WO2016125907A1 - 化粧シート及び該化粧シートを備える化粧部材 - Google Patents
化粧シート及び該化粧シートを備える化粧部材 Download PDFInfo
- Publication number
- WO2016125907A1 WO2016125907A1 PCT/JP2016/053590 JP2016053590W WO2016125907A1 WO 2016125907 A1 WO2016125907 A1 WO 2016125907A1 JP 2016053590 W JP2016053590 W JP 2016053590W WO 2016125907 A1 WO2016125907 A1 WO 2016125907A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- decorative
- layer
- resin
- decorative sheet
- sheet
- Prior art date
Links
Images
Classifications
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- 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
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
- B05D3/144—Pretreatment of polymeric substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
-
- 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
- B32B2307/41—Opaque
-
- 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
- B32B2307/412—Transparent
-
- 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
- B32B2307/416—Reflective
-
- 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
- B32B2419/00—Buildings or parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
Definitions
- the present invention relates to a decorative sheet and a decorative member including the decorative sheet.
- a vehicle interior / exterior member generally, a metal member such as a steel plate, a resin member, or a wood member is used as an adherend, and a decorative sheet is bonded thereto (for example, Patent Document 1).
- members such as exterior members, doors, and window frames are used in an environment where they are exposed to direct sunlight.
- heat of direct sunlight propagates through the members into the building and the temperature inside the building rises.
- carbon black which easily absorbs heat, is used as a pigment generally used for any layer constituting a decorative member, for example, an adherend, a base material, or a decorative layer, particularly a black pigment. It is remarkable.
- Patent Document 2 a thermal barrier decorative sheet characterized by using perelin black as a pigment used in a printed layer in the decorative sheet has been proposed (for example, Patent Document 2).
- Patent Document 3 a thermal insulation decorative sheet using an azomethine azo resin as a black pigment in a pattern layer.
- black pigments such as Fe-Cr are also known (for example, Patent Document 4).
- perelin black and azomethine azo resins which are pigments used in the printing layer, are organic pigments, and have a low lightness and a calm color tone because they have lower hiding power and coloring power than inorganic pigments. It is difficult to obtain the design characteristics. In such a case, for example, by increasing the thickness of the decorative layer, it is possible to obtain a design with a somewhat calm color tone. However, since an organic pigment is used, the design is not sufficient.
- the decorative layer is thick, if the decorative sheet and the decorative member are used in an environment where they are exposed to direct sunlight, it is difficult to obtain adhesion between the decorative layer and other layers (weather resistant adhesion). Will also occur.
- the pigment described in Patent Document 4 is an inorganic pigment
- black pigments such as Fe—Cr are containing chromium in the composition thereof, and movement to limit their use has been accelerated in recent years. For this reason, it is preferable to use a chromium-free material for the pigment.
- the present invention has been made under such circumstances, and an object of the present invention is to provide a decorative sheet having excellent heat shielding performance, weather resistance adhesion, and calm color design, and a decorative member including the decorative sheet. It is what.
- the present invention provides a decorative sheet having the following configuration, and a decorative member including the decorative sheet.
- the decorative sheet contains a composite oxide containing at least manganese element, and the thickness of the decorative layer is 0.7 to 13 ⁇ m.
- a decorative sheet is a decorative sheet.
- a decorative member comprising an adherend and the decorative sheet according to the above [1] or [2] so that the adherend and the base sheet of the decorative sheet face each other.
- the decorative member provided with the thermal insulation performance, the weather-proof adhesiveness, and the design property of the calm color tone, and a decorative member provided with this decorative sheet can be provided.
- the decorative sheet of the present invention is a decorative sheet having a base sheet, a decorative layer, and a surface protective layer, wherein the decorative layer contains a composite oxide containing at least manganese element, and the thickness of the decorative layer is 0. 7 to 13 ⁇ m.
- FIG. 1 shows an example of a preferred layer configuration of a decorative sheet 10 of the present invention.
- the decorative sheet 10 shown in FIG. 1 includes a base sheet 11, a decorative layer 12, a surface protective layer 14, and the decorative layer 12. And the surface protective layer 14 are preferably provided with a resin layer 13.
- polyester resin examples include polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer, polyarylate, and the like. Of these, polyethylene terephthalate and polybutylene terephthalate are more preferable, and polyethylene terephthalate is more preferable.
- polystyrene resin examples include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and polyethylene and polypropylene are more preferable.
- the thickness of the base sheet is preferably 20 to 130 ⁇ m, more preferably 30 to 100 ⁇ m, and still more preferably 40 to 90 ⁇ m, taking account of ease of handling.
- the base sheet is preferably a colored resin sheet made of a colored resin.
- a colored resin when a decorative sheet is attached to an adherend to make a decorative member, the surface hue can be well concealed when the surface hue of the adherend varies. Therefore, excellent design properties can be obtained, and stability of the color tone of the decorative layer provided as desired can be ensured. Moreover, it is preferable that it is white from a viewpoint of obtaining the outstanding heat insulation performance.
- the colorant used for the above-mentioned purpose may be appropriately selected depending on the application.
- the base sheet can be colored colored or colored and opaque. In general, since it is necessary to conceal the surface of the adherend, it is preferable to make it colored and opaque.
