WO2013183489A1 - 装飾成形用フィルム、および装飾成形体の製造方法 - Google Patents
装飾成形用フィルム、および装飾成形体の製造方法 Download PDFInfo
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- WO2013183489A1 WO2013183489A1 PCT/JP2013/064743 JP2013064743W WO2013183489A1 WO 2013183489 A1 WO2013183489 A1 WO 2013183489A1 JP 2013064743 W JP2013064743 W JP 2013064743W WO 2013183489 A1 WO2013183489 A1 WO 2013183489A1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14811—Multilayered articles
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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
- 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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
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- 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
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14827—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using a transfer foil detachable from the insert
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/002—Coloured
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
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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
- 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
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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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
- B32B2451/00—Decorative or ornamental articles
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- the present invention relates to a decorative molding film used for decorating a decorative body used in automobile parts, electrical appliances, portable terminals, etc., and a protective layer is formed at a high molding magnification portion even in a high temperature atmosphere.
- the present invention relates to a decorative molding film that is unlikely to crack or shrink and has a good surface appearance, and a method for producing a decorative molded body using the same.
- Existing film for decorative molding is expected to be molded at a low magnification, and it is difficult to adapt to a large-sized object or a complex-shaped object with irregularities.
- the decorative molding film has a laminated structure of a protective layer and a colored layer in order to impart a design to the decorative molded body, it is necessary to consider the physical properties of each coating film. Particularly in the high molding magnification portion, there is a problem that the coating film shrinks when left in a high temperature atmosphere, and a phenomenon such as a crack or shrinkage occurs in the decorative layer or the appearance deteriorates.
- the present invention has found that the above-described problems can be solved by making the storage elastic modulus of the protective layer and the colored layer have a specific relationship in the decorative molding film. That is, the present invention has the following configuration.
- a decorative molding film having a laminated structure in which a protective layer and a colored layer are arranged in this order on a base film, and the storage elastic modulus of the protective layer at 100 ° C. is defined as E′a (100 )
- the storage elastic modulus E′b (100) at 100 ° C. of the colored layer, E′a (100) and E′b (100) satisfy the following conditions (1) to (3):
- (1) E′a (100) / E′b (100) is 8 or less.
- E′a (100) is 10 MPa or more.
- E′b (100) is 12 MPa or less.
- the decorative molding film of the present invention has a high temperature atmosphere when it is decorated on an object to be decorated that requires a high draw ratio by setting the storage elastic modulus of the protective layer and the colored layer constituting the decorative molding film within a specific range. Even in the lower part, it is possible to obtain a decorative molded body in which cracking or shrinkage due to contraction of the coating film is difficult to occur and the appearance is hardly deteriorated.
- the decorative molding film of the present invention is a decorative molding film having a laminated structure in which a protective layer and a colored layer are arranged in this order on a base film, wherein the protective layer and the colored layer are at 100 ° C.
- E'a (100) and E'b (100) satisfy the following conditions (1) to (3), where E'a (100) and E'b (100) are the storage elastic moduli of It is characterized by that.
- (1) E′a (100) / E′b (100) is 8 or less.
- E′a (100) is 10 MPa or more.
- E′b (100) is 12 MPa or less.
- E'a (100) / E'b (100) is greater than 8
- softening and heat shrinkage may become prominent in a portion that is stretched by 200% or more in terms of surface magnification.
- E'a (100) / E'b (100) is 1 or more. It is desirable. More preferably, it is 2 or more from the viewpoint of surface hardness.
- E′a (100) / E′b (100) is less than 1, when the storage elastic modulus of the protective layer is low and the surface of the protective layer is deformed by applying pressure, the colored layer is In some cases, the deformation cannot be followed and a trace of the deformation tends to remain in the protective layer.
- Base film As the base film used in the present invention, a film having a breaking elongation at 100 ° C. of 200% or more is preferably used. Examples include films obtained by processing thermoplastic resins such as polyolefin, polyester, polyvinyl chloride, poly (meth) acrylic acid ester, polyamide, polyester amide, polyether, polystyrene, polyether ester, polycarbonate, etc. Any of a stretched film, a uniaxially stretched film, and a biaxially stretched film may be used.
- thermoplastic resins such as polyolefin, polyester, polyvinyl chloride, poly (meth) acrylic acid ester, polyamide, polyester amide, polyether, polystyrene, polyether ester, polycarbonate, etc. Any of a stretched film, a uniaxially stretched film, and a biaxially stretched film may be used.
- the surface of the base film on the protective layer side must have releasability from the protective layer. Having releasability means that the base film and the protective layer are peelable.
- a polyolefin film is provided on one side (protective layer side) of the base film.
- Examples include means for performing corona treatment on the (protective layer side) surface and adjusting the wetting tension.
