.
  • Talc, mica, kaolin, glass beads, glass flakes, wollastonite, carbon black and the like may also be contained for the purpose of improving properties of the laminate or increasing its volume.
  • Other agents such as lubricant, flame retardant, flame retarding assistant, coupling agent, antibacterial agent, mildewproofing agent, antioxidant, weather resistant agent, light stabilizer, plasticizer, antistatic agent, silicone oil, etc., may also be contained as required.
  • the molding method of the chromatic metalescent laminate of the present invention is not specified; for instance, it is possible to use such known molding method as heat compression molding, vacuum molding and blow molding.
  • the chromatic metalescent laminate of the present invention may be subjected to secondary processing such as coating.
  • the production method of the chromatic metalescent laminate according to the present invention is as described in any one of claims 1 to 3 , which comprises heating an uncemented first resin layer containing a dye and an uncemented second resin layer having a metallic film formed on at least one side thereof, thereby cementing together the said first and second resin layers in a way that the first resin layer faces the metallic film, while causing part of the dye to migrate into the said second resin layer.
  • the “uncemented first resin layer” is a layer which is to constitute the first resin layer of the chromatic metalescent laminate of the present invention
  • the “uncemented second resin layer” is a layer which is to serve as the second resin layer of the said laminate. At this stage, there is yet taking place no migration of the dye from the uncemented first resin layer to the uncemented second resin layer.
  • the uncemented first resin layer and the metallic film may be cemented together directly or with the intervention of other layer.
  • the “heating” conditions may be properly selected within limits allowing maintenance of the required properties of the respective resin layers. Usually, heating is carried out at 100 to 300° C. (preferably 120 to 270° C., more preferably 120 to 250° C.). At a temperature below 100° C., it may be hardly possible to cement together the resin layers even if pressure is applied as described later, and at a temperature above 300° C., the resin layers may be melted or decomposed to deform.
  • the heating time is optional, but usually it is set to be between one second and 30 minutes (preferably between 5 seconds and 20 minutes, more preferably between 10 seconds and 10 minutes). If the heating time is less than one second, the anticipated effect of heating may not be obtained. Also, elongation of the heating time over 30 minutes does not provide any further change.
  • Heating may be synchronized with pressing. Even after heating, pressing may be conducted while the remaining heat (usually around 100 to 300° C.) still remains.
  • the pressure to be applied may be optionally selected, but usually it is in the range of 0.5 to 50 MPa (preferably 1 to 40 MPa, more preferably 1 to 20 MPa). Below 0.5 MPa, the effect of pressing may not be obtained. Also, there is usually found no necessity of applying pressure in excess of 50 MPa.
  • the pressing time is also not prescribed, but usually it is set to be between one second and 30 minutes (preferably between 5 seconds and 20 minutes, more preferably between 10 seconds and 10 minutes). If the pressing time is less than one second, the effect of pressing may not be obtained. Also, even if the pressing time is elongated over 30 minutes, any additional change can hardly be obtained.
  • Another production method of the chromatic metalescent laminate according to the present invention is a production method of chromatic metalescent laminate as defined in one of claims 1 to 3 , which comprises heating a cemented laminate of a dye-containing cemented first resin layer, a metallic film and a cemented second resin layer, which are laminated in that order, thereby causing part of the dye to migrate into the said cemented second resin layer.
  • the “cemented first resin layer,” is a layer which is to constitute the first resin layer of the chromatic metalescent laminate of the present invention which is completed when all the layers are cemented together.
  • the “cemented second resin layer” is a layer serving as the second resin layer of the completed chromatic metalescent laminate of the present invention.
  • Heating is principally intended to cause migration of the dye from the cemented first resin layer to the cemented second resin layer. This heating may also have the effect of further strengthening cementation of the laminate. Heating is not specifically conditioned as far as it is sufficient to cause migration of the dye and to sustain the desired properties of the respective resin layers.
  • the ordinary range of temperature produced by this heating is the same as in the afore-mentioned embodiment of the invention. Also, as in the afore-mentioned embodiment, it is possible to change the amount and the type of the dye migrating from the first to the second resin layer and to obtain the desired depth and tone of color by controlling the heating temperature and heating time. Further, pressure may be applied during heating, or it may be applied after heating while the remaining heat still remains, as in the afore-mentioned embodiment of the invention.