- the colorant examples include inorganic pigments such as iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; Dyes; metal pigments composed of scaly foils such as aluminum and brass; pearlescent (pearl) pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate are preferably used.
- inorganic pigments such as iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue
- organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue
- Dyes organic pigments composed of scaly foils such as aluminum and brass
- pearlescent (pearl) pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate are
- the addition amount of carbon black (black) as the colorant is preferably 5.0 parts by mass or less with respect to 100 parts by mass of the resin forming the base sheet, 1.0 mass part or less is more preferable, and it is still more preferable not to add. Since carbon black (black) has the property of easily absorbing heat, the use of carbon black (black) in the decorative sheet makes it easier for the decorative sheet to absorb heat and reduces the heat shielding performance. is there. Further, when titanium oxide is used as the white pigment, it is not particularly limited, but the crystal type is known as a rutile type, anatase type, brookite type, etc., and has excellent whiteness, weather resistance and heat shielding.
- the rutile type is preferred from the characteristics such as performance.
- titanium oxide may deteriorate the resin by photocatalytic action, it is preferably surface-treated with a surface coating agent for the purpose of stabilizing the photocatalytic action, and the composition of the surface coating agent is limited.
- inorganic oxides such as silicon oxide, alumina, or zinc oxide can be used.
- the coating method of the surface coating agent is not particularly limited, and titanium oxide obtained by a known method can be used.
- the addition amount of the colorant is preferably 1 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the resin forming the base sheet so that the resin content is not extremely reduced in consideration of weather resistance. More preferred.
- the base sheet is made of a physical method such as an oxidation method or a concavo-convex method on one or both sides in order to enhance the interlayer adhesion between the base sheet and other layers, or to enhance the adhesion to various adherends.
- chemical surface treatments can be applied.
- the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method.
- These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
- an inorganic filler may be added to the base sheet as necessary.
- the inorganic filler include calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). And the like.
- the added amount of the inorganic filler is usually 1 to 50 parts by mass with respect to 100 parts by mass of the resin forming the base sheet.
- the various other additives for example, a foaming agent, a flame retardant, a lubricant, an antioxidant, a ultraviolet absorber, a light stabilizer, etc. may be mix
- the decorative layer is a layer that imparts decorative properties to the decorative sheet of the present invention, and contains a composite oxide containing at least a manganese element and has a thickness of 0.7 to 13 ⁇ m.
- composite oxide means an oxide containing at least two kinds of metal elements. Therefore, “a composite oxide containing at least a manganese element” means an oxide containing a manganese element and at least one metal element other than the manganese element.
- the composite oxide used for the decoration layer functions as a pigment, and is not particularly limited as long as it contains at least manganese element in its structure.
- the metal species other than manganese elements contained in the composite oxide include Group 2 elements such as calcium elements and barium elements; yttrium Elements, lanthanum elements, praseodymium elements; group 3 elements such as neodymium elements; group 4 elements such as titanium elements and zirconium elements; group 13 elements such as boron elements, aluminum elements, gallium elements and indium elements; antimony elements; Preferred are metal species such as Group 15 elements such as bismuth elements, and these can be used alone or in combination.
- Group 2 elements, Group 4 elements, and Group 15 elements are preferable, calcium elements, titanium elements, and bismuth elements are more preferable, calcium elements and titanium elements are further preferable, and calcium elements and titanium elements are particularly preferable.
- a composite oxide containing at least one of manganese, calcium, and titanium is particularly preferable.
- the structure of the complex oxide containing manganese element is not particularly limited, but a perovskite structure, an orthorhombic structure, a hexagonal structure, and the like are preferable from the viewpoint of obtaining a stable structure and excellent heat shielding performance and design.
- a perovskite structure is more preferable.
- the thickness of the decoration layer needs to be 0.7 to 13 ⁇ m. If the thickness of the decoration layer is less than 0.7 ⁇ m, the brightness cannot be lowered, so that a design with a calm color tone cannot be obtained. On the other hand, when the thickness of the decoration layer exceeds 13 ⁇ m, excellent weather resistance adhesion cannot be obtained.
- the thickness of the decorative layer is preferably 1 to 10 ⁇ m, and more preferably 3 to 8 ⁇ m, from the viewpoint of obtaining an excellent design with a calm color tone and weather resistance adhesion.
- binders As printing ink used for the decoration layer, in addition to the above complex oxide, binders, if necessary, colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. A suitable mixture is used.
- the binder is not particularly limited, and a curable resin such as a thermoplastic resin, a one-component curable resin, or a two-component curable resin can be used.
- the binder include urethane resin, acrylic resin, acrylic urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, polyester resin, polyamide resin, butyral. Any resin, polystyrene resin, nitrocellulose resin (nitrified cotton), cellulose acetate resin, etc. may be used alone or in combination of two or more.
- coloring agent it can select from the same thing illustrated as a coloring agent used for said base material sheet suitably as needed, and can use it. It is also the same that it is preferable not to use carbon black (black).
- the content of the composite oxide in the decorative layer is preferably 75% by mass or less, more preferably 30 to 75% by mass, and more preferably 50 to 75% by mass based on the solid content from the viewpoint of obtaining excellent weather resistance adhesion. Is more preferable.
