WO2014157232A1 - 加飾シート及び加飾樹脂成形品 - Google Patents
加飾シート及び加飾樹脂成形品 Download PDFInfo
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- WO2014157232A1 WO2014157232A1 PCT/JP2014/058333 JP2014058333W WO2014157232A1 WO 2014157232 A1 WO2014157232 A1 WO 2014157232A1 JP 2014058333 W JP2014058333 W JP 2014058333W WO 2014157232 A1 WO2014157232 A1 WO 2014157232A1
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- WIPO (PCT)
- Prior art keywords
- resin
- layer
- decorative sheet
- primer layer
- thin film
- Prior art date
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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
- 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
- B29C45/14688—Coating articles provided with a decoration
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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
- 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
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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
- 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
- B32B15/082—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 comprising vinyl resins; comprising acrylic resins
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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
- 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
- B32B15/085—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 comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B15/09—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 comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B15/095—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 comprising polyurethanes
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- 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
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- 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
- B32B2307/412—Transparent
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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
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B2307/538—Roughness
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
Definitions
- the present invention relates to a decorative sheet having a metallic design. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.
- a decorative resin molded product in which a decorative sheet having a metallic tone is laminated on the surface of the resin molded product is used as these members.
- a molding method in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding is used.
- Some decorative resin molded products have complex surface shapes such as three-dimensional curved surfaces. For this reason, the decorative sheet is required to have three-dimensional formability that can sufficiently follow the shape of the decorative resin molded product having a complicated surface shape.
- a resin layer for example, a base material layer and an adhesive layer
- a metal thin film layer formed of a metal tends to be a problem. Due to the low adhesion between the resin layer and the metal thin film layer, the resin layer and the metal thin film layer may be peeled off and floated when the decorative sheet is formed.
- Patent Document 1 discloses that a post-anchor layer formed of a resin is provided in order to improve the adhesion between the metal vapor deposition layer of the metal vapor deposition transfer material and the adhesive print layer.
- a decorative sheet that can follow the shape of a particularly complex decorative resin molded product.
- Such a decorative sheet has a maximum draw ratio, for example, in a portion corresponding to a curved portion of the resin molded product. May be stretched to 150% or more. This means that a part of the decorative sheet having the metal thin film layer is stretched by 2.5 times or more, which is a very strict molding condition.
- the conventional decorative sheet having a metal thin film layer cannot follow the shape of such a complicated decorative resin molded product, and the resin layer and the metal thin film layer can be used during the molding of the decorative sheet. There is a problem that peeling occurs between the two and the like, and floating occurs.
- a decorative sheet having a three-dimensional formability capable of sufficiently following the shape of a decorative resin molded product having a complicated surface shape is required.
- the main object of the present invention is to provide a decorative sheet having high three-dimensional formability that can sufficiently follow the shape of a decorative resin molded product having a complicated surface shape.
- the present inventor has intensively studied to solve the above problems.
- the first primer layer has a glass transition point of ⁇ 30 ° C. to 80 ° C. It has been found that by including a cured product of a resin at 0 ° C., it is possible to impart high three-dimensional moldability that can sufficiently follow the shape of a decorative resin molded product having a complicated surface shape to the decorative sheet.
- the present invention has been completed by further studies based on these findings.
- this invention provides the invention of the aspect hung up below.
- Item 1 At least a base material layer, a first primer layer, and a metal thin film layer are laminated in this order,
- the first primer layer is a decorative sheet containing a cured product of a resin having a glass transition point of ⁇ 30 ° C. to 80 ° C.
- Item 2. Used for decorating resin molded products with curved parts, Item 2. The decorative sheet according to Item 1, wherein the curved portion has a shape that requires stretching at a maximum stretching ratio of 150% or more with respect to the decorative sheet.
- Item 3. Item 1 or 2 is that the resin having a glass transition point of ⁇ 30 ° C. to 80 ° C.
- the decorative sheet as described. Item 4.
- the resin having a glass transition point of ⁇ 30 ° C. to 80 ° C. is a polyol resin.
- Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the first primer layer is formed of a cured product of the polyol resin and an isocyanate compound.
- Item 5. The decorative sheet according to Item 4, wherein the polyol resin in the first primer layer is a polyester polyol.
- Item 6. Item 6.
- Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, which has an adhesive layer between the base material layer and the first primer layer.
- Item 8. Item 8. The decorative sheet according to Item 7, wherein the adhesive layer contains a chlorine-based resin.
- Item 9. Item 9. The decorative sheet according to Item 8, wherein the first primer layer is formed of a resin composition containing a silane coupling agent. Item 10.
- the chlorinated resin is selected from the group consisting of polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polypropylene chloride, and chlorinated polypropylene.
- Item 10 The decorative sheet according to Item 8 or 9, which is at least one kind.
- Item 11. The decorative sheet according to any one of Items 1 to 10, wherein the first primer layer does not substantially contain a chlorine-based resin.
- the metal thin film layer is formed of at least one metal selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and an alloy containing at least one of these.
- Item 12. The decorative sheet according to any one of Items 1 to 11.
- Item 13. The decorative sheet according to any one of Items 1 to 12, wherein a surface protective layer is further laminated on the metal thin film layer.
- a second primer layer is further provided between the metal thin film layer and the surface protective layer, Item 14.
- the decorative sheet according to Item 13, wherein the second primer layer contains a cured product of a resin having a glass transition point of 55 ° C to 110 ° C.
- Item 15. Item 15.
- the resin having a glass transition point of 55 ° C. to 110 ° C. is a polyol resin.
- the decorative sheet according to Item 16 wherein the polyol resin in the second primer layer is at least one of polyester polyol and acrylic polyol.
- Item 19 The decorative sheet according to any one of Items 1 to 18, wherein a transparent film layer is further laminated on the metal thin film layer.
- Item 20. The decorative sheet according to any one of Items 1 to 19, wherein the first primer layer further contains a colorant.
- the first primer layer is a decorative resin molded product containing a cured product of a resin having a glass transition point of ⁇ 30 ° C. to 80 ° C. Item 22. Further comprising an adhesive layer containing a chlorine resin between the base material layer and the first primer layer, Item 22.
- a second primer layer and a surface protective layer are further laminated in this order on the metal thin film layer, Item 23.
- Item 24 A vacuum forming step of forming the decorative sheet according to any one of Items 1 to 20 into a three-dimensional shape in advance using a vacuum forming die, Trimming step of trimming an excess portion of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet into an injection mold, closing the injection mold, and injecting the resin in a fluid state into the injection mold
- the decorative resin molded product has a curved portion; Item 25.
- a decorative sheet having high three-dimensional formability that can sufficiently follow the shape of a decorative resin molded product having a complicated surface shape, and the decorative sheet are used.
- a decorative resin molded product can be provided.
- the decorative sheet of the present invention is composed of a laminate in which at least a base material layer, a first primer layer, and a metal thin film layer are laminated in this order, and the first primer layer is a glass transition. It includes a cured product of a resin having a point of ⁇ 30 ° C. to 80 ° C.
- the first primer layer provided between the base material layer and the metal thin film layer contains a cured product of a resin having a specific glass transition point as described above. High three-dimensional moldability that can sufficiently follow the shape of a decorative resin molded product having a complicated surface shape is imparted.
- the decorative sheet of the present invention will be described in detail.
- the decorative sheet of the present invention has a laminated structure having at least the base material layer 1, the first primer layer 3, and the metal thin film layer 4 in this order.
- an adhesive layer 2 is provided between the base material layer 1 and the first primer layer 3 as necessary for the purpose of improving the adhesion between these layers. Also good.
- the metal thin film layer 4 is formed on the metal thin film layer 4 for the purpose of enhancing the adhesion between the metal thin film layer 4 and the layer provided thereon.
- a second primer layer 6 may be provided as necessary.
- a color clear layer 7 may be provided on the metal thin film layer 4 as necessary for the purpose of further imparting gloss to the metal tone of the metal thin film layer 4.
- a third layer may be provided directly below the surface protective layer 5.
- a primer layer 8 may be provided.
- a second adhesive layer 10 or the like may be provided under the base material layer 1.
- a laminated structure of the decorative sheet of the present invention a laminated structure in which a base layer / first primer layer / metal thin film layer is laminated in this order; an adhesive layer / base material layer / first primer layer / metal thin film layer Laminated structure laminated in this order; base material layer / adhesive layer / first primer layer / metal thin film layer laminated structure in this order; base material layer / adhesive layer / first primer layer / metal thin film layer / Laminated structure in which surface protective layers are laminated in this order; Laminated structure in which base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / surface protective layer are laminated in this order; / Adhesive layer / first primer layer / metal thin film layer / color clear layer / third primer layer / surface protective layer in this order; laminated structure; base material layer / adhesive layer / first primer layer / metal Thin film layer / second primer layer / color clear layer / third Laminated structure in which primer layer
- FIG. 1 shows an example of a decorative sheet in which a base layer / adhesive layer / first primer layer / metal thin film layer / surface protective layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention.
- a schematic cross-sectional view is shown.
- FIG. 2 as one aspect of the laminated structure of the decorative sheet of the present invention, a base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / surface protective layer were laminated in this order.
- the schematic sectional drawing of an example of a decorating sheet is shown.
- FIG. 1 shows an example of a decorative sheet in which a base layer / adhesive layer / first primer layer / metal thin film layer / surface protective layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention.
- FIG. 2 shows an example of a decorative sheet in which a base layer / adhesive layer / first primer layer / metal thin film layer / surface protective layer are laminated in this
- stacked in this order is shown.
- a base layer / adhesive layer / first primer layer / metal thin film layer / transparent film layer / second primer layer / color clear layer / first 3 shows a schematic cross-sectional view of an example of a decorative sheet in which three primer layers / surface protective layers are laminated in this order.
- a base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / transparent film layer / color clear layer / first 3 shows a schematic cross-sectional view of an example of a decorative sheet in which three primer layers / surface protective layers are laminated in this order.
- the base material layer 1 is formed of a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention.
- the resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molded resin layer, and the like, and preferably a thermoplastic resin.
- thermoplastic resin examples include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylate resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET).
- ABS resin is preferable from the viewpoint of three-dimensional moldability.
- ABS resin component which forms the base material layer 1 only 1 type may be used and 2 or more types may be mixed and used.
- the base material layer 1 may be formed with the single layer sheet
- the method of improving the three-dimensional moldability of a decorating sheet by making the base material layer 1 into a multilayer sheet is also considered, in the decorating sheet of this invention, the specific 1st primer layer 3 mentioned later Therefore, even if the base material layer 1 is a single layer sheet, it has high three-dimensional formability.
- the base material layer 1 is physically or chemically such as an oxidation method or an unevenness method on one side or both sides as necessary.
- Surface treatment may be performed.
- the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method.
- corrugated method performed as surface treatment of the base material layer 1 a sandblasting method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.
- the base material layer 1 may be colored with a colorant or the like, painted for adjusting the color, formation of a pattern for imparting design properties, or the like.
- the thickness of the base material layer 1 is not particularly limited and is appropriately set according to the use of the decorative sheet, etc., but is usually about 50 to 800 ⁇ m, preferably about 100 to 600 ⁇ m, more preferably about 200 to 500 ⁇ m. Can be mentioned. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.
- the adhesive layer 2 is a layer provided between the base material layer 1 and the metal thin film layer 4 as necessary in order to improve the adhesion between the base material layer 1 and a first primer layer 3 described later. .