- the thickness of the base film is preferably 50 to 500 ⁇ m, more preferably 75 to 200 ⁇ m, in view of the breaking strength and shape retention of the decorative molded body after molding.
- the thickness can be calculated by measuring with a micrometer according to JIS C 2151 (2006 edition) every time each layer is formed, during the production process of the decorative molding film.
- the thickness of a base film can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- the protective layer used in the decorative molding film of the present invention is located in the outermost layer when applied to a decorative molded body, the resin used in the protective layer does not impair the moldability of the decorative molding film.
- the resin used in the protective layer is preferably a resin having design characteristics such as transparency and gloss, and coating characteristics such as scratch resistance, impact resistance, chemical resistance, and weather resistance.
- E′a (100) of the protective layer is preferably 10 MPa or more. If E'a (100) is less than 10 MPa, the heat resistance may be lowered such that a dent mark is formed when an object is placed on the decorative molded body in a high temperature atmosphere, and the role of the protective layer may not be achieved. Further, since the residual stress at the high draw ratio portion becomes large and the coating film shrinkage may occur in a high temperature atmosphere after molding, E′a (100) is preferably 50 MPa or less. In particular, 40 MPa or less is preferable.
- the stress at 100% stretching at 100 ° C. of the protective layer is preferably 0.3 MPa or less. When the stress at 100% stretching at 100 ° C. is greater than 0.3 MPa, coating shrinkage may occur in a high temperature atmosphere after molding, as in the case where E′a (100) is greater than 50 MPa.
- E′a (40) of the protective layer is preferably 400 to 700 MPa.
- E'a (40) refers to the storage elastic modulus of the protective layer at 40 ° C. If E'a (40) is less than 400 MPa, scratches are likely to occur, and the scratch resistance of the protective layer may be insufficient. If E'a (40) is larger than 700 MPa, the protective layer may be too hard when it is molded into a curved surface, and the protective layer may crack.
- the method for adjusting the storage elastic modulus of the protective layer in the present invention is not particularly limited, but it is possible to mix a plurality of resins, adjust the crosslinking density of the resins, and add a curing agent or a plasticizer to the resin paint. Can be adjusted.
- the storage elastic modulus of the protective layer it can be measured by the method described in the examples, but when the protective layer is already laminated with the base film and / or the colored layer, What is necessary is just to measure by grinding
- Examples of the resin used for the protective layer in the present invention include a thermosetting resin and a photocurable resin (including a UV curable resin).
- examples of the thermosetting resin include a polycarbonate resin, an acrylic resin, a polyester resin, a phenoxy resin, an epoxy resin, and a polyolefin resin.
- examples of the photocurable resin include a urethane acrylate resin, a polyester acrylate resin, You may use what mixed the photocuring initiator etc. with at least 1 sort (s) selected from the group which consists of unsaturated polyester resin, silicone acrylate resin, and epoxy acrylate resin as needed.
- these resins may be mixed with a curing agent, a curing accelerator, a binder, a surface conditioner, a pigment, an ultraviolet absorber, a light stabilizer and the like, if necessary.
- the resin may be a copolymer or a mixture of different resins.
- photocuring resin since a better moldability can be ensured, it is desirable to perform a curing treatment after molding.
- the total content of resins and additives other than the thermosetting resin or photocurable resin used in the protective layer is preferably 10% by mass or less based on the total mass of the protective layer, and is preferably 5% by mass. % Or less is more preferable. If a resin other than the thermosetting resin or the photocurable resin is contained in an amount greater than the above range, the original performance of the protective layer may not be obtained.
- the thickness of the protective layer in the present invention is preferably 10 to 70 ⁇ m, more preferably 20 to 50 ⁇ m.
- the thickness is 10 ⁇ m or more, the coating film characteristics can be further improved, which is preferable.
- the thickness can be calculated by measuring with a micrometer according to JIS C 2151 (2006 edition) every time each layer is formed, during the production process of the decorative molding film.
- the thickness of a protective layer can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- the colored layer used in the decorative molding film of the present invention is a layer having a function of giving a desired color and texture to an object to be decorated, and has a concealing property when formed into a decorative molded body.
- the colored layer include a layer composed of a colored resin obtained by mixing a binder resin and a pigment, an ink, a metal thin film, and the like.
- a layer composed of a colored resin mixed with a binder resin and a pigment (hereinafter also abbreviated as a colored resin layer) from the viewpoint that the moldability of the decorative molding film is not impaired and the storage elastic modulus in the present invention is easily adjusted. Most preferred).