- the content of the composite oxide is within the above range, excellent heat shielding performance and weather resistance adhesion can be obtained, brightness can be sufficiently lowered, and excellent design properties can be obtained.
- the content of the composite oxide in the decorative layer is the same as the content of the composite oxide based on the solid content contained in the printing ink forming the decorative layer.
- the content of the binder in the decoration layer is preferably 25% by mass or more, more preferably 25 to 70% by mass, and further preferably 25 to 50% by mass based on the solid content.
- the content of the binder in the decoration layer is the same as the solid content based content of the binder contained in the printing ink forming the decoration layer.
- the decorative layer may be a colored layer (so-called solid colored layer) covering the entire surface, or may be a pattern layer formed by printing various patterns using ink and a printing machine. Also, a combination of these may be used.
- the pattern may be a wood pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern imitating the surface of a rock, a fabric pattern imitating a cloth or cloth pattern, or tiling
- patterns, brickwork patterns, etc. and there are also patterns such as parquets and patchwork that combine these.
- These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.
- a design with a dark color tone with a brightness of 55 or less can be obtained, and a texture (tactile sensation) can be expressed by a concave shape described later, so that a realistic design and texture can be obtained.
- the wood grain pattern is suitable. Further, as described above, it is preferable not to use carbon black (black) from the viewpoint of heat shielding performance.
- the decorative layer includes a predetermined complex oxide and By having the thickness, it is possible to obtain an excellent design property even in the case of a dark color, and both excellent heat shielding performance and design property are achieved.
- the surface protective layer is located on the outermost surface of the decorative sheet of the present invention, which is provided directly on the decorative layer or on another layer, for example, a resin layer described later provided on the decorative layer as necessary. It is a layer that imparts surface properties such as scratch resistance, abrasion resistance, chemical resistance, etc. to the decorative sheet of the present invention and further to the decorative member using the decorative sheet.
- the surface protective layer is preferably composed of a cured product of a resin composition containing a curable resin. By comprising the hardened
- an ionizing radiation curable resin is preferably used in addition to a thermosetting resin such as a two-component curable resin, and a plurality of these are used, for example, ionizing radiation curing.
- a so-called hybrid type may be used in which a curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination. From the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the scratch resistance and wear resistance of the surface, ionizing radiation curable resins are preferable, and can be applied without solvent and handled. From the viewpoint of being easy, an electron beam curable resin is more preferable.
- An ionizing radiation curable resin is a resin that has an energy quantum that can crosslink and polymerize molecules in electromagnetic waves or charged particle beams, that is, a resin that crosslinks and cures when irradiated with ultraviolet rays or electron beams. is there. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.
- a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable.
- “(meth) acrylate” means “acrylate or methacrylate”.
- the polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.
- an oligomer having a radical polymerizable unsaturated group in the molecule for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And the like.
- other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain.
- an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.
- oligomers having a cationic polymerizable functional group there are oligomers having a cationic polymerizable functional group.
- a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate and the like as long as the purpose of the present invention is not impaired for the purpose of reducing the viscosity.
- These monofunctional (meth) acrylates may be used alone or in combination of two or more.
- the thickness of the surface protective layer is preferably 2 to 25 ⁇ m, more preferably 2 to 15 ⁇ m, from the viewpoint of obtaining excellent scratch resistance and durability, and surface properties such as wear resistance and chemical resistance. 10 ⁇ m is more preferable.
- the resin composition forming the surface protective layer can contain various additives other than those described above as long as the performance is not impaired.
- various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.
- the resin layer is a layer that is preferably provided from the viewpoint of protecting the decorative layer and improving scratch resistance.
- Preferred examples of the resin constituting the resin layer include an acrylic resin, a polycarbonate resin, a polyurethane resin, a polystyrene resin, a vinyl chloride resin, and a vinyl acetate resin in addition to the polyester resin and the polyolefin resin used as the base sheet. From the viewpoint of improvement of molding processability and scratch resistance, polyester resins and polyolefin resins are preferable, and polyolefin resins are more preferable. Further, from the same viewpoint, it is preferable that both the base sheet and the resin constituting the resin layer are polyolefin resins.
- the resin layer may be provided between the base sheet and the surface protective layer, and is preferably provided between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer.
- the resin layer may be transparent or opaque, and when provided between the decorative layer and the surface protective layer, the resin layer is preferably transparent from the viewpoint of making the decorative layer visible more clearly.
- transparent includes colorless and transparent as well as colored and translucent. In the case of being colored, preferred examples of the colorant used include those exemplified as the colorant used in the substrate sheet. It is also the same that it is preferable not to use carbon black (black).
- the thickness of the resin layer is preferably 20 to 130 ⁇ m, more preferably 30 to 100 ⁇ m, and still more preferably 40 to 90 ⁇ m. When the thickness of the resin layer is within the above range, the protective function of the decorative layer and the scratch resistance can be improved.
- the resin layer can be subjected to a physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one or both sides from the viewpoint of improving adhesiveness with each layer.
- a physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one or both sides from the viewpoint of improving adhesiveness with each layer.
- these physical or chemical surface treatments the same method as the surface treatment of the substrate sheet is preferably exemplified.
- the resin layer can be subjected to a treatment such as forming a primer layer or a back primer layer from the viewpoint of improving the adhesion with each layer.
- the decorative sheet of the present invention can have an adhesive layer as necessary.