- the resin that forms the adhesive layer 2 is not particularly limited as long as it can improve the adhesion between the base material layer 1 and the first primer layer 3, and examples thereof include a thermoplastic resin.
- the thermoplastic resin is not particularly limited.
- acrylic resin polyolefin resin such as polypropylene and polyethylene
- polycarbonate resin polycarbonate resin
- ABS resin polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- Polyvinyl chloride resins such as chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth) acrylic copolymer, polypropylene chloride And chlorinated resins such as chlorinated polypropylene.
- an acrylic resin or a chlorine-based resin is preferably used from the viewpoint of improving the adhesion between the base material layer 1 and the first primer layer 3.
- Preferred examples of the chlorine-based resin include a vinyl chloride resin and a vinyl chloride-vinyl acetate copolymer from the viewpoint of improving the adhesion between the base material layer 1 and the first primer layer 3, and more preferably a chloride chloride.
- a vinyl-vinyl acetate copolymer may be mentioned.
- resin which forms the contact bonding layer 2 you may use individually by 1 type, and may mix and use 2 or more types.
- “(meth) acryl” is a general term for “acryl” and “methacryl”, and other similar things with (meth) have the same meaning.
- the adhesive layer 2 is selected from the viewpoint of improving the adhesion between the base material layer 1 and the first primer layer 3.
- the mass ratio of the acrylic resin to the chlorine-based resin in the resin to be formed is preferably about 20/80 to 80/20, and more preferably about 30/70 to 70/30.
- a chlorine-based resin is suitable as a resin for forming the adhesive layer 2 in that high adhesion can be obtained, but has a problem that the metal constituting the metal thin film layer is oxidized to cause the metal thin film layer to fade.
- a first primer layer 3 to be described later is disposed between the adhesive layer 2 and the metal thin film layer 4, in the case of using a chlorine-based resin as a resin for forming the adhesive layer 2 Also, fading of the metal thin film layer 4 is suppressed.
- the acid value of the chlorine resin is not particularly limited. However, from the viewpoint of further improving the adhesion between the base material layer 1 and the first primer layer 3, the acid value is 1 mgKOH / g or more. It is preferably 4 mg KOH / g or more, more preferably 6 mg KOH / g or more.
- the metal thin film layer 4 is protected by the first primer layer 3 as described above even when the adhesive layer 2 is formed of a highly oxidized chlorine resin, for example, a chlorine resin with oxidation exceeding 6 mgKOH.
- the base material layer 1 and the metal thin film layer 4 can be adhered with high adhesion, and the three-dimensional formability of the decorative sheet can be improved.
- the fading of the metal thin film layer 4 may be promoted if the acid value of the chlorinated resin is too large, it is usually preferably 12 mgKOH / g or less.
- the thickness of the adhesive layer 2 is not particularly limited. However, from the viewpoint of improving the adhesion between the base material layer 1 and a first primer layer 3 described later, about 0.6 to 3.5 ⁇ m. The thickness may preferably be about 1 to 2 ⁇ m.
- the method for forming the adhesive layer 2 is not particularly limited.
- the adhesive layer 2 can be formed, for example, by applying the above-described resin on the surface of either the base material layer 1 or the first primer layer 3 described later, and heat sealing or dry laminating.
- the first primer layer 3 gives a high three-dimensional formability to the decorative sheet of the present invention, and makes it a decorative sheet that can sufficiently follow the shape of a decorative resin molded product having a complicated surface shape. It is a layer provided. Specifically, when the 1st primer layer 3 is used for the decoration use of the resin molded product in which the decorating sheet of this invention has a curved part, the said curved part is with respect to the decorated sheet of this invention. For example, even if it is a shape that requires stretching at a maximum draw ratio of 150% or more, and further about 200%, it is provided in order to be able to follow such a shape.
- the first primer layer 3 is characterized by containing a cured resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C.
- Tg glass transition point
- high three-dimensional formability as described above is imparted.
- the upper limit of the maximum draw ratio is preferably about 250%.
- the first primer layer 3 has a function of bringing the base material layer 1 and the metal thin film layer 4 into close contact with each other.
- the adhesive layer 2 is provided between the base material layer 1 and the first primer layer 3, the adhesive layer 2 is in close contact with the base material layer 1 and the first primer layer 3, The first primer layer 3 brings the adhesive layer 2 and the metal thin film layer 4 into close contact.
- the adhesive layer 2 and the metal thin film layer 4 Can be effectively prevented from fading of the metal thin film layer 4 caused by direct contact.
- the first primer layer 3 preferably contains a cured product of a resin having a glass transition point of ⁇ 20 to 70 ° C., more preferably a glass transition point of ⁇ 10. It includes a cured product of a resin having a temperature of ⁇ 40 ° C., and more preferably a cured product of a resin having a glass transition point of 0 to 20 ° C. If the glass transition point of the resin contained in the first primer layer 3 is too low, the adhesiveness with the metal thin film layer 4 is lowered, and peeling occurs between the respective layers due to heating at the time of molding the decorative sheet, and the like occurs.
- the metal thin film layer 4 is likely to fade.
- the glass transition point of the resin contained in the first primer layer 3 is too high, the first primer layer 3 is thermally contracted due to heating at the time of molding the decorative sheet, and peels off between each layer of the decorative sheet. , Floating may occur.
- the glass transition point (Tg) is a value obtained by differential scanning calorimetry (DSC) based on JIS K7121-1987.
- the content of the resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C. is preferably 50% by mass or more, more preferably 70% by mass. Above, more preferably 90% or more.
- the resin that forms the first primer layer 3 by curing is particularly preferably only a resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C.
- the resin that cures to form the first primer layer 3 has a glass transition point (Tg) in the range of ⁇ 30 ° C. to 80 ° C., and can be cured by drying or chemical reaction to form a coating film. If it is resin, it will not restrict
- the polyester-based resin, polyurethane-based resin, polyacrylic resin, and polyolefin-based resin are not particularly limited. However, the three-dimensional formability of the decorative sheet is improved, and the adhesive layer 2 contains a chlorine-based resin.
- a polyester polyol that is a polyester resin a urethane polyol that is a polyurethane resin, such as a polyester urethane polyol or an acrylic urethane polyol; an acrylic polyol that is a polyacrylic resin
- the polyolefin resin include polyolefin polyols such as polyethylene polyol, polypropylene polyol, polybutadiene polyol, and polyisoprene polyol.
- polyester polyol examples include a condensed polyester diol obtained by reacting a low-molecular diol and a dicarboxylic acid, a polylactone diol obtained by ring-opening polymerization of a lactone, and a polycarbonate diol.
- dicarboxylic acid examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid and fumaric acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.
- lactone for example, ⁇ -caprolactone is used.
- polyester polyol examples include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene adipate
- polyester polyol examples include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene adipate
- examples thereof include zetate, polyethylene sebacate, polybutylene azate, polybutylene sebacate, polyhexamethylene carbonate diol, and the like.
- the first primer layer 3 of the present invention is preferably formed of a cured product of the above resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C. and a curing agent. Further, the first primer layer 3 of the present invention is made of a reaction-curable urethane resin obtained by a polyol resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C. and a curing agent made of an isocyanate compound. More preferably, it is formed.
- the polyol resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C. is not particularly limited, and is, for example, the polyester resin, polyurethane resin, polyacrylic resin, or polyolefin resin exemplified above. And polyols.
- isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4 '-Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, polymethylene polyphenylene polyisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4 '-Diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenyle Aromatic isocyanates such
- the content of the curing agent is not particularly limited, but the metal thin film layer 4 while improving the adhesion between the base material layer 1 and the metal thin film layer 4.
- the amount is preferably about 1 to 15 parts by weight, more preferably about 3 to 10 parts by weight with respect to 100 parts by weight of the resin forming the first primer layer 3. Can be mentioned.
- the reaction-curable urethane resin that forms the first primer layer 3 may be either a one-component curable type or a two-component curable type, preferably a two-component curable type.
- the first primer layer 3 when the adhesive layer 2 includes a chlorinated resin, the first primer layer 3 includes a silane coupling agent, thereby suppressing the fading of the metal thin film layer 4 and the resin.
- the formed adhesion layer 2 and the metal thin film layer 4 formed of metal can be bonded with high adhesion by the first primer layer 3.
- silane coupling agent contained in the resin composition which forms the 1st primer layer 3
- a vinyl-type silane coupling agent for example, a vinyl-type silane coupling agent, a mercapto type silane coupling agent, (meth) acrylic-type silane coupling Agents, epoxy silane coupling agents, amino silane coupling agents, and the like.
- Examples of the vinyl-based silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, and the like.
- Examples of the mercapto silane coupling agent include 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.
- Examples of the (meth) acrylic silane coupling agent include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like.
- Examples of the epoxy silane coupling agent include 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.
- Examples of the amino silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and the like.
- silane coupling agent from the viewpoint of enhancing the moldability of the decorative sheet while suppressing the fading of the metal thin film layer 4 while improving the adhesion between the adhesive layer 2 and the metal thin film layer 4, Vinyl-based silane coupling agents and mercapto-based silane coupling agents are preferred.
- a silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more types.
- the content of the silane coupling agent contained in the first primer layer 3 is not particularly limited, but is about 1 to 10 parts by mass with respect to 100 parts by mass of the resin contained in the first primer layer 3. Preferably, the amount is about 5 to 15 parts by mass.
- the decorative sheet of the present invention in which the first primer layer 3 is provided, when the silane coupling agent is included in the first primer layer 3, the adhesion formed by the resin.
- the first primer layer 3 can bond the layer 2 and the metal thin film layer 4 made of metal with high adhesion.
- the decorative sheet of the present invention having the specific first primer layer 3 as described above is also excellent in three-dimensional formability.
- the 1st primer layer 3 does not contain chlorine resin substantially from a viewpoint of suppressing the fading of the metal thin film layer 4 more effectively.
- the fact that the first primer layer 3 does not substantially contain a chlorine resin is, for example, that the ratio of the chlorine resin contained in the first primer layer 3 is 1% by mass or less. That means.
- the acid value of resin which forms the 1st primer layer 3 is 6 mgKOH / g or less.
- the first primer layer 3 may further contain a colorant in addition to the above resin for the purpose of adjusting the color of the decorative sheet or improving the design.
- a colorant in addition to the above resin for the purpose of adjusting the color of the decorative sheet or improving the design.
- the first primer layer 3 includes a colorant having the same color as that of the metal thin film layer 4, for example, even when the metal thin film layer 4 is discolored, the effect of reducing the metallic design of the decorative sheet is effective. Can be suppressed. What is necessary is just to select suitably what can exhibit a metallic tone with the metal thin film layer 4 by mix
- colorants include carbon black (black), iron black, titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Pigments.
- a black colorant such as carbon black may be used in combination with a white colorant such as titanium oxide as a base.
- a colorant of another system according to the type of metal forming the metal thin film layer 4 so as to exhibit a color closer to the metal thin film layer 4.
- tin and chromium have a yellowish metallic tone, so when these metals are used, a yellow colorant may be further added, and indium and aluminum have a pale metallic tone.
- a blue colorant may be further added.
- the (resin: colorant) is preferably about 90:10 to 60:40, more preferably about 80:20 to 70:30.
- the thickness of the first primer layer 3 is not particularly limited, but is preferably about 0.5 to 3 ⁇ m, more preferably about 1 to 2 ⁇ m from the viewpoint of improving the three-dimensional formability of the decorative sheet.