  • the chromatic metalescent laminate (III) according to the present invention comprises a first resin layer containing a dye and a metallic film, the said metallic film containing the dye which has migrated from the first resin layer, and the said laminate having chromatic metallic luster at least on its metallic layer side. (See FIG. 1( b ).)
  • This embodiment of the invention is the same as the afore-mentioned embodiment except for the absence of the second resin layer.
  • the “metallic film” in this embodiment may be formed on the first resin layer surface.
  • the uncemented first resin layer and the uncemented metallic film are cemented together and heated to cause the dye contained in the uncemented first resin layer to migrate into the uncemented metallic film. Similar migration of the dye may be also effected by heating a cemented laminate comprising a cemented first resin layer and a cemented metallic film.
  • the chromatic metalescent laminate (I) according to the present invention comprises a first resin layer and a metallic film containing a dye.
  • This embodiment is an invention expressed as a perfect product as opposed to the afore-mentioned embodiment which involves a process element as suggested by the definition of “has migrated from the first resin layer” regarding the dye. Therefore, details of this chromatic metalescent laminate (I) will be easily understood by those skilled in the art from the explanation relating to the afore-mentioned embodiment.
  • ABS resin ABS resin (ABS330 produced by Techno Polymer Co., Ltd.)
  • Dye A Yellow heterocyclic compound (DIAREGIN YELLOW 3G produced by Mitsubishi Chemical Corporation)
  • Dye B Orange perinone compound (DIAREGIN ORANGE HS produced by Mitsubishi Chemical Corporation)
  • Dye C Red thioindigo compound (HOSTASOL RED 5B produced by Hoechst AG)
  • Dye D Purple anthraquinone compound (DIAREGIN VIOLET D produced by Mitsubishi Chemical Corporation)
  • Dye E Blue anthraquinone compound (MACROLEX BLUE RR produced by BASF Inc.)
  • Dye F Green anthraquinone compound (MACROLEX GREEN G produced by BASF Inc.)
  • Dye G Brown monoazo compound (DIAREGIN BROWN A produced by Mitsubishi Chemical Corporation)
  • the uncemented second resin layer and metallic film there was used a commercial resin film having a deposited metal film and already provided with a releasable protective layer and an adhesion layer.
  • the composition of this resin film (overall thickness being 26 ⁇ m) is as shown below.
  • Releasable protective layer polyethylene terephthalate (15 ⁇ m)
  • Uncemented second resin layer polyurethane (10 ⁇ m)
  • Metallic film chromium film (40 nm)
  • Adhesion layer polyurethane containing silica particles (1.2 ⁇ m)
  • Pellets for forming the uncemented first resin layer obtained by the method described in (1) were supplied into an extrusion molding machine to mold a sheet-like uncemented first resin layer, and the said resin film (uncemented second resin layer and metallic film) was cemented to the uncemented first resin layer by laminate molding.
  • Temperature of the uncemented first resin layer was 250° C. in Run Nos. 1, 7, 12, 16 and 27, and the uncemented first resin layer and resin film contact time (heating time) at this temperature was set to be about 10 seconds.
  • temperature of the uncemented first resin layer was 230° C., and the contact time was set to be about 5 seconds.
  • color difference ⁇ E was determined in a visual field of 10° by a color difference meter (Type “Aucolor 7e” mfd. by Kurashiki Boseki KK) with light source D65, using the color difference formula of CIE1976 (L*a*b).
  • the present invention is not limited to the embodiments described above but can be further embodied in various other ways within the scope of the invention according to the purpose of use of the laminate.
  • the chromatic metalescent laminate according to the present invention finds its particularly useful application to various types of exterior trims and containers, but it can be also offered to various other applications as well. Its typical applications as exterior or interior trims include exterior fittings of bags such as suitcase, interior fixtures of housing, and exterior trimmings of furniture (kitchen shelves, washing utensil holders, various types of racks, cabinets, etc.).
  • the laminate can also be advantageously applied to various types of labels, stickers, panels, handles and the like.
  • the chromatic metalescent laminate according to the present invention has a chromatic metalescent appearance, and is easy to work and lightweight. Also, with the chromatic metalescent laminate of the present invention, it is possible to readily obtain prominent decorative effect of metallic luster with desired coloration. Further, coloration and the tint of color can be adjusted by heating. According to the production method of the present invention, it is possible to obtain very easily an excellent chromatic metalescent laminate such as described above and to easily adjust coloration and the tint of-color.