- the resin layer when the resin layer is provided, it is effective to provide an adhesive layer when improving the adhesion between the resin layer and the decorative layer.
- an adhesive constituting the adhesive layer an adhesive usually used in a decorative sheet can be used, and its thickness is about 0.1 to 50 ⁇ m, and 1 to 30 ⁇ m from the viewpoint of obtaining sufficient adhesiveness. A range is preferred.
- the adhesive is not particularly limited, and examples thereof include urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives, etc. Among them, urethane adhesives are preferable in terms of adhesive strength. .
- a urethane type adhesive agent for example, a two-component curable type containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.
- An adhesive using a urethane resin may be mentioned.
- Acrylic-polyester-vinyl chloride resins and the like are also suitable adhesives that can easily exhibit adhesiveness by heating and maintain adhesive strength even when used at high temperatures.
- the adhesive layer can be formed by a known forming method such as a coating method using an adhesive composition composed of these resins and the like.
- the decorative sheet of the present invention can have a primer layer and a back primer layer in any one of the respective layers as necessary in order to improve the adhesion between the respective layers.
- a decorative member excellent in interlayer adhesion can be obtained by providing a primer layer as a back primer layer on the substrate sheet side between the adherend and the substrate sheet.
- a surface protective layer and another layer for example, a resin layer
- providing a primer layer between the resin layers is effective from the viewpoint of obtaining excellent scratch resistance of the decorative sheet of the present invention.
- the primer layer is a transparent or translucent layer, and can be formed using, for example, the resin exemplified as the binder resin used in the decorative layer.
- the thickness of the primer layer is usually about 0.5 to 20 ⁇ m, preferably 0.5 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
- the decorative sheet of the present invention preferably has a concave shape at least on the surface protective layer. Since the decorative sheet of the present invention has a concave shape, it is particularly excellent in texture (tactile feel). This concave shape should just exist in the surface protective layer at least, and there may exist what reaches a base material sheet. From the viewpoint of obtaining an excellent texture (tactile sensation), it is preferable to combine not only those that remain in the surface protective layer but also those that extend to the resin layer, those that extend to the decorative layer, and those that extend to the base sheet. In addition, in this specification, when the said surface protective layer etc. have the said concave shape, the thickness of this surface protective layer etc. means the thickness measured in the location which does not have the said concave shape.
- the maximum depth of the concave shape is preferably 15% or more and less than 100% with respect to the total thickness of the decorative sheet, more preferably 15 to 80%, and even more preferably 25 to 80%. Further, the maximum depth of the concave shape is preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and further preferably 30 ⁇ m or more. By having such a maximum depth, the decorative sheet does not break during concave processing, for example, embossing, and it does not end up as if the concave shape was crushed. A texture (tactile sensation) is obtained, and as a result, excellent design properties are obtained.
- the measurement of the maximum depth of the concave shape is carried out by measuring the height from the lowest point of the concave shape to the surface of the surface protective layer using a surface roughness shape measuring instrument.
- Cut-off value 2.50 mm
- Cut-off filter type 2RC
- Inclination correction method Measured under linear measurement conditions, with the deepest being the maximum depth.
- embossing may be performed by a normal method using a known single-wafer or rotary embossing machine.
- the brightness (CIE (International Lighting Commission) L * a * b * L * value in the color system) defined in JIS Z 8730: 2009 is preferably 55 or less, more preferably 45 or less. Preferably, 35 or less is more preferable.
- the “lightness” is a value measured from the surface side of the decorative sheet of the present invention, that is, the surface protective layer side.
- the solar reflectance in the wavelength range of 780 to 2500 nm calculated according to JIS K 5602: 2008 is preferably 20% or more, more preferably 25% or more, and 35% or more. More preferably.
- the solar reflectance of the decorative sheet is calculated according to JIS K 5602: 2008 (how to obtain the solar reflectance of the coating film, wavelength range: 780 to 2500 nm).
- the spectrophotometer was used to measure the spectral reflectance of the decorative sheet at an incident angle of 10 °, and using the obtained data, JIS K 5602: 2008 (How to determine the solar reflectance of a coating film, wavelength range: 780 to 2500 nm) Calculated according to
- the decorative sheet of the present invention includes, for example, a step (1) of providing a decorative layer on a base sheet, a step (2) of providing a resin layer on the decorative layer, and applying a curable resin composition on the resin layer. It can manufacture by passing through the process (3) which hardens
- Step (1) is a step of providing a decorative layer on the base sheet.
- a decoration layer is formed by apply
- the ink is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.
- the primer layer is formed by applying a resin composition forming the primer layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. Can do.
- Step (2) is a step of providing a resin layer on the decorative layer.
- the resin layer is formed by applying an adhesive to the base material sheet having the decorative layer as necessary to form an adhesive layer, and then using the resin composition for forming the resin layer to extrude and dry the resin layer. It can be formed by laminating by adhesion and pressure bonding by a method such as lamination, wet lamination, thermal lamination or the like.
- Step (3) is a step in which a curable resin composition is applied on the resin layer and cured to form a surface protective layer.
- the surface protective layer is obtained by applying and curing an ionizing radiation curable resin composition containing the ionizing radiation curable resin on a resin layer or a primer layer provided on the resin layer as desired. It is done.