- the first primer layer 3 is formed using a primer composition containing the above resin.
- the first primer layer 3 is composed of a gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, silk using a primer composition. It is formed by a usual coating method such as a solid coating by screen, wire bar coating, flow coating, comma coating, flow-through coating, brush coating, spray coating, or transfer coating method.
- the transfer coating method is a method in which a coating film of the first primer layer 3 is formed on a thin sheet (film base material), and then the surface of the target layer in the decorative sheet is coated.
- the metal thin film layer 4 is a layer that is provided on the first primer layer 3 and gives the decorative sheet a metallic design similar to that of the metal surface.
- the metal forming the metal thin film layer 4 is not particularly limited as long as it is a metal that can impart a metallic design to the decorative sheet.
- a metal that can impart a metallic design to the decorative sheet For example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum , Zinc, and alloys containing at least one of them.
- tin, indium, and chromium are preferable from the viewpoint of excellent extensibility.
- the metal thin film layer 4 is formed of a metal having excellent extensibility, there is an advantage that cracks are hardly generated when the decorative sheet is three-dimensionally formed.
- the metal thin film layer 4 may be formed of one kind of metal or may be formed of two or more kinds of metals.
- the formation method in particular of the metal thin film layer 4 is not restrict
- the vacuum deposition method is preferable in that it is low cost and causes little damage to the deposition target.
- the conditions for the vapor deposition may be appropriately set according to the melting temperature or the evaporation temperature of the metal to be used.
- a method of applying a paste containing the above metal, a plating method using the above metal, or the like can also be used.
- the thickness of the metal thin film layer 4 is not particularly limited, but the optical density (OD) value is preferably about 0.6 to 1.8, more preferably from the viewpoint of improving the designability and formability of the decorative sheet. Is about 0.8 to 1.4.
- the surface protective layer 5 is a layer provided on the outermost surface of the decorative sheet as necessary for the purpose of enhancing the scratch resistance, weather resistance, etc. of the decorative sheet.
- the material which forms the surface protective layer 5 is not specifically limited, Usually, resin is used, Preferably ionizing radiation curable resin is used.
- ionizing radiation curable resin is used.
- the case where the surface protective layer 5 is formed of an ionizing radiation curable resin will be described in detail.
- the ionizing radiation curable resin used for the formation of the surface protective layer 5 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. And a mixture of at least one of prepolymers, oligomers, monomers, and the like, as appropriate.
- ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and ⁇ rays, and charged particle rays such as ⁇ rays and ion rays.
- the electron beam curable resin can be made solvent-free, does not require a photopolymerization initiator, and provides stable curing characteristics. Used for.
- a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
- the polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule.
- polyfunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (me
- the oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule.
- a polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred.
- Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
- Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.
- the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid.
- the polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton.
- the urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.
- the acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer.
- Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and a polyisocyanate compound with (meth) acrylic acid.
- Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used.
- Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid.
- the polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
- Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer.
- Silicone (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain.
- These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.
- polycarbonate (meth) acrylate is preferably used from the viewpoint of obtaining excellent three-dimensional formability. Moreover, it is more preferable to use combining a polycarbonate (meth) acrylate and urethane (meth) acrylate from a viewpoint which makes three-dimensional moldability and scratch resistance compatible.
- curable resins may be used alone or in combination of two or more.
- additives can be blended in the ionizing radiation curable resin composition forming the surface protective layer 5 according to desired physical properties to be provided in the surface protective layer 5.
- the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used.
- the ultraviolet absorber or light stabilizer a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.
- the thickness of the surface protective layer 5 after curing is not particularly limited, and examples thereof include 1 to 1000 ⁇ m, preferably 1 to 50 ⁇ m, and more preferably 1 to 30 ⁇ m. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and when the surface protective layer 4 is formed using an ionizing radiation curable resin. Since it is possible to irradiate ionizing radiation uniformly, it is possible to cure uniformly, which is economically advantageous.
- the decorative sheet of the present invention can provide a sufficiently high three-dimensional formability even when the thickness of the surface protective layer 5 is larger than that of the conventional one. It is also useful as a decorative sheet for a member required for the vehicle, for example, a vehicle exterior part.
- the surface protective layer 5 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying it, and crosslinking and curing it.
- the viscosity of the ionizing radiation curable resin composition may be a viscosity that can form an uncured resin layer on the surface of the second primer layer 6, the metal thin film layer 4, and the like by a coating method described later.
- the prepared coating solution is applied to the gravure coat, the bar coat, the roll on the metal thin film layer 4 and a second primer layer 6 which will be described later if necessary so as to have the thickness.
- It coat covers by well-known systems, such as a coat, a reverse roll coat, a comma coat, Preferably gravure coat, and forms an uncured resin layer.
- the surface-protecting layer 5 is formed by irradiating the uncured resin layer thus formed with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer.
- ionizing radiation such as an electron beam and ultraviolet rays
- the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.
- the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protective layer 5, the electron beam transmission depth and the surface protection are used.
- the acceleration voltage is selected so that the thicknesses of the layers 5 are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the surface protective layer 5 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.
- the irradiation dose is preferably such that the crosslinking density of the surface protective layer 5 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
- the electron beam source is not particularly limited.
- various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.
- ultraviolet rays In the case where ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted.
- the ultraviolet ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.
- a hard coat function By adding various additives to the surface protective layer 5 thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, You may perform the process which provides functions, such as an infrared shielding coat function.
- the third primer layer 8 is a layer provided under the surface protective layer 5 as necessary for the purpose of improving the adhesion between the surface protective layer 5 and the layer located therebelow.
- the third primer layer 8 is, for example, as shown in FIG. 3 or 4 between the surface protective layer 5 and a color clear layer 7 described later, or between the surface protective layer 5 and a transparent film layer 9 described later.
- the material for forming the third primer layer 8 is not particularly limited as long as it can improve the adhesion between these layers, and examples thereof include acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, Examples thereof include resins such as polyester resins.
- the thickness of the third primer layer 8 is not particularly limited, but is usually about 0.5 to 2.5 ⁇ m, preferably about 1 to 2 ⁇ m.
- the third primer layer 8 can be mixed with a colorant to adjust the color and improve the design, and further, a pattern from a design viewpoint can be formed.
- the method for forming the third primer layer 8 is not particularly limited. For example, among the metal thin film layer 4, the color clear layer 7, the transparent film layer 9, and the like, the surface of the layer located immediately below the third primer layer 8 is used. The method etc. which apply
- the color clear layer 7 is a layer provided on the metal thin film layer 4 as necessary for the purpose of giving the metal tone of the metal thin film layer 4 a more glossy or the like. Although it does not specifically limit as a raw material which forms the color clear layer 7, For example, the transparent resin colored with the coloring agent etc. is mentioned. Although there is no restriction
- the transparent resin is not particularly limited, and examples thereof include acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, and polyester resins.
- the thickness of the color clear layer 7 is not particularly limited, but is usually about 0.5 to 4 ⁇ m, preferably about 1 to 3 ⁇ m.
- the method for forming the color clear layer 7 is not particularly limited. For example, a layer located immediately below the color clear layer 7 among the second primer layer 6 described later, the transparent film layer 9 described later, the metal thin film layer 4 and the like. And a method of applying the above-described resin on the surface of a layer located immediately above the color clear layer 7 such as the third primer layer 8.
- the second primer layer 6 is a layer provided as necessary for the purpose of improving the adhesion between the metal thin film layer and the layer laminated thereon.
- the second primer layer 6 is made of a metal as necessary for the purpose of improving the adhesion between the metal thin film layer 4 and the layer provided thereon. It can be provided immediately above the thin film layer 4.
- the second primer layer 6 is used for the purpose of improving the adhesion between the color clear layer 7 and the layer located thereunder, as necessary. It can also be provided under the color clear layer 7.
- the second primer layer 6 is, for example, between the metal thin film layer 4 and the surface protective layer 5 as shown in FIG.
- the material for forming the second primer layer 6 is not particularly limited as long as it can improve the adhesion between these layers.
- an acrylic resin, a polyurethane resin, an acrylic-urethane copolymer resin examples thereof include resins such as polyester resins.
- the second primer layer 6 when the second primer layer 6 is provided immediately above the metal thin film layer 4, the second primer layer 6 includes a cured product of a resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. Is preferred.
- Tg glass transition point
- the moldability of the decorating sheet of this invention can be improved more, and the discoloration by thermoforming can be suppressed effectively.
- the second primer layer 6 provided on the metal thin film layer 4 includes a cured product of the resin having the specific glass transition point as described above, thereby allowing formability.
- the glass transition point (Tg) of the second primer layer 6 is a value obtained by differential scanning calorimetry (DSC) based on JIS K7121-1987.
- the content of the resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. is preferably 50% by mass or more, more preferably 70% by mass or more. More preferably, 90 mass% or more is mentioned.
- the resin that cures to form the second primer layer 6 is particularly preferably only a resin having a glass transition point (Tg) of 55 ° C. to 110 ° C.
- the resin having a glass transition point (Tg) in the range of 55 ° C. to 110 ° C. is not particularly limited as long as it is a resin that can be cured by drying or chemical reaction to form a coating film.
- examples thereof include curable resins and thermoplastic resins, and preferred examples include polyester resins, polyurethane resins, polyacrylic resins, and polyolefin resins.
- polyester resins and polyacrylic resins are more preferable from the viewpoint of imparting high formability to the decorative sheet and suppressing discoloration during heat molding.
- a resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. may be used alone or in combination of two or more.
- polyester polyol which is a polyester-type resin
- Polyurethane polyols such as polyester urethane polyols and acrylic urethane polyols
- acrylic polyols such as polyacrylic resins
- polyolefin polyols such as polyethylene polyols, polypropylene polyols, polybutadiene polyols, and polyisoprene polyols.
- polyester polyol examples include those exemplified above.
- the acrylic polyol is not particularly limited as long as it is an acrylic resin having a plurality of hydroxyl groups.
- the second primer layer 6 of the present invention is preferably formed of a cured product of the above resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. and a curing agent.
- the second primer layer 6 is formed of a reaction curable urethane resin obtained by a polyol resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. and a curing agent made of an isocyanate compound or the like. It is more preferable.
- the polyol resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. is not particularly limited, and is, for example, the polyester resin, polyurethane resin, polyacrylic resin, or polyolefin resin exemplified above.
- a polyol etc. are mentioned.
- polyester polyol or acrylic polyol is particularly preferred from the viewpoint of enhancing the moldability of the decorative sheet and effectively suppressing discoloration due to heat molding. preferable.
- Examples of the isocyanate compound include those exemplified above.
- the amount is preferably about 1 to 15 parts by mass, more preferably about 3 to 10 parts by mass with respect to 100 parts by mass of the resin that is cured to form the second primer layer 6.
- the reaction-curable urethane resin that forms the second primer layer 6 may be either a one-component curable type or a two-component curable type, preferably a two-component curable type.
- the thickness of the second primer layer 6 is not particularly limited, but is usually about 0.5 to 2.5 ⁇ m, preferably about 1 to 2 ⁇ m.
- the second primer layer 6 can be mixed with a colorant to adjust the color and improve the design, and further, a pattern from a design viewpoint can be formed.
- the method for forming the second primer layer 6 is not particularly limited.