- the E′b (100) of the colored layer is preferably 12 MPa or less. If E'b (100) is greater than 12 MPa, the molding stress at the time of stretching becomes high, the orientation of the pigment contained in the colored layer is disturbed, and the appearance may be deteriorated. In addition, when the decorative body is left in a high temperature atmosphere, the colored layer softens, and the protective layer cannot withstand the heat shrinkage and may cause wrinkles and cracks. Therefore, E′b (100) is 5 MPa or more. It is preferable that The stress at 100% stretching at 100 ° C. of the colored layer is preferably 0.2 MPa or less. When the stress at 100% stretching at 100 ° C. is greater than 0.2 MPa, the orientation of the pigment contained in the colored layer is disturbed and the appearance is deteriorated, as in the case where E′b (100) is greater than 12 MPa. There is.
- the E′b (40) of the colored layer is preferably 15 to 25 MPa.
- E′b (40) refers to the storage elastic modulus of the colored layer at 40 ° C. If E'b (40) is less than 15 MPa, the colored layer may be deformed and a trace may easily remain when pressure is applied from above the compact. On the other hand, if E'b (40) is greater than 25 MPa, it may not be possible to follow the deformation from above the molded body and cracks may occur.
- the method for adjusting the storage elastic modulus of the colored layer in the present invention is not particularly limited, but a method of mixing a plurality of resins, a method of adjusting the crosslink density of the resin, and adding a curing agent or a plasticizer to the resin paint. And a method for changing the amount of the pigment contained in the resin.
- the storage elastic modulus of the colored layer it can be measured by the method described in the examples. However, when the colored layer is already laminated with the base film and / or the protective layer, the other layer can be measured. After polishing and removing, the measurement may be performed by the method described in Examples.
- thermosetting resin examples include unsaturated polyester resin, phenol resin, epoxy resin, acrylic resin, urethane resin, melamine resin, urea resin, and polycarbonate resin.
- thermoplastic resin examples include polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, and polystyrene resin.
- photo-curable resin examples include urethane acrylate resin, polyester acrylate resin, unsaturated polyester resin, silicone acrylate resin, epoxy acrylate resin, and the like. It may be used. You may use what selected and mixed 1 or more resin from said resin.
- the resin should be a solvent solution or an aqueous dispersion. Is preferred.
- a method for producing the solvent solution or the aqueous dispersion a known method can be used.
- these resins may be mixed with a curing agent, a curing accelerator, a binder, a surface conditioner, a dye, a plasticizer, an ultraviolet absorber, a light stabilizer, and the like, if necessary.
- the resin may be a copolymer or a mixture of different resins.
- a thermosetting resin can be preferably used.
- the pigment for example, aluminum powder, carbon black, titanium dioxide, mica, phthalocyanine green, dioxazine violet, etc., any of inorganic pigments and organic pigments may be used, and the pigment may be used alone. Well, you may use it in mixture of 2 or more types.
- the pigment concentration can be adjusted within a range that does not impair the elongation at break of the binder resin.
- the thickness of the colored layer of the present invention is preferably 15 to 50 ⁇ m, more preferably 20 to 40 ⁇ m.
- the thickness of 15 ⁇ m or more is preferable because a colored layer having a desired color can be easily obtained.
- the thickness is 50 ⁇ m or less, the flatness of the surface becomes better, and it is preferable because the adhesive layer can be easily formed on the colored layer.
- the thickness can be calculated by measuring with a micrometer according to JIS C 2151 (2006 edition) every time each layer is formed, during the production process of the decorative molding film.
- the thickness of a colored layer can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- the decorative molding film in the present invention may further include an adhesive layer on the colored layer. It is preferable to use an adhesive that reacts with heat such as hot melt or thermosetting because the film for decorative molding is stretched by heat during molding and can be attached to the object to be decorated.
- the component of the adhesive layer is not particularly limited as long as it has adhesion to the object to be decorated, and examples thereof include acrylic adhesives, urethane adhesives, polyester adhesives, olefin adhesives, and the like. It is done.
- Examples of the method for producing a decorative molded body according to the present invention include a method for producing a decorative molded body produced by attaching the above-described decorative molding film to a body to be decorated and then peeling the base film.
- the decorative molding film can be affixed to a three-dimensional decorative object such as a reduced pressure molding method (sometimes referred to as a vacuum molding method) or a compressed air molding method when the decorative molding film is applied to the decorative object. It is preferable to apply a known thermoforming method.
- the decorative molding film of the present invention is heated to a temperature above the softening point under reduced pressure conditions, and the film is bonded.
- the decoration method by spray coating which has conventionally required a multi-step process, it is necessary to adopt a molding method in which a layer is brought into contact with the surface of the object to be decorated and then attached to the object by thermoforming. It is possible to reduce the number of steps for decorating, and this is preferable because the production efficiency of the decorative molded body is improved.