- a curable resin composition may be apply
- Application of the resin composition for forming the surface protective layer is preferably gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. so that the thickness after curing is usually about 1 to 20 ⁇ m.
- the known method is more preferably performed by gravure coating.
- the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as an electron beam or ultraviolet ray to form a cured product. It becomes a protective layer.
- ionizing radiation such as an electron beam or ultraviolet ray
- the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
- the irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin 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, and for example, various electron beam accelerators such as a cockroft 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 are used. be able to.
- ultraviolet rays When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted.
- an ultraviolet-ray source For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
- thermosetting resin composition for formation of a surface protective layer
- the decorative sheet obtained as described above has excellent heat shielding performance, weather resistance adhesion, and design with a calm color tone, for example, in a form laminated with an adherend, a wall, a ceiling, Interior and exterior members of buildings such as floors, window frames, doors, handrails, skirting boards, edges, malls and other fittings, cabinets, furniture or light electrical appliances, cabinet surface decoration boards for OA equipment, vehicle interiors, It is suitably used as a decorative member used for various applications such as exteriors.
- the decorative member 20 of the present invention includes an adherend 21 and the decorative sheet 10 of the present invention, and the adherend 21 and the base sheet 11 of the decorative sheet 10 face each other. It prepares to do.
- FIG. 2 is a schematic cross-sectional view showing an example of a preferred layer configuration of the decorative member of the present invention.
- adherend examples include plate materials such as flat plates and curved plates, three-dimensional articles, sheets (or films), and the like.
- wood members such as wood fiber boards such as wood veneer, wood plywood, particle board, and MDF (medium density fiber board), and three-dimensional articles; Or metal members used as sheets, etc .; glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, etc.
- Ceramic materials such as: acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber plate, etc.
- the present invention may be appropriately selected from the above according to the application, and it is a member for interior and exterior of a building such as a wall, ceiling, floor, window frame, door, handrail, skirting board, surrounding edge, mall, etc.
- a wood member, a metal member, a resin member, and a member combining these are preferable.
- the thickness of the adherend may be appropriately selected depending on the application and material, and is usually preferably 0.1 to 5 mm, more preferably 0.1 to 3 mm.
- the adherend 21 and the decorative sheet 10 are preferably bonded together through an adhesive layer 22 in order to obtain excellent adhesiveness.
- a well-known adhesive agent can be used,
- adhesive agents such as a heat sensitive adhesive and a pressure sensitive adhesive, are mentioned preferably.
- the resin used for the adhesive constituting the adhesive layer include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and styrene-acrylic copolymers. At least one resin selected from polymer resins, polyester resins, polyamide resins and the like is used.
- a two-component curable polyurethane adhesive or polyester adhesive using an isocyanate or the like as a curing agent can also be applied.
- An adhesive can also be used for the adhesive layer.
- the pressure-sensitive adhesive an acrylic, urethane, silicone, rubber, or other pressure-sensitive adhesive can be appropriately selected and used.
- the adhesive layer is formed by applying and drying the above resin in a form that can be applied, such as a solution or emulsion, by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. can do.
- the thickness of the adhesive layer is not particularly limited, but is usually in the range of 1 to 100 ⁇ m. By setting it within this range, excellent adhesiveness can be obtained.
- the decorative member of the present invention comprises, for example, a decorative sheet produced from the decorative sheet of the present invention by, for example, the above steps (1) to (3), an adherent, a base sheet of the decorative sheet, and the adherend. Can be manufactured through the step (4) of laminating the layers.
- Examples of the method of laminating the adherend and the decorative sheet include, for example, a laminating method in which a decorative sheet is pressed onto a plate-shaped adherend with a pressure roller and an adhesive is interposed therebetween.
- the decorative sheet is supplied through the wrapping process in which the decorative sheet is sequentially pressure-bonded and laminated to the plurality of side surfaces constituting the adherend by a plurality of different rollers, and fixed to the fixed frame.
- Preferable examples include vacuum forming processing in which the decorative sheet is firmly attached to the vacuum forming mold.
- the heating temperature is usually 160 to 200 ° C., depending on the type of resin constituting the adhesive, and with reactive hot melt adhesives Usually about 100 to 130 ° C.
- the vacuum forming process is generally performed while heating, and is usually performed at about 80 to 130 ° C., preferably about 90 to 120 ° C.
- the decorative member obtained as described above can be arbitrarily cut and subjected to optional decoration such as grooving and chamfering on the surface and the end of the mouth using a cutting machine such as a router or a cutter.
- a cutting machine such as a router or a cutter.
- interior and exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, edges, moldings, etc., kitchens, furniture or light electrical appliances, OA equipment, etc. It can be used for a surface decorative board of a cabinet, an interior or exterior of a vehicle.
- UV lamp M04-L21WB / SUV (model number)” manufactured by Iwasaki Electric Co., Ltd.
- lamp jacket (“WJ50-SUV (model number)” manufactured by Iwasaki Electric Co., Ltd.)
- illuminometer trade name “UVD- 365PD “(manufactured by Iwasaki Electric Co., Ltd.)
- super accelerated weathering test apparatus I Super UV Tester SUV-W131 (model number) "manufactured by Iwasaki Electric Co., Ltd.) were used.