- the second primer layer 6 is adjacent to the second primer layer 6 on the surface of the color clear layer 7 or the transparent film layer 9 or the metal thin film layer 4 described later. The method of apply
- the transparent film layer 9 serves as a support that enhances the scratch resistance and weather resistance of the decorative sheet of the present invention and enhances moldability, and is a resin provided on the metal thin film layer 4 as necessary. It is a film. Since the moldability is improved by providing the transparent film layer 9, and the metal thin film layer 4 is less likely to crack when the decorative sheet is three-dimensionally formed, a metal other than tin, indium, chromium, which has excellent extensibility (for example, When forming the metal thin film layer 4 using aluminum etc., it is preferable to provide the transparent film layer 9.
- the resin film for forming the transparent film layer 9 is not particularly limited as long as it does not enhance the moldability of the decorative sheet and conceal the metallic design by the metal thin film layer 4.
- the thickness of the transparent film layer 9 is not particularly limited, but is usually about 15 to 200 ⁇ m, preferably about 30 to 150 ⁇ m.
- the method for forming the transparent film layer 9 is not particularly limited. For example, among the metal thin film layer 4, the surface protective layer 5, the second primer layer 6, the color clear layer 7, the third primer layer 8, and the like, it is transparent. The method of laminating
- the second adhesive layer 10 is a layer provided on the back surface of the base material layer 1 as necessary for the purpose of improving the adhesion and adhesion between the decorative sheet and the molding resin.
- the resin that forms the second adhesive layer 10 is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molding resin, for example, a thermoplastic resin or thermosetting. Resin is used.
- the thermoplastic resin include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. .
- thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- thermosetting resin include a urethane resin and an epoxy resin.
- thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- the 2nd contact bonding layer 10 is not necessarily a required layer, applying the decorating sheet of this invention to the decorating method by sticking on the resin molded object prepared beforehand, such as the vacuum press-bonding method mentioned later. When assumed, it is preferable to be provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 8 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.
- the thickness of the second adhesive layer 10 is not particularly limited, but may be, for example, about 0.1 to 30 ⁇ m, preferably about 0.5 to 20 ⁇ m, and more preferably about 1 to 8 ⁇ m.
- the decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention comprises at least a molded resin layer, a base material layer 1, a primer layer 3, and a metal thin film layer 4 laminated in this order, and the primer layer 3 Includes a cured product of the above resin having a glass transition point of ⁇ 30 ° C. to 80 ° C.
- the above-described surface protective layer 5, the second primer layer 6, the color clear layer 7, the third primer layer 8, the transparent film layer 9, At least one layer such as the second adhesive layer 10 may be further provided.
- the first primer layer 3 includes the silane coupling agent, thereby suppressing the fading of the metal thin film layer 4 and forming the adhesive layer 2 made of resin and the metal.
- the metal thin film layer 4 can be adhered with high adhesion by the first primer layer 3.
- the second primer layer 6 is a resin cured product having a glass transition point (Tg) of 55 ° C to 110 ° C.
- the decorative resin molded product of the present invention is produced by using the decorative sheet of the present invention, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding.
- various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding.
- an insert molding method and an injection molding simultaneous decorating method are preferable.
- the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made.
- the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained.
- This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, a decorative resin molded product is manufactured.
- the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
- the decorative sheet of the present invention has high three-dimensional formability. For this reason, for example, when the decorative resin molded product has a curved portion, in at least one of the vacuum forming step and the integration step, the decorative sheet positioned in the curved portion is at a maximum draw ratio of 150% or more. Further, it may be stretched by about 200%. The upper limit of the maximum draw ratio is preferably about 250%.
- the decorative sheet may be heated and molded.
- the heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like.
- the temperature can be usually about 100 to 250 ° C., preferably about 130 to 200 ° C.
- the temperature of the resin in the fluidized state is not particularly limited, but is usually about 180 to 320 ° C., preferably about 220 to 280 ° C.
- the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold.
- preliminary molding in-line preliminary molding
- the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding simultaneously with the injection molding
- a decorative resin molded product is manufactured.
- the decorated resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
- the decorative sheet of the present invention is installed so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape
- the decorative sheet is heated
- a pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.
- the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like.
- the temperature can usually be about 70 to 130 ° C.
- the temperature of the resin in the fluidized state is not particularly limited, but can usually be about 180 to 320 ° C., preferably about 220 to 280 ° C.
- the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine the decorative sheet is the first.
- the vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state.
- the resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down.
- the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface.
- the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.
- the vacuum pressure bonding method it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the moldability before the step of pressing the above-mentioned molded body against the decorative sheet.
- the vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method.
- the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, the temperature can be about 60 to 200 ° C.
- the decorative sheet positioned in the curved portion has a maximum draw ratio. You may extend
- the molded resin layer may be formed by selecting a resin according to the application.
- the resin forming the molded resin layer may be a thermoplastic resin or a thermosetting resin.
- thermoplastic resin examples include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- thermosetting resin examples include urethane resin and epoxy resin. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- the decorative resin molded product of the present invention has high adhesion to each layer, can be molded into a complicated shape, and has a high-quality and high-quality metallic tone.
- an interior material of a vehicle such as an automobile Or exterior materials; fittings such as window frames and door frames; interior materials of buildings such as walls, floors, and ceilings; housings of home appliances such as television receivers and air conditioners; containers and the like.
- Examples 1A to 10A and Comparative Examples 1A to 3A> (Preparation of decorative sheet A) An acrylic-urethane block copolymer resin is coated on a biaxially stretched polyethylene terephthalate sheet (E5001 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m) as a release sheet, and a transparent third primer 2 ⁇ m thick A layer was formed. Next, an acrylic-urethane block copolymer resin containing a colorant is applied onto the third primer layer, and the color clear layer (thickness 2 ⁇ m) and the second primer layer (thickness 2 ⁇ m) are sequentially formed. Formed.
- E5001 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m
- a transparent third primer 2 ⁇ m thick A layer was formed.
- an acrylic-urethane block copolymer resin containing a colorant is applied onto the third primer layer, and the color clear layer (thickness 2 ⁇ m) and the second primer layer (thick
- tin was vapor-deposited on the surface of the second primer layer to form a metal thin film layer having an optical density value (OD) of 1.2.
- a first primer layer (thickness: 2 ⁇ m) having the composition and glass transition point (Tg) shown in Table 1A was formed on the metal thin film layer.
- Tg glass transition point
- 30 parts by mass of a colorant (including titanium oxide and carbon black) having the same color as the metal thin film layer was blended with 70 parts by mass of the resin of the first primer layer.
- the resin described in Table 1A was applied to a thickness of 2 ⁇ m to form an adhesive layer.
- a sheet made of ABS resin having a thickness of 400 ⁇ m is brought into contact with the adhesive layer to form a base material layer, and release sheet / third primer layer / color clear layer / second primer layer / metal thin film layer A laminate in which / first primer layer / adhesive layer / base material layer was laminated in this order was obtained.
- a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 4.0 ⁇ m and a ten-point average roughness RzJIS of 16 ⁇ m is arranged on the base material layer side of the laminate, and on the release layer side.
- a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 ⁇ m was placed, and the laminate was hot press-molded with this metal plate and mirror plate.
- the conditions for hot press molding were a temperature of 150 ° C., a pressure of 0.5 MPa, and a heating / pressurization time of 10 minutes.
- the release sheet is peeled from the laminate, and an ionizing radiation curable resin is applied on the surface of the first primer layer by gravure reverse so that the thickness after curing is 10 ⁇ m, and is uncured.
- a resin layer was formed.
- This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- the base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / color clear layer / third primer layer / having the structure shown in Table 1A / A decorative sheet in which the surface protective layers were laminated in this order was obtained.
- a mixture of 80 parts by mass of a bifunctional polycarbonate acrylate (weight average molecular weight 10,000) and 20 parts by mass of a hexafunctional urethane acrylate oligomer (weight average molecular weight 6000) was used.
- the first primer layer was not provided.
- HDI 1,6-hexamethylene diisocyanate
- XDI xylene-1,3-diisocyanate
- the first primer layer containing a cured product of a resin having a glass transition point (Tg) of ⁇ 30 ° C. to 80 ° C. was provided between the adhesive layer and the metal thin film layer.
- Tg glass transition point
- the decorative sheet of 10A it became clear that all were excellent in a moldability and adhesiveness, and the fading of the metal thin film layer was also suppressed.
- the first primer layer of the decorative sheets of Examples 3A and 9A is blended with a colorant having the same color as the metal thin film layer, respectively. And the decorative sheet of 10A had more excellent fading resistance.
- the decorative sheets of Examples 1A to 10A did not show any peeling even when heated after being used as a decorative resin molded product, or peeled to such a degree that there was no practical problem.
- the decorative resin molded product obtained from the decorative sheet of Example 1A no peeling was observed even after the heat resistance test.
- the first primer layer was provided, in Comparative Example 1A using a resin having a glass transition point (Tg) higher than 80 ° C., the moldability was poor and the decorative resin molded product was heated. Peeling also had a practical problem.
- Tg glass transition point
- Examples 1B to 8B, 11B and Comparative Examples 1B to 4B> (Preparation of decorative sheet B) An acrylic-urethane block copolymer resin is coated on a biaxially stretched polyethylene terephthalate sheet (A5101, manufactured by Toyobo Co., Ltd., 25 ⁇ m thick) as a release sheet, and a transparent third primer having a thickness of 2 ⁇ m. A layer was formed. Next, an acrylic-urethane block copolymer resin containing a colorant and a transparent acrylic-urethane block copolymer resin are sequentially coated on the third primer layer, and a color clear layer (thickness 3 ⁇ m) And the 2nd primer layer (2 micrometers in thickness) was formed in order.
- A5101 manufactured by Toyobo Co., Ltd., 25 ⁇ m thick
- Example 11B the metal described in Table 1B was deposited on the surface of the second primer layer to form a metal thin film layer having an optical density value (OD) of 1.2.
- a first primer layer (thickness: 2 ⁇ m) having the composition described in Table 1B was formed on each metal thin film layer.
- a colorant including titanium oxide and carbon black
- a sheet made of ABS resin having a thickness of 400 ⁇ m is brought into contact with the adhesive layer to form a base material layer, and release sheet / third primer layer / color clear layer / second primer layer / metal thin film layer A laminate in which / first primer layer / adhesive layer / base material layer was laminated in this order was obtained.
- a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 4.0 ⁇ m and a ten-point average roughness RzJIS of 16 ⁇ m is arranged on the base material layer side of the laminate, and on the release layer side.
- a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 ⁇ m was placed, and the laminate was hot press-molded with this metal plate and mirror plate.
- the conditions for hot press molding were a temperature of 150 ° C., a pressure of 0.5 MPa, and a heating / pressurization time of 10 minutes.
- the release sheet is peeled from the laminate, and an ionizing radiation curable resin is applied on the surface of the third primer layer by gravure reverse so that the thickness after curing is 10 ⁇ m, and is uncured.
- a resin layer was formed.
- This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- the base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / color clear layer / third primer layer / having the structure shown in Table 1B / A decorative sheet in which the surface protective layers were laminated in this order was obtained.
- a mixture of 80 parts by mass of a bifunctional polycarbonate acrylate (weight average molecular weight 10,000) and 20 parts by mass of a hexafunctional urethane acrylate oligomer (weight average molecular weight 6000) was used.
- a bifunctional polycarbonate acrylate weight average molecular weight 10,000
- a hexafunctional urethane acrylate oligomer weight average molecular weight 6000
- Examples 9B and 10B The metal described in Table 1B was deposited on one surface of a biaxially stretched polyethylene terephthalate film (thickness 38 ⁇ m) as a transparent film layer to form a metal thin film layer having an optical density value (OD) of 1.2. . Next, on the metal thin film layer, a first primer layer (thickness 2 ⁇ m) having the composition described in Table 1B and an adhesive layer having a resin coating amount described in Table 1B were sequentially formed by coating.