- the sample was cut into a rectangle having a length of 60 mm and a width of 10 mm, and the storage elastic modulus at 40 ° C. and 100 ° C. was determined using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc., DMS6100) under the following conditions.
- the measurement is performed by setting a film sample in a constant temperature bath set at a temperature of 100 ° C., preheating for 60 seconds, performing a tensile test in the constant temperature layer, and measuring the stress at 100% stretching (when the sample reaches 40 mm). Asked. The measurement was performed at three points for each sample, and evaluation was performed with an average value of the three points.
- the standard value of 100% stretching stress of the protective layer is 0.3 MPa
- the standard value of 100% stretching stress of the colored layer is 0.2 MPa
- the 100% stretching stress of the protective layer and the colored layer are both below the standard value.
- the others were designated as formability B. Those having moldability A were considered to have good moldability for decorative molding films.
- Molding temperature 110 ° C Heater output: 200% for rapid heating, 80% for normal heating Rapid heating time: 10 seconds Vacuum pressure: 0 kPa Air pressure: 300kPa Air pressure time: 15 seconds Minute release: 2 seconds
- a flat resin molded body of length 250 mm ⁇ width 100 mm ⁇ thickness 3 mm made of polyolefin resin (TSOP GP6BS, manufactured by Prime Polymer Co., Ltd.) was used as the decorative molded body.
- a crack means a state in which any one or more of each layer has a crack
- a shrinkage means a state in which the coating film is contracted by 5 mm or more from the end of the decorative molded body. The case where no shrinkage or cracking was seen in the appearance was A, and the others were B.
- the intensity of swell at each swell wavelength W1 to W4 was measured using a microwave scan T (BYK-Gardner).
- the intensity of the undulation at each of the undulation wavelengths W1 to W4 is obtained by scanning while irradiating the sample surface with the laser beam, and detecting and analyzing the intensity (diffusion, condensing) of the reflected beam with a sensor and digitizing it.
- the reference intensity values for each wave wavelength and wave intensity are shown below. All the undulation intensities at each undulation wavelength were designated as “A” when the intensity was less than the reference intensity value, and as “B” including at least one greater than the reference intensity value.
- Waviness wavelength W1 (wavelength 2.4 mm or more): reference intensity value 22 Waviness wavelength W2 (wavelength 0.8 mm or more and less than 2.4 mm): reference intensity value 40 Waviness wavelength W3 (wavelength 0.32 mm or more and less than 0.8 mm): reference intensity value 35 Waviness wavelength W4 (wavelength less than 0.32 mm): reference intensity value 20
- Pencil hardness Set the pencil (6B) at a 45 degree angle on the protective layer side of the decorative molded body produced by the same method as in Section 3 above, and scratch it for about 10 mm with a load of 200 g from above to check whether there is a dent on the surface. It was confirmed visually. A with no flaws, A with a slight dent but no problem in practical use, and C with a clear dent. The sample of A or B was regarded as having good pencil hardness, and the sample of C was regarded as having poor pencil hardness. The results are shown in Table 1.
- Example 1 As a base film, a 100 ⁇ m thick unstretched polyethylene terephthalate film (FL10, manufactured by Toray Industries, Inc.) and a 40 ⁇ m thick unstretched polypropylene film (SC, manufactured by Tohello) were dry-laminated with a urethane-based adhesive. It was.
- FL10 unstretched polyethylene terephthalate film
- SC 40 ⁇ m thick unstretched polypropylene film
- a carbodiimide-based curing agent (“Carbodilite” (registered trademark) with respect to 100 parts by mass of a polycarbonate-based polyurethane resin emulsion paint (“Permarin” (registered trademark) UA-310, manufactured by Sanyo Chemical Industries)) ) V-02, manufactured by Nisshinbo Chemicals Co., Ltd.) was added and mixed with an applicator method so that the thickness after drying was 40 ⁇ m, and then dried at 80 ° C. for 30 minutes to form a protective layer. did.
- a paint for forming an adhesive layer (M-28, manufactured by Toyobo Co., Ltd.) was applied on the formed colored layer by an applicator method so that the thickness after drying was 20 ⁇ m, and then at 80 ° C. for 30 minutes. An adhesive layer was formed by drying to obtain a decorative molding film.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 2 For the formation of the colored layer, an isocyanate paint ("Takenate” (registered trademark) 500, manufactured by Mitsui Chemicals Co., Ltd.) with respect to 100 parts by mass of the paint (R2325, manufactured by Nippon Bee Chemical Co., Ltd.) for forming the colored layer.