- the decorative member was irradiated for 20 hours under the conditions of a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm 2 , and then a cycle of condensation for 4 hours was repeated.
- a cellophane tape was applied to the surface protective layer surface of a 25 mm wide sample at room temperature (23 ° C.) and a relative humidity of 50%, and one end of the cellophane tape was attached.
- the peeled part was peeled off at a peeling speed of 100 mm / min using a tensile tester (Tensilon tester), the peel strength was measured three times, and the average value was evaluated according to the following criteria. .
- a sunshine weather meter WEL-300 manufactured by Suga Test Instruments Co., Ltd. was used for 120 minutes at a black panel temperature of 63 ° C. A weather resistance test was conducted under the condition of 18-minute rainfall, and after 4,000 hours, visual observation was performed.
- Example 1 Polypropylene resin sheet subjected to double-sided corona discharge treatment (white colored resin sheet, thickness: 60 ⁇ m, containing 0.01 parts by mass of carbon black as a pigment with respect to 100 parts by mass of polypropylene resin, combined with titanium oxide, 10 parts by mass Part) as a base sheet, and a two-component curable acrylic-urethane resin as a binder on one side of the base sheet, a composite oxide (pigment A, composite oxide containing manganese element, calcium element and titanium element, A printing ink containing 70% by mass of “MPT-370 (trade name)” manufactured by Ishihara Sangyo Co., Ltd.
- MPT-370 trade name
- a gravure printing method to provide a wood grain pattern decoration layer (thickness: 1 ⁇ m).
- a two-part curable urethane / nitrified cotton mixed resin composition was applied to the other surface to form a back primer layer (thickness: 2 ⁇ m).
- a transparent polyurethane resin adhesive is applied on the decorative layer to form an adhesive layer (thickness after drying: 3 ⁇ m), and the transparent polypropylene resin is heated and melt-extruded by a T-die extruder to obtain a transparent layer.
- a resin layer (thickness: 80 ⁇ m) was formed.
- the surface of the resin layer is subjected to corona discharge treatment, and then a two-component curable acrylic-urethane resin composition is applied by a gravure printing method to form a primer layer (thickness after drying: 1 ⁇ m), and further transparent
- An electron beam curable resin composition (electron beam curable resin: trifunctional urethane acrylate) was applied by a gravure coating method (solid content: 3 g / m 2 ), dried to form an uncured resin layer, and an oxygen concentration
- the surface of the uncured resin layer was cured by irradiation with an electron beam (pressurized voltage: 125 KeV, 5 Mrad) in an environment of 200 ppm to obtain a surface protective layer (thickness: 3 ⁇ m).
- Example 2 to 5 Comparative Examples 1 to 3 In Example 1, except that the thickness and brightness of the decorative layer, the type and content (%, solid content basis) of the composite oxide contained in the decorative layer, and the base sheet were changed as shown in Table 1. In the same manner as in Example 1, decorative sheets of Examples 2 to 5 and Comparative Examples 1 to 3 were produced. About the obtained decorative sheet, said evaluation is performed and the evaluation result is shown in Table 1.
- Example 6 In Example 1, a decorative sheet and a decorative member were produced in the same manner as in Example 1 except that the amount of titanium oxide in the polypropylene resin sheet subjected to the double-sided corona discharge treatment was increased to 30 parts by mass of the pigment. About the obtained decorative sheet, said evaluation is performed and the evaluation result is shown in Table 1.
- Pigment A Composite oxide containing calcium element, titanium element and manganese element ("MPT-370 (trade name)", manufactured by Ishihara Sangyo Co., Ltd.)
- Pigment B Complex oxide containing bismuth element and manganese element (“Black 6301 (trade name)”, manufactured by Asahi Kasei Kogyo Co., Ltd.)
- Pigment C Perylene black (“NBD-0744 (trade name)”, manufactured by Nihongo Bix Co., Ltd.)
- the decorative sheet of the present invention has a design with a calm color tone (preferably a lightness of 55 or less), a high solar reflectance, an excellent heat shielding performance, and an excellent weather resistance adhesion. It was confirmed that The decorative sheet of Example 3 using the base sheet not containing carbon black does not contain carbon black in the decorative layer, and therefore does not contain carbon black at all. However, the brightness is as low as 40 and is calm. It was confirmed that the design of the color tone was obtained and that the solar panel had better solar reflectance than the other examples using the base sheet containing carbon black. Further, from the comparison with Examples 2 and 5, the composite oxide (pigment A) containing calcium element, titanium element, and manganese element has better solar reflectance and exhibits better heat shielding performance. confirmed.
- the weather resistance appearance evaluation was inferior to that of Example 1 and the like.
- the decorative sheet of Comparative Example 1 in which the thickness of the decorative layer was as thin as 0.5 ⁇ m and the brightness was as high as 60 was not able to obtain a calm color design.
- the decorative sheet of Comparative Example 2 had a thick decorative layer of 15 ⁇ m, the brightness was 25 and a design with a calm color tone was obtained, but sufficient performance was not obtained in terms of weather resistance adhesion.
- the decorative sheet of Comparative Example 3 had a lightness of 60 because the hiding power and coloring power of the pigment C were weak, and a design with a calm color tone could not be obtained.