- a first primer layer thickness 2 ⁇ m
- an adhesive layer having a resin coating amount described in Table 1B were sequentially formed by coating.
- an acrylic-urethane block copolymer resin is sequentially applied to the surface of the transparent film layer on which the metal thin film layer is not formed, and a transparent second primer layer (thickness 2 ⁇ m), color clear layer (thickness) 3 ⁇ m) and a transparent third primer layer (thickness 2 ⁇ m).
- an uncured resin layer was formed on the third primer layer by applying an ionizing radiation curable resin by gravure reverse so that the thickness after curing was 10 ⁇ m.
- This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- a base layer / adhesive layer / first layer having the structure shown in Table 1B is formed by laminating a sheet made of 400 ⁇ m thick ABS resin on the adhesive layer to form a base layer.
- a decorative sheet in which a primer layer / metal thin film layer / transparent film layer / second primer layer / color clear layer / third primer layer / surface protective layer were laminated in this order was obtained.
- the ionizing radiation curable resin the same mixtures as in Examples 1B to 8B and 11B and Comparative Examples 1B to 4B were used.
- ⁇ E * ab ⁇ ( ⁇ L *) 2+ ( ⁇ a *) 2+ ( ⁇ b *) 2
- the decorative sheets of Examples 1B to 11B and Comparative Examples 1B to 4B before being subjected to the fading resistance evaluation test were used, respectively.
- the color fading resistance evaluation test when the color difference ⁇ E * ab is 5 or less, the color fading is evaluated as small ( ⁇ ), and when the color difference ⁇ E * ab is 5 or more, the color fading is evaluated as large ( ⁇ ).
- Tg represents a glass transition point.
- XDI represents xylene diisocyanate.
- Examples 1C to 7C and Comparative Examples 1C to 3C> (Production C of decorative sheet) An acrylic-urethane block copolymer resin is coated on a biaxially stretched polyethylene terephthalate sheet (E5001 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m) as a release sheet to form a transparent third primer layer having a thickness of 2 ⁇ m. did. Next, an acrylic-urethane block copolymer resin containing about 3% by weight of a colorant was applied on the third primer layer to form a color clear layer (thickness 2 ⁇ m). Next, a second primer layer having the composition described in Table 1C was formed to a thickness of 2 ⁇ m.
- E5001 manufactured by Toyobo Co., Ltd., thickness 25 ⁇ m
- an acrylic-urethane block copolymer resin containing about 3% by weight of a colorant was applied on the third primer layer to form a color clear layer (thickness 2 ⁇ m).
- tin was vapor-deposited on the surface of the second primer layer to form a metal thin film layer having an optical density value (OD) of 1.2.
- an acrylic-urethane block copolymer resin was applied on the metal thin film layer to form a first primer layer (thickness 2 ⁇ m).
- a vinyl chloride-vinyl acetate copolymer was applied on the first primer layer to a thickness of 2 ⁇ m to form an adhesive layer.
- a sheet made of ABS resin having a thickness of 400 ⁇ m is brought into contact with the adhesive layer to form a base material layer, and a release sheet / third primer layer / color clear layer / second primer layer / metal thin film layer / A laminate in which the first primer layer / adhesive layer / base material layer was laminated in this order was obtained.
- a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 4.0 ⁇ m and a ten-point average roughness RzJIS of 16 ⁇ m is disposed on the base layer side of the laminate, and the release sheet side.
- a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 ⁇ m was placed, and the laminate was hot press-molded with this metal plate and mirror plate.
- the conditions for hot press molding were a temperature of 150 ° C., a pressure of 0.5 MPa, and a heating / pressurization time of 10 minutes.
- the release layer is peeled from the laminate, and an ionizing radiation curable resin is applied on the surface of the third primer layer by gravure reverse so that the thickness after curing is 10 ⁇ m, and the uncured resin is applied.
- a layer was formed.
- This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the uncured resin layer to form a surface protective layer.
- the base layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / color clear layer / third primer layer / having the configuration shown in Table 1C / A decorative sheet in which the surface protective layers were laminated in this order was obtained.
- ionizing radiation curable resin a mixture of 80 parts by mass of bifunctional polycarbonate acrylate (weight average molecular weight 10,000) and 20 parts by mass of hexafunctional urethane acrylate oligomer (weight average molecular weight 6,000) was used.
- the second primer layer was not provided.
- HDI 1,6-hexamethylene diisocyanate
- XDI xylene-1,3-diisocyanate
- the decorative sheets of Examples 1C to 7C in which a second primer layer containing a cured product of a resin having a glass transition point (Tg) of 55 ° C. to 110 ° C. is provided on the metal thin film layer In all, the moldability was excellent and discoloration due to heating was effectively suppressed. In contrast, although the second primer layer was provided, in Comparative Example 1C using a resin having a glass transition point (Tg) lower than 55 ° C., the moldability was excellent, but the discoloration due to heating was large. .
- the 2nd primer layer was provided, in the comparative example 2C using the resin whose glass transition point (Tg) is larger than 110 degreeC, the discoloration by heating was suppressed, but the moldability was bad. Also in Comparative Example 3 in which the third primer layer was not provided, the moldability was excellent, but the color change due to heating was large.