- a decorative molded body was obtained in the same manner as in Example 1 except that 5 parts by mass was added and mixed.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 3 For forming the protective layer, a carbodiimide-based curing agent (“Carbodilite” (registered trademark) V-) for 100 parts by mass of the polycarbonate-based polyurethane resin emulsion paint (“Permarin” (registered trademark) UA-310, manufactured by Sanyo Chemical Industries) 02, manufactured by Nisshinbo Chemicals Co., Ltd.) was used to obtain a decorative molded body in the same manner as in Example 1 except that 0.5 part by mass was added and mixed.
- Carbodilite registered trademark
- Permarin registered trademark
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 4 For the formation of the colored layer, an isocyanate paint ("Takenate” (registered trademark) 500, manufactured by Mitsui Chemicals Co., Ltd.) with respect to 100 parts by mass of the paint (R2325, manufactured by Nippon Bee Chemical Co., Ltd.) for forming the colored layer.
- a decorative molded body was obtained in the same manner as in Example 3 except that 5 parts by mass of added and mixed were used.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 5 For forming a colored layer, an isocyanate paint ("Takenate” (registered trademark) 500, manufactured by Mitsui Chemicals) is used with respect to 100 parts by mass of a paint (R2325, manufactured by Nippon B Chemical Co., Ltd.) for forming the colored layer.
- a decorative molded body was obtained in the same manner as in Example 1 except that 5 parts by mass was added and mixed.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 6 For forming a colored layer, an isocyanate paint ("Takenate” (registered trademark) 500, manufactured by Mitsui Chemicals) is used with respect to 100 parts by mass of a paint (R2325, manufactured by Nippon B Chemical Co., Ltd.) for forming the colored layer.
- a decorative molded body was obtained in the same manner as in Example 3 except that 5 parts by mass of added and mixed were used.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Example 7 The decorative molded body was formed in the same manner as in Example 5 except that only the polycarbonate-based polyurethane resin emulsion paint ("Permarin” (registered trademark) UA-310, manufactured by Sanyo Chemical Industries) was used for forming the protective layer. Obtained.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Comparative Example 2 For forming the protective layer, a carbodiimide-based curing agent (“Carbodilite” (registered trademark) V-) for 100 parts by mass of the polycarbonate-based polyurethane resin emulsion paint (“Permarin” (registered trademark) UA-310, manufactured by Sanyo Chemical Industries) 02, manufactured by Nisshinbo Chemicals Co., Ltd.) was used to obtain a decorative molded body in the same manner as in Comparative Example 1 except that 0.5 parts by mass was added and mixed.
- Carbodilite registered trademark
- Permarin registered trademark
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- a carbodiimide-based curing agent (“Carbodilite” (registered trademark) V-) for 100 parts by mass of the polycarbonate-based polyurethane resin emulsion paint (“Permarin” (registered trademark) UA-310, manufactured by Sanyo Chemical Industries) 02, manufactured by Nisshinbo Chemicals Co., Ltd.) was used in the same manner as in Example 1 except that 2 parts by mass of added and mixed were used.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Comparative Example 4 For the formation of the colored layer, an isocyanate paint ("Takenate” (registered trademark) 500, manufactured by Mitsui Chemicals Co., Ltd.) with respect to 100 parts by mass of the paint (R2325, manufactured by Nippon Bee Chemical Co., Ltd.) for forming the colored layer.
- a decorative molded body was obtained in the same manner as in Comparative Example 3 except that a mixture in which 5 parts by mass were added and mixed was used.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- Table 1 shows the evaluation results of the obtained decorative layer and decorative molded body.