- the decorative sheet and the decorative member of the present invention have excellent heat shielding performance, weather resistance adhesion, and calm color tone design, members for interior and exterior of buildings such as walls, ceilings, floors, window frames, In addition to doors, handrails, skirting boards, peripheral edges, malls and other fittings, it is suitably used for decorative panels on cabinets such as kitchens, furniture or light electrical appliances, OA equipment, and interior / exterior members of vehicles. In particular, taking advantage of its heat shielding performance, it is suitably used for members used in environments exposed to direct sunlight, such as exterior members, doors, and window frames.
Abstract
Description
[2]装飾層と表面保護層との間に、樹脂層を有する上記[1]に記載の化粧シート。
[3]被着材と上記[1]又は[2]に記載の化粧シートとを、該被着材と該化粧シートの基材シートとが対向するように備える化粧部材。
本発明の化粧シートは、基材シート、装飾層、及び表面保護層を有する化粧シートであって、該装飾層が少なくともマンガン元素を含む複合酸化物を含有し、該装飾層の厚さが0.7~13μmであることを特徴とするものである。
以下、図1を参照しながら、本発明の化粧シートの構成について詳細に説明する。図1は本発明の化粧シート10の好ましい層構成の一例を示すものであり、図1に示される化粧シート10は、基材シート11、装飾層12、表面保護層14、及び該装飾層12と表面保護層14との間に好ましく設けられる樹脂層13を有するものである。
基材シートは、通常化粧シートの基材シートとして用いられるものを制限なく採用することができ、取り扱いが容易であることから、ポリエステル樹脂、ポリオレフィン樹脂により構成される基材シートが好ましい。
ポリエステル樹脂としては、例えば、ポリエチレンテレフタレート(以下「PET」ということがある。)、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート、ポリカーボネート、エチレンテレフタレート-イソフタレート共重合体、ポリアリレート等が好ましく挙げられ、なかでもポリエチレンテレフタレート、ポリブチレンテレフタレートがより好ましく、さらにポリエチレンテレフタレートが好ましい。
ポリオレフィン樹脂としては、ポリエチレン(低密度、中密度、高密度)、ポリプロピレン、ポリメチルペンテン、ポリブテン、エチレン-プロピレン共重合体、プロピレン-ブテン共重合体等が好ましく挙げられ、ポリエチレン、ポリプロピレンがより好ましい。
着色剤としては、鉄黒、チタン白、アンチモン白、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルー等の無機顔料;キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルー等の有機顔料又は染料;アルミニウム、真鍮等の鱗片状箔片からなる金属顔料;二酸化チタン被覆雲母、塩基性炭酸鉛等の鱗片状箔片からなる真珠光沢(パール)顔料等が好ましく用いられる。本発明においては、優れた遮熱性能を得る観点から、着色剤としてカーボンブラック(墨)の添加量として、基材シートを形成する樹脂100質量部に対して5.0質量部以下が好ましく、1.0質量部以下がより好ましく、添加しないことが更に好ましい。カーボンブラック(墨)は熱を吸収しやすい特性を有するため、化粧シートにカーボンブラック(墨)が用いられることにより、化粧シートが熱を吸収しやすくなり、遮熱性能が低下してしまうからである。また、白色顔料として酸化チタンを用いる場合は、特に限定されるものではないが、結晶型として、ルチル型、アナターゼ型、ブルッカイト型などが知られており、優れた白色度と耐候性及び遮熱性能などの特性からルチル型が好ましい。また、酸化チタンは、光触媒作用によって樹脂を劣化させる可能性があることから、光触媒作用を安定させる目的で、表面被覆剤で表面処理されていることが好ましく、該表面被覆剤の組成としては限定的ではないが、例えば、酸化ケイ素やアルミナ、又は、酸化亜鉛などの無機酸化物が挙げられる。表面被覆剤の被覆方法についても特に限定されたものではなく、公知の方法で得られた酸化チタンを使用することができる。
着色剤の添加量は、耐候性を考慮し樹脂分が極端に少なくならないよう、上述の基材シートを形成する樹脂100質量部に対し、1~30質量部が好ましく、1~20質量部がより好ましい。
上記酸化法としては、例えばコロナ放電処理、クロム酸化処理、火炎処理、熱風処理、オゾン・紫外線処理法等が挙げられ、凹凸化法としては、例えばサンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理は、基材の種類に応じて適宜選択されるが、一般にはコロナ放電処理法が効果及び操作性等の面から好ましく用いられる。
また、基材シートと各層との層間密着性の強化等を目的として、プライマー層や裏面プライマー層を形成する等の処理を施してもよい。