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Abstract
Description
項1. 少なくとも、基材層と、第1のプライマー層と、金属薄膜層とがこの順に積層された積層体からなり、
前記第1のプライマー層は、ガラス転移点が-30℃~80℃の樹脂の硬化物を含む、加飾シート。
項2. 曲部を有する樹脂成形品の加飾用途に用いられ、
前記曲部が、前記加飾シートに対して最大延伸倍率150%以上の延伸を必要とする形状である、項1に記載の加飾シート。
項3. 前記ガラス転移点が-30℃~80℃の樹脂が、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、及びポリオレフィン系樹脂からなる群から選択された少なくとも1種である、項1または2に記載の加飾シート。
項4. 前記ガラス転移点が-30℃~80℃の樹脂が、ポリオール樹脂であり、
前記第1のプライマー層が、前記ポリオール樹脂とイソシアネート化合物との硬化物により形成されている、項1~3のいずれかに記載の加飾シート。
項5. 前記第1のプライマー層における前記ポリオール樹脂が、ポリエステルポリオールである、項4に記載の加飾シート。
項6. 前記第1のプライマー層における前記イソシアネート化合物が、脂肪族イソシアネート化合物である、項4または5に記載の加飾シート。
項7. 前記基材層と前記第1のプライマー層との間に接着層を有する、項1~6のいずれかに記載の加飾シート。
項8. 前記接着層が、塩素系樹脂を含む、項7に記載の加飾シート。
項9. 前記第1のプライマー層が、シランカップリング剤を含む樹脂組成物により形成されている、項8に記載の加飾シート。
項10. 前記塩素系樹脂が、ポリ塩化ビニル、塩素化ポリエチレン、ポリ塩化ビニリデン、エチレン-塩化ビニル共重合体、塩化ビニル-酢酸ビニル共重合体、ポリ塩化プロピレン、及び塩素化ポリプロピレンからなる群から選択された少なくとも1種である、項8または9に記載の加飾シート。
項11. 前記第1のプライマー層が、塩素系樹脂を実質的に含まない、項1~10のいずれかに記載の加飾シート。
項12. 前記金属薄膜層が、スズ、インジウム、クロム、アルミニウム、ニッケル、銅、銀、金、白金、亜鉛、及びこれらのうち少なくとも1種を含む合金からなる群から選択された少なくとも1種の金属により形成されている、項1~11のいずれかに記載の加飾シート。
項13. 前記金属薄膜層の上に表面保護層がさらに積層されている、項1~12のいずれかに記載の加飾シート。
項14. 前記金属薄膜層と前記表面保護層の間にさらに第2のプライマー層を有し、
前記第2のプライマー層は、ガラス転移点が55℃~110℃の樹脂の硬化物を含む、項13に記載の加飾シート。
項15. 前記ガラス転移点が55℃~110℃の樹脂が、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、及びポリオレフィン系樹脂からなる群から選択された少なくとも1種である、項14に記載の加飾シート。
項16. 前記ガラス転移点が55℃~110℃の樹脂が、ポリオール樹脂であり、
前記第2のプライマー層が、前記ポリオール樹脂とイソシアネート化合物との硬化物により形成されている、項14または15に記載の加飾シート。
項17. 前記第2のプライマー層における前記ポリオール樹脂が、ポリエステルポリオール及びアクリルポリオールの少なくとも一方である、項16に記載の加飾シート。
項18. 前記第2のプライマー層における前記イソシアネート化合物が、脂肪族イソシアネート化合物及び芳香族イソシアネート化合物の少なくとも一方である、項16または17に記載の加飾シート。
項19. 前記金属薄膜層の上に透明フィルム層がさらに積層されている、項1~18のいずれかに記載の加飾シート。
項20. 前記第1のプライマー層が、着色剤をさらに含む、項1~19のいずれかに記載の加飾シート。
項21. 少なくとも、成形樹脂層と、基材層と、第1のプライマー層と、金属薄膜層とがこの順に積層された積層体からなり、
前記第1のプライマー層は、ガラス転移点が-30℃~80℃の樹脂の硬化物を含む、加飾樹脂成形品。
項22. 前記基材層と前記第1のプライマー層の間に塩素系樹脂を含む接着剤層をさらに有し、
前記第1のプライマー層がシランカップリング剤を含む樹脂組成物により形成されている、項21に記載の加飾樹脂成形品。
項23. 前記金属薄膜層の上にさらに第2のプライマー層と表面保護層とがこの順に積層されており、
前記第2のプライマー層が、ガラス転移点が55℃~110℃の樹脂の硬化物を含む、項21または22に記載の加飾樹脂成形品。
項24. 項1~20のいずれかに記載の加飾シートを真空成形型により予め立体形状に成形する真空成形工程、
前記真空成形された加飾シートの余分な部分をトリミングして成形シートを得るトリミング工程、及び
前記成形シートを射出成形型に挿入し、前記射出成形型を閉じ、流動状態の樹脂を前記射出成形型内に射出して前記樹脂と前記成形シートとを一体化する一体化工程、
を備える、加飾樹脂成形品の製造方法。
項25. 前記加飾樹脂成形品が曲部を有し、
前記真空成形工程及び前記一体化工程の少なくとも一方の工程において、前記曲部に位置する加飾シートを最大延伸倍率150%以上に延伸する、項24に記載の加飾樹脂成形品の製造方法。
本発明の加飾シートは、少なくとも、基材層と、第1のプライマー層と、金属薄膜層とがこの順に積層された積層体からなり、当該第1のプライマー層が、ガラス転移点が-30℃~80℃の樹脂の硬化物を含むことを特徴とする。本発明の加飾シートにおいては、基材層と金属薄膜層との間に設けられた当該第1のプライマー層が、上記のような特定のガラス転移点を有する樹脂の硬化物を含むことにより、複雑な表面形状を有する加飾樹脂成形品の形状に十分に追従し得る、高い三次元成形性が付与されている。以下、本発明の加飾シートについて詳述する。
本発明の加飾シートは、少なくとも、基材層1と、第1のプライマー層3と、金属薄膜層4とをこの順に有する積層構造を有する。本発明の加飾シートにおいて、基材層1と第1のプライマー層3との間には、これらの層間の密着性を高めることなどを目的として、必要に応じて、接着層2を設けてもよい。また、金属薄膜層4の上には、加飾シートの耐傷付き性、耐候性を高めることなどを目的として、必要に応じて、表面保護層5を設けてもよい。また、表面保護層5などの層を金属薄膜層4の上に設ける場合には、金属薄膜層4とその上に設けられる層との密着性を高めることを目的として、金属薄膜層4の上に、必要に応じて第2のプライマー層6を設けてもよい。金属薄膜層4の上には、金属薄膜層4の金属調にさらに光沢性を付与すること等を目的として、必要に応じて、カラークリア層7を設けてもよい。また、表面保護層5の下には、表面保護層5の下面に隣接する層との密着性を向上させることなどを目的として、表面保護層5の直下に、必要に応じて、第3のプライマー層8を設けてもよい。また、金属薄膜層4の上には、加飾シートの成形性を高めることなどを目的として、必要に応じて、透明フィルム層9などを設けてもよい。さらに、基材層1の下に、第2の接着層10などを設けてもよい。
[基材層1]
基材層1は、本発明の加飾シートにおいて支持体としての役割を果たす樹脂シート(樹脂フィルム)により形成されている。基材層1に使用される樹脂成分については、特に制限されず、三次元成形性や成形樹脂層との相性等に応じて適宜選定すればよいが、好ましくは、熱可塑性樹脂が挙げられる。熱可塑性樹脂としては、具体的には、アクリロニトリル-ブタジエン-スチレン樹脂(以下「ABS樹脂」と表記することもある);アクリロニトリル-スチレン-アクリル酸エステル樹脂;アクリル樹脂;ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂;ポリカーボネート樹脂;塩化ビニル系樹脂;ポリエチレンテレフタラート(PET)等が挙げられる。これらの中でも、ABS樹脂が三次元成形性の観点から好ましい。基材層1を形成する樹脂成分としては、1種類のみを用いてもよいし、2種類以上を混合して用いてもよい。また、基材層1は、これら樹脂の単層シートで形成されていてもよく、また同種又は異種樹脂による複層シートで形成されていてもよい。なお、基材層1を複層シートとすることで、加飾シートの三次元成形性を高める手法も考えられるが、本発明の加飾シートにおいては、後述する特定の第1のプライマー層3を有するため、基材層1が単層シートであっても、高い三次元成形性を有する。
接着層2は、基材層1と後述の第1のプライマー層3との密着性を向上させるため、必要に応じて、基材層1と金属薄膜層4との間に設けられる層である。
第1のプライマー層3は、本発明の加飾シートに高い三次元成形性を付与し、複雑な表面形状を有する加飾樹脂成形品の形状に十分に追従し得る加飾シートとするために設けられている層である。具体的には、第1のプライマー層3は、本発明の加飾シートが曲部を有する樹脂成形品の加飾用途に用いられる場合に、当該曲部が、本発明の加飾シートに対して、例えば最大延伸倍率150%以上、さらには約200%の延伸を必要とする形状であったとしても、このような形状に追従することを可能とするために設けられる。本発明においては、当該第1のプライマー層3は、ガラス転移点(Tg)が-30℃~80℃の樹脂の硬化物を含むことを特徴としており、このような特徴により、加飾シートに対して上記のような高い三次元成形性が付与されている。なお、上記の最大延伸倍率の上限値は、好ましくは250%程度である。
金属薄膜層4は、第1のプライマー層3の上に設けられ、加飾シートに金属表面と同様な金属調の意匠を付与する層である。
表面保護層5は、加飾シートの耐傷付き性、耐候性などを高めることを目的として、必要に応じて、加飾シートの最表面に設けられる層である。表面保護層5を形成する素材は、特に限定されないが、通常は樹脂が用いられ、好ましくは電離放射線硬化性樹脂が用いられる。以下、表面保護層5が電離放射線硬化性樹脂により形成される場合について詳述する。
表面保護層5の形成に使用される電離放射線硬化性樹脂とは、電離放射線を照射することにより、架橋、硬化する樹脂であり、具体的には、分子中に重合性不飽和結合又はエポキシ基を有する、プレポリマー、オリゴマー、及びモノマーなどのうち少なくとも1種を適宜混合したものが挙げられる。ここで電離放射線とは、電磁波又は荷電粒子線のうち、分子を重合あるいは架橋しうるエネルギー量子を有するものを意味し、通常紫外線(UV)又は電子線(EB)が用いられるが、その他、X線、γ線等の電磁波、α線、イオン線等の荷電粒子線も含むものである。電離放射線硬化性樹脂の中でも、電子線硬化性樹脂は、無溶剤化が可能であり、光重合用開始剤を必要とせず、安定な硬化特性が得られるため、表面保護層5の形成において好適に使用される。
表面保護層5を形成する電離放射線硬化性樹脂組成物には、表面保護層5に備えさせる所望の物性に応じて、各種添加剤を配合することができる。この添加剤としては、例えば紫外線吸収剤や光安定剤等の耐候性改善剤、耐摩耗性向上剤、重合禁止剤、架橋剤、赤外線吸収剤、帯電防止剤、接着性向上剤、レベリング剤、チクソ性付与剤、カップリング剤、可塑剤、消泡剤、充填剤、溶剤、着色剤等が挙げられる。これらの添加剤は、常用されるものから適宜選択して用いることができる。また、紫外線吸収剤や光安定剤として、分子内に(メタ)アクリロイル基等の重合性基を有する反応性の紫外線吸収剤や光安定剤を用いることもできる。
表面保護層5の硬化後の厚さについては、特に制限されないが、例えば、1~1000μm、好ましくは1~50μm、更に好ましくは1~30μmが挙げられる。このような範囲の厚さを満たすと、耐傷付き性、耐候性等の表面保護層としての十分な物性が得られると共に、表面保護層4を電離放射線硬化性樹脂を用いて形成する場合には電離放射線を均一に照射することが可能であるため、均一に硬化することが可能となり、経済的にも有利になる。更に、表面保護層5の硬化後の厚さが前記範囲を充足することによって、加飾シートの三次元成形性が一層向上するため自動車内装用途等の複雑な三次元形状に対して高い追従性を得ることができる。このように、本発明の加飾シートは表面保護層5の厚さを従来のものより厚くしても、十分に高い三次元成形性が得られることから、特に表面保護層5に高い膜厚を要求される部材、例えば車両外装部品等の加飾シートとしても有用である。
表面保護層5の形成は、例えば、電離放射線硬化性樹脂を含む電離放射線硬化性樹脂組成物を調製し、これを塗布し、架橋硬化することにより行われる。なお、電離放射線硬化性樹脂組成物の粘度は、後述の塗布方式により、第2のプライマー層6、金属薄膜層4などの表面に未硬化樹脂層を形成し得る粘度であればよい。
第3のプライマー層8は、表面保護層5とその下に位置する層との密着性を高めることなどを目的として、必要に応じて、表面保護層5の下に設けられる層である。第3のプライマー層8は、例えば、図3または図4に示すように表面保護層5と後述のカラークリア層7との間、あるいは表面保護層5と後述の透明フィルム層9との間などに設けられる。第3のプライマー層8を形成する素材は、これらの層間の密着性を向上させ得るものであれば、特に限定されず、例えば、アクリル系樹脂、ポリウレタン系樹脂、アクリル-ウレタン共重合体樹脂、ポリエステル系樹脂などの樹脂が挙げられる。