- the decorative molding film of the present invention can be preferably used for decorating automobile parts, electrical appliances, and the like, and can be preferably applied to applications that require design and functions such as heat resistance.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
Description
(1)E’a(100)/E’b(100)が8以下である。
(2)E’a(100)が10MPa以上である。
(3)E’b(100)が12MPa以下である。
(1)E’a(100)/E’b(100)が8以下である。
(2)E’a(100)が10MPa以上である。
(3)E’b(100)が12MPa以下である。
本発明において用いられる基材フィルムとしては、100℃における破断伸度が200%以上のフィルムが好ましく用いられる。たとえば、ポリオレフィン、ポリエステル、ポリ塩化ビニル、ポリ(メタ)アクリル酸エステル、ポリアミド、ポリエステルアミド、ポリエーテル、ポリスチレン、ポリエーテルエステル、ポリカーボネート等の熱可塑性樹脂を加工して得られるフィルムが挙げられ、未延伸フィルム、1軸延伸フィルム、2軸延伸フィルムの何れであってもよい。
本発明の装飾成形用フィルムに用いられる保護層は、装飾成形体に適用されるとき、最表層に位置することとなるため、保護層に用いられる樹脂は装飾成形用フィルムの成形性を損なわない樹脂であると共に、透明性や光沢性といった意匠特性、耐擦過性や耐衝撃性、耐薬品性、耐候性といった塗膜特性を兼ね備えた樹脂であることが好ましい。
本発明の装飾成形用フィルムに用いられる着色層は、目的とする色や風合を装飾する被装飾体に与える機能を有する層である、また、装飾成形体に成形したときに隠蔽性を有する層である。着色層としては例えば、バインダー樹脂と顔料を混合した着色樹脂、インク、金属薄膜などで構成される層が挙げられる。装飾成形用フィルムの成形性を損なわないことや本発明における貯蔵弾性率の調整がし易い点からバインダー樹脂と顔料を混合した着色樹脂で構成される層(以降、着色樹脂層と略記することもある)が最も好ましい。
本発明における装飾成形用フィルムは、着色層上にさらに接着層を備えていてもよい。成形時の熱により装飾成形用フィルムを延伸させると同時に被装飾体への貼り付けが可能となる点からホットメルトや熱硬化といった熱で反応する接着剤を使用することが好ましい。接着層の成分としては、被装飾体との接着性を有するものであれば特に制限はなく、例えば、アクリル系接着剤、ウレタン系接着剤、ポリエステル系接着剤、オレフィン系接着剤、等が挙げられる。
本発明にかかる装飾成形体の製造方法としては、前述の装飾成形用フィルムを、被装飾体に貼り付けた後、基材フィルムを剥離することにより作製する装飾成形体の製造方法が挙げられる。装飾成形用フィルムを、被装飾体に貼り付ける際に減圧成形法(真空成形法と言う場合もある)や圧空成形法など3次元形状の被装飾体に装飾成形用フィルムを貼り付け可能な、既知の熱成形方法を適用することが好ましい。中でも、本発明の装飾成形用フィルムの成形性や被装飾体との接着性の点から、減圧条件下において、本発明の装飾成形用フィルムを軟化点以上の温度に加熱し、該フィルムの接着層を被装飾体の表面に接触せしめて熱成形にて被装飾体に貼り付ける成形方法を採ることが、従来多段階の工程が必要であったスプレー塗装による装飾方法と比べて、被装飾体に装飾する工程数を減らすことが可能となり、装飾成形体の生産効率が向上することから好ましい。
1.保護層および着色層の40℃および100℃の貯蔵弾性率
サンプル作成用に離型フィルム(“セラピール”(登録商標)、東レフィルム加工社製)を用い、該離型フィルムの離型面に、測定する塗料を乾燥後の厚さが40μmとなるようアプリケーター法により塗布した後、80℃で30分間乾燥し、単層のサンプルを作製した。
試長:20mm
最小荷重:約10mN
振幅:10μm
測定温度範囲:25℃~150℃
昇温速度:2℃/分
前記1項で作成したのと同様の方法で保護層および着色層の単層のサンプルを作成し、サンプルを10mm幅、50mm長に裁断して測定サンプルとした。引張試験機(オリエンテック製、テンシロンUCT-100)を用いて、引張チャック間の距離が20mmになるようにセットし、引張速度を200mm/分で引張試験を行った。測定は100℃の温度に設定した恒温槽中にフィルムサンプルをセットし、60秒間予熱した後、恒温層中で引張試験を行い、100%延伸時(サンプルが40mmになった時点)の応力を求めた。測定は各サンプル3点ずつ行い、3点の平均値で評価を行った。保護層の100%延伸応力の基準値を0.3MPa、着色層の100%延伸応力の基準値を0.2MPaとし、保護層と着色層の100%延伸応力がいずれも基準値以下であるものを成形性Aとし、それ以外を成形性Bとした。成形性Aのものを装飾成形用フィルムの成形性が良好であるとした。
TOM成形機(布施真空株式会社製、NGF0406-T)を用いて、装飾成形用フィルムの接着層側と被加飾成形体の最も面積の大きい面とが相対するようにフィルムをセットし、以下の条件で成型を行い、装飾成形体を作製した。装飾成形用フィルムの延伸倍率は、TOM成型機の箱型の窪みの深さを調整した。具体的には、セットしたフィルムから箱型の窪みの底面までの距離を85mmとした。
ヒーター出力:急加熱時 200%、通常加熱時 80%
急加熱時間:10秒
真空圧力:0kPa
圧空圧力:300kPa
圧空時間:15秒
微量開放:2秒
前記3項と同等の方法で作製した装飾成形体の保護層側上を、マイクロウェーブスキャンT(BYK-Gardner社製)を用いて、各うねり波長W1~W4におけるうねりの強度を測定した。ここで、各うねり波長W1~W4におけるうねりの強度は、レーザービームを試料表面に照射しながら走査し、その反射ビームの強度(拡散、集光)をセンサーで検出、解析し数値化したものであり、数値が小さい程各うねり波長W1~W4に対応するうねりが少なく、試料表面が平滑であることを表す。