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US10/487,872 2001-09-14 2002-09-06 Laminate having color and metallic gloss, and method for production thereof Abandoned US20040258945A1 (en)

Priority Applications (3)

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US11/152,347 US20060151103A1 (en) 2001-09-14 2005-06-15 Laminate having chromatic color and metallic luster, and process for producing the same
US11/350,281 US20060172129A1 (en) 2001-09-14 2006-02-09 Laminate having chromatic color and metallic luster, and process for producing the same
US12/591,529 US20100071840A1 (en) 2001-09-14 2009-11-23 Laminate having chromatic color and metallic luster, and process for producing the same

Applications Claiming Priority (3)

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JP2001280632 2001-09-14
JP2001-280632 2001-09-14
PCT/JP2002/009089 WO2003024710A1 (fr) 2001-09-14 2002-09-06 Stratifie presentant un brillant metallique et colore, et son procede de production

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US11/152,347 Division US20060151103A1 (en) 2001-09-14 2005-06-15 Laminate having chromatic color and metallic luster, and process for producing the same
US11/350,281 Continuation-In-Part US20060172129A1 (en) 2001-09-14 2006-02-09 Laminate having chromatic color and metallic luster, and process for producing the same

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US11/152,347 Abandoned US20060151103A1 (en) 2001-09-14 2005-06-15 Laminate having chromatic color and metallic luster, and process for producing the same

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KR (2) KR100892831B1 (ja)
CN (1) CN1314535C (ja)
DE (1) DE10297147T5 (ja)
WO (1) WO2003024710A1 (ja)

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US20070204948A1 (en) * 2006-02-21 2007-09-06 Werner Co. Fiberglass reinforced plastic products having increased weatherability, system and method
WO2008135253A1 (de) * 2007-05-08 2008-11-13 Rehau Ag + Co. Profilleiste
EP2275243A1 (en) * 2009-07-14 2011-01-19 Pacific Industrial Co., Ltd. Metallic resin cover and method of producing the same, and door handle for vehicle
US20180271210A1 (en) * 2015-09-18 2018-09-27 Asics Corporation Shoe sole member and shoe

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JP3802041B1 (ja) * 2005-05-25 2006-07-26 三菱樹脂株式会社 反射光線のゆらぎを防止可能な銘板作製用積層体
US8280594B2 (en) * 2009-09-28 2012-10-02 Aisin Seiki Kabushiki Kaisha Door opening/closing apparatus and coating film forming method
CN106626569A (zh) * 2016-08-31 2017-05-10 广州钰鑫新材料有限公司 一种彩色金属聚氨酯膜及其制作方法和应用
EP3851553A4 (en) * 2018-09-11 2021-11-03 Mitsubishi Engineering-Plastics Corporation METAL-COATED MOLDED ARTICLES OF RESIN AND METHOD FOR THEIR MANUFACTURING

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WO2008135253A1 (de) * 2007-05-08 2008-11-13 Rehau Ag + Co. Profilleiste
EP2275243A1 (en) * 2009-07-14 2011-01-19 Pacific Industrial Co., Ltd. Metallic resin cover and method of producing the same, and door handle for vehicle
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US10856604B2 (en) * 2015-09-18 2020-12-08 Asics Corporation Shoe sole member and shoe

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KR100892831B1 (ko) 2009-04-10
KR100850852B1 (ko) 2008-08-06
WO2003024710A1 (fr) 2003-03-27
CN1314535C (zh) 2007-05-09
CN1549772A (zh) 2004-11-24
KR20080050635A (ko) 2008-06-09
DE10297147T5 (de) 2004-07-22
US20060151103A1 (en) 2006-07-13
KR20040041156A (ko) 2004-05-14

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