カラークリア層7は、金属薄膜層4の金属調にさらに光沢などを持たせること等を目的として、必要に応じて、金属薄膜層4の上に設けられる層である。カラークリア層7を形成する素材としては、特に限定されないが、例えば、着色剤などにより着色された透明樹脂が挙げられる。着色剤としては、特に制限はないが、例えば、着色顔料、染料などが挙げられる。また、透明樹脂としては、特に制限はないが、例えば、アクリル系樹脂、ポリウレタン系樹脂、アクリル-ウレタン共重合体樹脂、ポリエステル系樹脂などが挙げられる。カラークリア層7の厚さは、特に限定されないが、通常0.5~4μm程度、好ましくは1~3μm程度である。カラークリア層7の形成方法は、特に制限されないが、例えば、後述の第2のプライマー層6、後述の透明フィルム層9、金属薄膜層4などのうち、カラークリア層7の直下に位置する層の表面上や、第3のプライマー層8など、カラークリア層7の直上に位置する層の表面上に上記の樹脂を塗布する方法などが挙げられる。
第2のプライマー層6は、金属薄膜層とその上に積層される層との密着性を向上させることなどを目的として、必要に応じて設けられる層である。例えば図3または図5に示されるように、第2のプライマー層6は、金属薄膜層4とその上に設けられる層との密着性を向上させることなどを目的として、必要に応じて、金属薄膜層4の直上に設けることができる。また、例えば図3または図4に示されるように、第2のプライマー層6は、カラークリア層7とその下に位置する層との密着性を高めること等を目的として、必要に応じて、カラークリア層7の下に設けることもできる。第2のプライマー層6は、例えば、図2に示すように金属薄膜層4と表面保護層5との間や、図3に示すように金属薄膜層4とカラークリア層7との間や、図4に示すようにカラークリア層7と後述の透明フィルム層9との間や、図5に示すように金属薄膜層4と透明フィルム層9との間に設けられる。また、第2のプライマー層6は、図2に示すように金属薄膜層4と表面保護層5との間に設けられた場合、上述の第3のプライマー8の項目で説明した役割を兼ねて果たすことになる。第2のプライマー層6を形成する素材は、これらの層間の密着性を向上させ得るものであれば、特に限定されず、例えば、アクリル系樹脂、ポリウレタン系樹脂、アクリル-ウレタン共重合体樹脂、ポリエステル系樹脂などの樹脂が挙げられる。
透明フィルム層9は、本発明の加飾シートの耐傷付き性や耐候性を高めると共に、成形性を高める支持体としての役割を果たし、必要に応じて、金属薄膜層4の上に設けられる樹脂フィルムである。透明フィルム層9を備えることで成形性が高まり、加飾シートを三次元成形した際に金属薄膜層4にクラックが発生しにくくなるので、伸展性に富むスズ、インジウム、クロム以外の金属(例えばアルミニウムなど)を用いて金属薄膜層4を形成する場合には、透明フィルム層9を備えることが好ましい。透明フィルム層9を形成する樹脂フィルムとしては、加飾シートの成形性を高め、金属薄膜層4による金属調の意匠を隠蔽するものでなければ、特に限定されないが、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル樹脂、またはアクリル樹脂などのフィルムが挙げられる。透明フィルム層9の厚さは、特に限定されないが、通常15~200μm程度、好ましくは30~150μm程度である。透明フィルム層9を形成する方法は、特に制限されないが、例えば、金属薄膜層4、表面保護層5、第2のプライマー層6、カラークリア層7、第3のプライマー層8などのうち、透明フィルム層9と隣接する層の表面上に上記の樹脂フィルムを積層する方法などが挙げられる。
第2の接着層10は、加飾シートと成形樹脂との接着性や密着性を向上させることなどを目的として、基材層1の裏面に必要に応じて設けられる層である。第2の接着層10を形成する樹脂としては、加飾シートと成形樹脂との接着性や密着性を向上させることができるものであれば、特に制限されず、例えば、熱可塑性樹脂または熱硬化性樹脂が用いられる。熱可塑性樹脂としては、例えば、アクリル樹脂、アクリル変性ポリオレフィン樹脂、塩素化ポリオレフィン樹脂、塩化ビニル-酢酸ビニル共重合体、熱可塑性ウレタン樹脂、熱可塑性ポリエステル樹脂、ポリアミド樹脂、ゴム系樹脂などが挙げられる。熱可塑性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。また、熱硬化性樹脂としては、例えば、ウレタン樹脂、エポキシ樹脂等挙げられる。熱硬化性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。
本発明の加飾樹脂成形品は、本発明の加飾シートに成形樹脂を一体化させることにより成形されてなるものである。即ち、本発明の加飾樹脂成形品は、少なくとも、成形樹脂層と、基材層1と、プライマー層3と、金属薄膜層4とがこの順に積層された積層体からなり、当該プライマー層3が、ガラス転移点が-30℃~80℃の上記の樹脂の硬化物を含むことを特徴とする。本発明の加飾樹脂成形品では、必要に応じて、加飾シートに上述の表面保護層5、第2のプライマー層6、カラークリア層7、第3のプライマー層8、透明フィルム層9、第2の接着層10などの少なくとも1層がさらに設けられていてもよい。
真空成形された加飾シートの余分な部分をトリミングして成形シートを得るトリミング工程、及び
成形シートを射出成形型に挿入し、射出成形型を閉じ、流動状態の樹脂を射出成形型内に射出して樹脂と成形シートを一体化する一体化工程。
成形面に沿って密着された加飾シートを有する可動金型と固定金型とを型締めした後、両金型で形成されるキャビティ内に、流動状態の樹脂を射出、充填して固化させることにより樹脂成形体を形成し、樹脂成形体と加飾シートを積層一体化させる一体化工程、及び
可動金型を固定金型から離間させて、加飾シート全層が積層されてなる樹脂成形体を取り出す取出工程。
(加飾シートの作製A)
剥離シートとしての2軸延伸ポリエチレンテレフタレートシート(東洋紡績社製のE5001、厚さ25μm)の上に、アクリル-ウレタンブロック共重合体樹脂を塗工して、厚さ2μmの透明な第3のプライマー層を形成した。次に、第3のプライマー層上に、着色剤を含むアクリル-ウレタンブロック共重合体樹脂を塗工して、カラークリア層(厚さ2μm)及び第2のプライマー層(厚さ2μm)を順に形成した。次に、第2のプライマー層の表面上にスズを蒸着して光学濃度値(OD)が1.2の金属薄膜層を形成した。次に、金属薄膜層の上に、それぞれ、表1Aに記載の組成及びガラス転移点(Tg)を有する第1のプライマー層(厚さ2μm)を形成した。なお、実施例9A及び10Aにおいては、第1のプライマー層の樹脂70質量部に対して、金属薄膜層と同系色を有する着色剤(酸化チタン、カーボンブラックを含む)を30質量部配合した。次に、第1のプライマー層の上に、表1Aに記載の樹脂を厚さ2μmとなるように塗工して接着層を形成した。次に、接着層の上に厚さ400μmのABS樹脂からなるシートを接触させて基材層を形成し、剥離シート/第3のプライマー層/カラークリア層/第2のプライマー層/金属薄膜層/第1のプライマー層/接着層/基材層がこの順に積層された積層体を得た。次に、この積層体の基材層側に、算術平均粗さRaが4.0μm、十点平均粗さRzJISが16μmの梨地柄の入ったステンレス製の金属板を配置し、剥離層側に算術平均粗さRaが0.05μmのステンレス製の鏡面板を配置し、この金属板と鏡面板で積層体を熱プレス成形した。熱プレス成形の条件は、温度150℃、圧力0.5MPa、加熱・加圧時間を10分間とした。次に、積層体から剥離シートを剥離し、第1のプライマー層の表面上に電離放射線硬化性樹脂を、硬化後の厚さが10μmとなるようにしてグラビアリバースにて塗布して未硬化の樹脂層を形成した。この未硬化の樹脂層に加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、未硬化の樹脂層を硬化させて表面保護層を形成した。以上のようにして、表1Aに示されるような構成を有する、基材層/接着層/第1のプライマー層/金属薄膜層/第2のプライマー層/カラークリア層/第3のプライマー層/表面保護層がこの順に積層された加飾シートを得た。なお、電離放射線硬化性樹脂としては、2官能ポリカーボネートアクリレート(重量平均分子量10000)80質量部と、6官能ウレタンアクリレートオリゴマー(重量平均分子量6000)20質量部との混合物を用いた。また、比較例3Aでは、第1のプライマー層を設けなかった。
実施例1A~10A及び比較例1A~3Aの加飾シートを、それぞれ赤外線ヒーターで160℃に加熱し、軟化させた。次に、真空成形用型を用い、最大延伸倍率が150%になる条件で真空成形し、真空成形用型の内部形状となるように加飾シートを成形した。次に、加飾シートを冷却後、真空成形用型から離型した。離型した加飾シートの表面保護層に割れや白化が全く見られず、真空成形用型の内部形状に良好に追従していたものを、成形性が良好(○)と評価した。離型した加飾シートの表面保護層に割れや白化が見られ、真空成形用型の内部形状に追従できていなかったものを、成形性が悪い(×)と評価した。結果を表1Aに示す。
実施例1A~10A及び比較例1A~3Aの加飾シートを、上記の成形性評価試験と同様の方法で真空成形した。次に、離型した加飾シートの表面保護層の表面に、それぞれカッターナイフを用いて2mm間隔で縦10本、横10本の碁盤状の切れ込みを入れた。次に、切れ込みを入れた部分にニチバン製セロテープ(登録商標)を圧着し、90°方向に急激剥離した。密着性評価試験の結果、加飾シートに剥離が全くなかったものを、密着性が良好(○)と評価した。加飾シートに切れ込みに沿って極軽微な切れ込みが見られたが実用上問題ないものを、密着性がやや良好(△)と評価した。加飾シートに明らかな剥離がみられたものを、密着性が悪い(×)と評価した。結果を表1Aに示す。
実施例1A~10A及び比較例1A~3Aの加飾シートを、上記の成形性評価試験と同様の方法で真空成形した後、それぞれ60℃、湿度90%の環境下で72時間静置した。次に、分光測色計(コニカミノルタ社製のCM-3700d)を用いて、色差ΔE*ab(JIS Z8729-1994に規定された国際照明委員会(CIE)のL*a*b表色系に準拠している)を測定した。色差ΔE*abは下記式で表される。
ΔE*ab=√(ΔL*)2+(Δa*)2+(Δb*)2
なお、色差の基準としては、それぞれ、耐退色性評価試験に供する前の実施例1A~10A及び比較例1A~3Aの加飾シートを用いた。耐退色性評価試験の結果、色差ΔE*abが3未満の場合に、退色が小さい(○)と評価し、色差ΔE*abが3以上5未満の場合に退色がやや大きい(△)、色差ΔE*abが5以上の場合に、退色が大きい(×)と評価した。結果を表1Aに示す。
実施例1A~10A及び比較例1A~3Aの加飾シートを、上記の成形性評価試験と同様の方法で真空成形し、射出成形に用いた。射出樹脂としてABS樹脂[日本エイアンドエル(株)製、商品名「クララスチックMTH-2」]を用い、これを230℃にて溶融状態にしてから、キャビティ内に射出した。金型温度が30℃になった時点で、金型から加飾樹脂成形品を取り出し、それぞれ実施例1A~10A及び比較例1A~3Aの加飾シートが射出樹脂と一体化した加飾樹脂成形品を得た。次に、得られた加飾樹脂成形品を、それぞれ、100℃、湿度65%の環境下で168時間静置した後、加飾樹脂成形品の表面を目視で観察し、加飾シートの剥がれの有無を観察した。加飾シートの剥がれが全くないものを○、加飾シートにごく軽微な剥がれはあるが、実用上全く問題ないものを○△、加飾シートに軽微な剥がれはあるが、実用上問題ないものを△、加飾シートの剥がれがあり、実用上問題があるものを×と評価した。結果を表1Aに示す。また、実施例1A及び比較例1Aの加飾シートを用いて得られた加飾樹脂成形品の耐熱性試験後の表面写真をそれぞれ図6及び図7に示す。
(加飾シートの作製B)