うねり波長W1(波長 2.4mm以上 ):基準強度値22
うねり波長W2(波長 0.8mm以上 2.4mm未満):基準強度値40
うねり波長W3(波長 0.32mm以上0.8mm未満):基準強度値35
うねり波長W4(波長 0.32mm未満 ):基準強度値20
前記3項と同等の方法で作製した装飾成形体の保護層側に鉛筆(6B)を45度の角度でセットして、上から200gの荷重をかけて10mm程度引っかき、表面の凹みの有無を目視で確認した。傷が付いていないものをA、若干凹みがあるが実用上問題ないものをB、凹みが明確なものをCとした。AまたはBのものを鉛筆硬度が良好であるとし、Cのものを鉛筆硬度が不良であるとした。結果を表1に示す。
基材フィルムとして、厚さ100μmの未延伸ポリエチレンテレフタレートフィルム(FL10、東レ社製)と厚さ40μmの未延伸ポリプロピレンフィルム(SC、東セロ社製)とをウレタン系接着剤でドライラミネートしたものを用いた。基材フィルムのポリプロピレンフィルム側に、ポリカーボネート系ポリウレタン樹脂エマルション塗料(“パーマリン”(登録商標)UA-310、三洋化成工業社製)100質量部に対してカルボジイミド系硬化剤(“カルボジライト”(登録商標) V-02、日清紡ケミカルズ社製)を1質量部添加・混合したものを、乾燥後の厚さが40μmとなるようアプリケーター法により塗布した後、80℃で30分間乾燥し、保護層を形成した。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)0.5質量部を添加・混合したものを用いたこと以外は実施例1と同様の方法にて装飾成形体を得た。
保護層の形成に、ポリカーボネート系ポリウレタン樹脂エマルション塗料(“パーマリン”(登録商標)UA-310、三洋化成工業社製)100質量部に対してカルボジイミド系硬化剤(“カルボジライト”(登録商標) V-02、日清紡ケミカルズ社製)を0.5質量部添加・混合したものを用いたこと以外は実施例1と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)0.5質量部を添加・混合したものを用いたこと以外は実施例3と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)1.5質量部を添加・混合したものを用いたこと以外は実施例1と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)1.5質量部を添加・混合したものを用いたこと以外は実施例3と同様の方法にて装飾成形体を得た。
保護層の形成に、ポリカーボネート系ポリウレタン樹脂エマルション塗料(“パーマリン”(登録商標)UA-310、三洋化成工業社製)のみを用いたこと以外は実施例5と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)2質量部を添加・混合したものを用いたこと以外は実施例1と同様の方法にて装飾成形体を得た。
保護層の形成に、ポリカーボネート系ポリウレタン樹脂エマルション塗料(“パーマリン”(登録商標)UA-310、三洋化成工業社製)100質量部に対してカルボジイミド系硬化剤(“カルボジライト”(登録商標) V-02、日清紡ケミカルズ社製)を0.5質量部添加・混合したものを用いたこと以外は比較例1と同様の方法にて装飾成形体を得た。
保護層の形成に、ポリカーボネート系ポリウレタン樹脂エマルション塗料(“パーマリン”(登録商標)UA-310、三洋化成工業社製)100質量部に対してカルボジイミド系硬化剤(“カルボジライト”(登録商標) V-02、日清紡ケミカルズ社製)を2質量部添加・混合したものを用いたこと以外は実施例1と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)0.5質量部を添加・混合したものを用いたこと以外は比較例3と同様の方法にて装飾成形体を得た。
着色層の形成に、着色層を形成するための塗料(R2325、日本ビー・ケミカル社製)100質量部に対して、イソシアネート塗料(“タケネート”(登録商標)500、三井化学社製)2質量部を添加・混合したものを用いたこと以外は比較例3と同様の方法にて装飾成形体を得た。
2 保護層
3 着色層
4 接着層
Claims (6)
- 基材フィルムの上に保護層と着色層とがこの順で配された積層構造を有する装飾成形用フィルムであって、前記保護層の100℃における貯蔵弾性率をE’a(100)とし、前記着色層の100℃における貯蔵弾性率をE’b(100)としたとき、E’a(100)およびE’b(100)が以下の(1)~(3)の条件を満たすことを特徴とする装飾成形用フィルム。
(1)E’a(100)/E’b(100)が8以下である。
(2)E’a(100)が10MPa以上である。
(3)E’b(100)が12MPa以下である。 - 前記保護層の100℃における100%延伸時応力が0.3MPa以下である、請求項1に記載の装飾成形用フィルム。
- 前記保護層の40℃における貯蔵弾性率E’a(40)が400~700MPaである、請求項1または2に記載の装飾成形用フィルム。
- 前記着色層の100℃における100%延伸時応力が0.2MPa以下である、請求項1~3のいずれかに記載の装飾成形用フィルム。
- 前記着色層の40℃における貯蔵弾性率E’b(40)が15~25MPaである、請求項1~4のいずれかに記載の装飾成形用フィルム。
- 請求項1~5のいずれかに記載の装飾成形用フィルムを被装飾体に貼り付けた後、基材フィルムを剥離することにより装飾成形体を作製することを特徴とする装飾成形体の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP13800401.5A EP2860029A4 (en) | 2012-06-08 | 2013-05-28 | FILM FOR DECORATIVE MOLDING AND METHOD FOR PRODUCING DECORATIVE MOLDED PART |
CN201380026164.5A CN104321192B (zh) | 2012-06-08 | 2013-05-28 | 装饰成型用膜、和装饰成型体的制造方法 |