剥離シートとしての2軸延伸ポリエチレンテレフタレートシート(東洋紡績社製のA5101、厚さ25μm)の上に、アクリル-ウレタンブロック共重合体樹脂を塗工して、厚さ2μmの透明な第3のプライマー層を形成した。次に、第3のプライマー層上に、着色剤を含むアクリル-ウレタンブロック共重合体樹脂、及び透明なアクリル-ウレタンブロック共重合体樹脂を順に塗工して、カラークリア層(厚さ3μm)及び第2のプライマー層(厚さ2μm)を順に形成した。次に、第2のプライマー層の表面上に表1Bに記載の金属を蒸着して光学濃度値(OD)が1.2の金属薄膜層を形成した。次に、金属薄膜層の上に、それぞれ、表1Bに記載の組成を有する第1のプライマー層(厚さ2μm)を形成した。なお、実施例11Bにおいては、第1のプライマー層の樹脂70質量部に対して、金属薄膜層と同系色を有する着色剤(酸化チタン、カーボンブラックを含む)を30質量部配合した。次に、第1のプライマー層の上に、表1Bに記載の樹脂の塗布量となるように塗工して接着層を形成した。次に、接着層の上に厚さ400μmのABS樹脂からなるシートを接触させて基材層を形成し、剥離シート/第3のプライマー層/カラークリア層/第2のプライマー層/金属薄膜層/第1のプライマー層/接着層/基材層がこの順に積層された積層体を得た。次に、この積層体の基材層側に、算術平均粗さRaが4.0μm、十点平均粗さRzJISが16μmの梨地柄の入ったステンレス製の金属板を配置し、剥離層側に算術平均粗さRaが0.05μmのステンレス製の鏡面板を配置し、この金属板と鏡面板で積層体を熱プレス成形した。熱プレス成形の条件は、温度150℃、圧力0.5MPa、加熱・加圧時間を10分間とした。次に、積層体から剥離シートを剥離し、第3のプライマー層の表面上に電離放射線硬化性樹脂を、硬化後の厚さが10μmとなるようにしてグラビアリバースにて塗布して未硬化の樹脂層を形成した。この未硬化の樹脂層に加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、未硬化の樹脂層を硬化させて表面保護層を形成した。以上のようにして、表1Bに示されるような構成を有する、基材層/接着層/第1のプライマー層/金属薄膜層/第2のプライマー層/カラークリア層/第3のプライマー層/表面保護層がこの順に積層された加飾シートを得た。なお、電離放射線硬化性樹脂としては、2官能ポリカーボネートアクリレート(重量平均分子量10000)80質量部と、6官能ウレタンアクリレートオリゴマー(重量平均分子量6000)20質量部との混合物を用いた。比較例1Bでは、第1のプライマー層にシランカップリング剤を配合しなかった。比較例2B及び3Bでは、第1のプライマー層を設けなかった。比較例4Bでは、接着層を設けなかった。
透明フィルム層としての2軸延伸ポリエチレンテレフタレートフィルム(厚さ38μm)の一方の面に対し、表1Bに記載の金属を蒸着して光学濃度値(OD)が1.2の金属薄膜層を形成した。次に、金属薄膜層の上に、表1Bに記載の組成を有する第1のプライマー層(厚さ2μm)と、表1Bに記載の樹脂の塗布量の接着層を塗工により順に形成した。次に、透明フィルム層の金属薄膜層を形成しなかった面に、アクリル-ウレタンブロック共重合樹脂を順次塗工して、透明な第2のプライマー層(厚さ2μm)、カラークリア層(厚さ3μm)及び透明な第3のプライマー層(厚さ2μm)を形成した。次に、第3のプライマー層上に、電離放射線硬化性樹脂を硬化後の厚さが10μmとなるようにグラビアリバースにて塗工して未硬化の樹脂層を形成した。この未硬化の樹脂層に加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、未硬化の樹脂層を硬化させて表面保護層を形成した。次いで、接着層の上に厚さ400μmのABS樹脂からなるシートを積層して基材層を形成することにより、表1Bに示されるような構成を有する、基材層/接着層/第1のプライマー層/金属薄膜層/透明フィルム層/第2のプライマー層/カラークリア層/第3のプライマー層/表面保護層がこの順に積層された加飾シートを得た。なお、電離放射線硬化性樹脂としては実施例1B~8B、11B及び比較例1B~4Bと同様の混合物を用いた。
実施例1B~11B及び比較例1B~4Bの加飾シートを、それぞれ赤外線ヒーターで160℃に加熱し、軟化させた。次に、真空成形用型を用い、最大延伸倍率が150%になる条件で真空成形し、真空成形用型の内部形状となるように加飾シートを成形した。次に、加飾シートを冷却後、真空成形用型から離型した。離型した加飾シートの表面保護層に割れや白化が全く見られず、真空成形用型の内部形状に良好に追従していたものを、成形性が良好(○)と評価した。成形性評価試験の結果、離型した加飾シートの三次元成形部や最大延伸部の一部に微細な割れや白化が認められたが実用上問題ないものを、成形性がやや良好(○△)と評価した。離型した加飾シートの表面保護層に割れや白化が見られ、真空成形用型の内部形状に追従できていなかったものを、成形性が悪い(×)と評価した。
実施例1B~11B及び比較例1B~4Bの加飾シートを、上記の成形性評価試験と同様の方法で真空成形した。次に、離型した加飾シートの表面保護層の表面に、それぞれカッターナイフを用いて2mm間隔で縦10本、横10本の碁盤状の切れ込みを入れた。次に、切れ込みを入れた部分にニチバン製セロテープ(登録商標)を圧着し、急激剥離した。密着性評価試験の結果、加飾シートに剥離が全くなかったものを、密着性が良好(○)と評価した。加飾シートに切れ込みに沿って極軽微な切れ込みが見られたが実用上問題ないものを、密着性がやや良好(○△)と評価した。加飾シートに明らかな剥離がみられたものを、密着性が悪い(×)と評価した。
実施例1B~11B及び比較例1B~4Bの加飾シートを、上記の成形性評価試験と同様の方法で真空成形した後、それぞれ60℃、湿度90%の環境下で168時間静置した。次に、分光測色計(コニカミノルタ社製のCM-3700d)を用いて、色差ΔE*ab(JIS Z8729-1994に規定された国際照明委員会(CIE)のL*a*b表色系に準拠している)を測定した。色差ΔE*abは下記式で表される。
ΔE*ab=√(ΔL*)2+(Δa*)2+(Δb*)2
なお、色差の基準としては、それぞれ、耐退色性評価試験に供する前の実施例1B~11B及び比較例1B~4Bの加飾シートを用いた。耐退色性評価試験の結果、色差ΔE*abが5以下の場合に、退色が小さい(○)と評価し、色差ΔE*abが5以上の場合に、退色が大きい(×)と評価した。
(加飾シートの作製C)
剥離シートとしての2軸延伸ポリエチレンテレフタレートシート(東洋紡績社製のE5001、厚み25μm)の上に、アクリル-ウレタンブロック共重合樹脂を塗工して、厚み2μmの透明な第3のプライマー層を形成した。次に、第3のプライマー層上に、3質量%程度の着色剤を含むアクリル-ウレタンブロック共重合樹脂を塗工して、カラークリア層(厚み2μm)を形成した。次に、表1Cに記載の組成を有する第2のプライマー層を厚み2μmとなるように形成した。次に、第2のプライマー層の表面上にスズを蒸着して光学濃度値(OD)が1.2の金属薄膜層を形成した。次に、金属薄膜層の上に、アクリル-ウレタンブロック共重合樹脂を塗工して第1のプライマー層(厚み2μm)を形成した。次に、第1のプライマー層の上に、塩化ビニル-酢酸ビニル共重合体を厚み2μmとなるように塗工して接着層を形成した。次に、接着層の上に厚み400μmのABS樹脂からなるシートを接触させて基材層を形成し、剥離シート/第3のプライマー層/カラークリア層/第2のプライマー層/金属薄膜層/第1のプライマー層/接着層/基材層がこの順に積層された積層体を得た。
実施例1C~7C及び比較例1C~3Cの加飾シートを、それぞれ赤外線ヒーターで160℃に加熱し、軟化させた。次に、真空成形用型を用い、最大延伸倍率が150%になる条件で真空成形し、真空成形用型の内部形状となるように加飾シートを成形した。次に、加飾シートを冷却後、真空成形用型から離型した。離型した加飾シートに割れや白化が全く見られず、真空成形用型の内部形状に良好に追従していたものを、成形性が良好(○)と評価した。離型した加飾シートにごく軽微な割れや白化が見られたが実使用上全く問題ないものを(○△)と評価した。離型した加飾シートに軽微な割れや白化が見られたが、実用上問題ないものを(△)と評価した。離型した加飾シートに割れや白化が見られ、真空成形用型の内部形状に追従できておらず、成形性が悪くて実用上問題があるものを(××)と評価した。結果を表1Cに示す。
実施例1C~7C及び比較例1C~3Cの加飾シートを、上記の成形性評価試験と同様の方法で真空成形した。真空成形後の加飾シートの表面を目視で観察し、変色が全く見られないものを(○)、ごく軽微な変色が見られるが実用上全く問題ないものを(○△)、軽微な変色が見られるが実用上問題ないものを(△)、変色が見られ実用上問題があるものを(××)と評価した。結果を表1Cに示す。
2…接着層
3…第1のプライマー層
4…金属薄膜層
5…表面保護層
6…第2のプライマー層
7…カラークリア層
8…第3のプライマー層
9…透明フィルム層
Claims (25)
- 少なくとも、基材層と、第1のプライマー層と、金属薄膜層とがこの順に積層された積層体からなり、
前記第1のプライマー層は、ガラス転移点が-30℃~80℃の樹脂の硬化物を含む、加飾シート。 - 曲部を有する樹脂成形品の加飾用途に用いられ、
前記曲部が、前記加飾シートに対して最大延伸倍率150%以上の延伸を必要とする形状である、請求項1に記載の加飾シート。 - 前記ガラス転移点が-30℃~80℃の樹脂が、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、及びポリオレフィン系樹脂からなる群から選択された少なくとも1種である、請求項1または2に記載の加飾シート。
- 前記ガラス転移点が-30℃~80℃の樹脂が、ポリオール樹脂であり、
前記第1のプライマー層が、前記ポリオール樹脂とイソシアネート化合物との硬化物により形成されている、請求項1~3のいずれかに記載の加飾シート。 - 前記第1のプライマー層における前記ポリオール樹脂が、ポリエステルポリオールである、請求項4に記載の加飾シート。
- 前記第1のプライマー層における前記イソシアネート化合物が、脂肪族イソシアネート化合物である、請求項4または5に記載の加飾シート。
- 前記基材層と前記第1のプライマー層との間に接着層を有する、請求項1~6のいずれかに記載の加飾シート。
- 前記接着層が、塩素系樹脂を含む、請求項7に記載の加飾シート。
- 前記第1のプライマー層が、シランカップリング剤を含む樹脂組成物により形成されている、請求項8に記載の加飾シート。
- 前記塩素系樹脂が、ポリ塩化ビニル、塩素化ポリエチレン、ポリ塩化ビニリデン、エチレン-塩化ビニル共重合体、塩化ビニル-酢酸ビニル共重合体、ポリ塩化プロピレン、及び塩素化ポリプロピレンからなる群から選択された少なくとも1種である、請求項8または9に記載の加飾シート。
- 前記第1のプライマー層が、塩素系樹脂を実質的に含まない、請求項1~10のいずれかに記載の加飾シート。
- 前記金属薄膜層が、スズ、インジウム、クロム、アルミニウム、ニッケル、銅、銀、金、白金、亜鉛、及びこれらのうち少なくとも1種を含む合金からなる群から選択された少なくとも1種の金属により形成されている、請求項1~11のいずれかに記載の加飾シート。
- 前記金属薄膜層の上に表面保護層がさらに積層されている、請求項1~12のいずれかに記載の加飾シート。
- 前記金属薄膜層と前記表面保護層の間にさらに第2のプライマー層を有し、
前記第2のプライマー層は、ガラス転移点が55℃~110℃の樹脂の硬化物を含む、請求項13に記載の加飾シート。 - 前記ガラス転移点が55℃~110℃の樹脂が、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、及びポリオレフィン系樹脂からなる群から選択された少なくとも1種である、請求項14に記載の加飾シート。
- 前記ガラス転移点が55℃~110℃の樹脂が、ポリオール樹脂であり、
前記第2のプライマー層が、前記ポリオール樹脂とイソシアネート化合物との硬化物により形成されている、請求項14または15に記載の加飾シート。 - 前記第2のプライマー層における前記ポリオール樹脂が、ポリエステルポリオール及びアクリルポリオールの少なくとも一方である、請求項16に記載の加飾シート。
- 前記第2のプライマー層における前記イソシアネート化合物が、脂肪族イソシアネート化合物及び芳香族イソシアネート化合物の少なくとも一方である、請求項16または17に記載の加飾シート。
- 前記金属薄膜層の上に透明フィルム層がさらに積層されている、請求項1~18のいずれかに記載の加飾シート。
- 前記第1のプライマー層が、着色剤をさらに含む、請求項1~19のいずれかに記載の加飾シート。
- 少なくとも、成形樹脂層と、基材層と、第1のプライマー層と、金属薄膜層とがこの順に積層された積層体からなり、
前記第1のプライマー層は、ガラス転移点が-30℃~80℃の樹脂の硬化物を含む、加飾樹脂成形品。 - 前記基材層と前記第1のプライマー層の間に塩素系樹脂を含む接着剤層をさらに有し、
前記第1のプライマー層がシランカップリング剤を含む樹脂組成物により形成されている、請求項21に記載の加飾樹脂成形品。 - 前記金属薄膜層の上にさらに第2のプライマー層と表面保護層とがこの順に積層されており、
前記第2のプライマー層が、ガラス転移点が55℃~110℃の樹脂の硬化物を含む、請求項21または22に記載の加飾樹脂成形品。 - 請求項1~20のいずれかに記載の加飾シートを真空成形型により予め立体形状に成形する真空成形工程、
前記真空成形された加飾シートの余分な部分をトリミングして成形シートを得るトリミング工程、及び
前記成形シートを射出成形型に挿入し、前記射出成形型を閉じ、流動状態の樹脂を前記射出成形型内に射出して前記樹脂と前記成形シートとを一体化する一体化工程、
を備える、加飾樹脂成形品の製造方法。 - 前記加飾樹脂成形品が曲部を有し、
前記真空成形工程及び前記一体化工程の少なくとも一方の工程において、前記曲部に位置する加飾シートを最大延伸倍率150%以上に延伸する、請求項24に記載の加飾樹脂成形品の製造方法。
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