JP2013529465A JP6167901B2 (ja) | 2012-06-08 | 2013-05-28 | 装飾成形用フィルム、および装飾成形体の製造方法 |
US14/400,468 US9757973B2 (en) | 2012-06-08 | 2013-05-28 | Film for decorative forming and production method for decorative formed body |
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JP2012-130559 | 2012-06-08 |
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CN (1) | CN104321192B (ja) |
WO (1) | WO2013183489A1 (ja) |
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WO2015159748A1 (ja) * | 2014-04-15 | 2015-10-22 | 東レ株式会社 | 積層フィルム、および積層フィルムの製造方法 |
WO2020067535A1 (ja) * | 2018-09-28 | 2020-04-02 | 帝人株式会社 | 表面被覆フィルム並びに表面被覆繊維強化樹脂成形品及びその製造方法 |
JP2021079617A (ja) * | 2019-11-19 | 2021-05-27 | 東レ株式会社 | 積層体、樹脂フィルム |
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DE102016120781A1 (de) * | 2016-10-31 | 2018-05-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verbundfolie zur Beschichtungsstoffübertragung, deren Verwendung und ein Verfahren zur Herstellung der Verbundfolie sowie ein Verfahren zur Herstellung eines beschichteten Kunststoffbauteiles |
US11292165B2 (en) * | 2017-09-29 | 2022-04-05 | Lg Chem, Ltd. | Method for selecting material of injection-molded article and method for manufacturing injection-molded article |
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- 2013-05-28 US US14/400,468 patent/US9757973B2/en active Active
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Cited By (10)
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WO2015159748A1 (ja) * | 2014-04-15 | 2015-10-22 | 東レ株式会社 | 積層フィルム、および積層フィルムの製造方法 |
KR20160145546A (ko) * | 2014-04-15 | 2016-12-20 | 도레이 카부시키가이샤 | 적층 필름 및 적층 필름의 제조 방법 |
JPWO2015159748A1 (ja) * | 2014-04-15 | 2017-04-13 | 東レ株式会社 | 積層フィルム、および積層フィルムの製造方法 |
KR102242709B1 (ko) | 2014-04-15 | 2021-04-22 | 도레이 카부시키가이샤 | 적층 필름 및 적층 필름의 제조 방법 |
WO2020067535A1 (ja) * | 2018-09-28 | 2020-04-02 | 帝人株式会社 | 表面被覆フィルム並びに表面被覆繊維強化樹脂成形品及びその製造方法 |
JPWO2020067535A1 (ja) * | 2018-09-28 | 2021-08-30 | 帝人株式会社 | 表面被覆フィルム並びに表面被覆繊維強化樹脂成形品及びその製造方法 |
JP6994584B2 (ja) | 2018-09-28 | 2022-01-14 | 帝人株式会社 | 表面被覆フィルム並びに表面被覆繊維強化樹脂成形品及びその製造方法 |
US11787129B2 (en) | 2018-09-28 | 2023-10-17 | Teijin Limited | Surface-coated film, surface-coated fiber-reinforced resin molded product, and manufacturing method thereof |
JP2021079617A (ja) * | 2019-11-19 | 2021-05-27 | 東レ株式会社 | 積層体、樹脂フィルム |
JP7419761B2 (ja) | 2019-11-19 | 2024-01-23 | 東レ株式会社 | 積層体、樹脂フィルム |
Also Published As
Publication number | Publication date |
---|---|
EP2860029A4 (en) | 2016-01-13 |
CN104321192B (zh) | 2016-03-02 |
JP6167901B2 (ja) | 2017-07-26 |
CN104321192A (zh) | 2015-01-28 |
EP2860029A1 (en) | 2015-04-15 |
US9757973B2 (en) | 2017-09-12 |
JPWO2013183489A1 (ja) | 2016-01-28 |
US20150129120A1 (en) | 2015-05-14 |
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