また、基材シートには、必要に応じてその他の各種添加剤、例えば、発泡剤、難燃剤、滑剤、酸化防止剤、紫外線吸収剤、光安定剤等が配合されていてもよい。
装飾層は、本発明の化粧シートに装飾性を付与する層であり、少なくともマンガン元素を含む複合酸化物を含有し、その厚さが0.7~13μmの層である。
なお、本明細書において、「複合酸化物」とは、少なくとも2種の金属元素を含む酸化物を意味する。従って、「少なくともマンガン元素を含む複合酸化物」とは、マンガン元素と、マンガン元素以外の少なくとも1種の金属元素を含む酸化物を意味する。
バインダーとしては特に制限はなく、熱可塑性樹脂、1液硬化型樹脂や2液硬化型樹脂等の硬化性樹脂を用いることができる。バインダーとしては、例えば、ウレタン樹脂、アクリル樹脂、アクリルウレタン樹脂、塩化ビニル/酢酸ビニル共重合体樹脂、塩化ビニル/酢酸ビニル/アクリル共重合体樹脂、塩素化ポリプロピレン樹脂、ポリエステル樹脂、ポリアミド樹脂、ブチラール樹脂、ポリスチレン樹脂、ニトロセルロース樹脂(硝化綿)、酢酸セルロース樹脂等の中から任意のものが、1種単独で又は2種以上を混合して用いられる。
また、装飾層中のバインダーの含有量は、固形分基準で25質量%以上であることが好ましく、25~70質量%がより好ましく、25~50質量%がさらに好ましい。ここで、装飾層中のバインダーの含有量は、該装飾層を形成する印刷インキ中に含まれる該バインダーの固形分基準の含有量と同じである。
装飾層が絵柄を有する場合、その模様としては、木目模様、大理石模様(例えばトラバーチン大理石模様)等の岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様等があり、これらを複合した寄木、パッチワーク等の模様もある。これらの模様は通常の黄色、赤色、青色、および黒色のプロセスカラーによる多色印刷によって形成される他、模様を構成する個々の色の版を用意して行う特色による多色印刷等によっても形成される。
本発明においては、明度55以下という濃色の落ち着いた色調の意匠性が得られ、また後述する凹形状により質感(触感)を表現することもできるため、リアルな意匠性と質感が得られる観点から木目模様が適している。また、上記のように遮熱性能の観点からカーボンブラック(墨)を用いないことが好ましいが、本発明は、カーボンブラックを用いなくとも、装飾層が所定の複合酸化物を含み、かつ所定の厚さを有することで、濃色の場合でも優れた意匠性を得ることを可能とし、優れた遮熱性能と意匠性とを両立している。
表面保護層は、装飾層の上に直接、又は他の層、例えば必要に応じて装飾層の上に設けられる後述する樹脂層の上に設けられる、本発明の化粧シートの最表面に位置する層であり、本発明の化粧シート、さらには該化粧シートを用いる化粧部材に耐傷性、耐摩耗性、耐薬品性等の表面特性を付与する層である。表面保護層は、好ましくは硬化性樹脂を含有する樹脂組成物の硬化物で構成される。硬化性樹脂組成物の硬化物により構成されることで、化粧シート、さらには該化粧シートを用いる化粧部材の表面特性を向上させることができる。
表面保護層を形成する樹脂の架橋密度を高め、表面の耐傷性や耐摩耗性を向上させ得るとの観点から、電離放射線硬化性樹脂が好ましく、また、無溶媒で塗布することができ、取り扱いが容易との観点から、電子線硬化性樹脂がより好ましい。
電離放射線硬化性樹脂とは、電磁波または荷電粒子線の中で分子を架橋、重合させ得るエネルギー量子を有するもの、すなわち、紫外線または電子線等を照射することにより、架橋、硬化する樹脂のことである。具体的には、従来電離放射線硬化性樹脂として慣用されている重合性モノマー及び重合性オリゴマーないしはプレポリマーの中から適宜選択して用いることができる。
さらに、重合性オリゴマーとしては、他にポリブタジエンオリゴマーの側鎖に(メタ)アクリレート基をもつ疎水性の高いポリブタジエン(メタ)アクリレート系オリゴマー、主鎖にポリシロキサン結合をもつシリコーン(メタ)アクリレート系オリゴマー、小さな分子内に多くの反応性基をもつアミノプラスト樹脂を変性したアミノプラスト樹脂(メタ)アクリレート系オリゴマー、あるいはノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、脂肪族ビニルエーテル、芳香族ビニルエーテル等の分子中にカチオン重合性官能基を有するオリゴマー等がある。
樹脂層は、装飾層の保護、耐傷性の向上の観点から、好ましく設けられる層である。
樹脂層を構成する樹脂としては、上記の基材シートとして用いられるポリエステル樹脂、ポリオレフィン樹脂の他、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリスチレン樹脂、塩化ビニル樹脂、酢酸ビニル樹脂等が好ましく挙げられる。成型加工性の向上、耐傷性の向上の観点から、ポリエステル樹脂、ポリオレフィン樹脂が好ましく、ポリオレフィン樹脂がより好ましい。また、これと同様の観点から、上記の基材シート及び樹脂層を構成する樹脂がともにポリオレフィン樹脂であることが好ましい。
樹脂層は透明であっても不透明でもよく、装飾層と表面保護層との間に設けられる場合は、装飾層をより鮮明に視認できるようにする観点から、透明であることが好ましい。ここで、透明とは、無色透明の他、着色透明及び半透明も含むものである。着色されている場合、用いられる着色剤としては、上記の基材シートに用いられる着色剤として例示したものを好ましく挙げることができる。また、カーボンブラック(墨)を用いないことが好ましいことも、同じである。
本発明の化粧シートは、必要に応じて接着層を有することができる。特に、上記の樹脂層を有する場合、該樹脂層と装飾層との間の接着性を向上させるときに、接着層を設けることは有効である。接着層を構成する接着剤としては、通常化粧シートで用いられる接着剤を用いることができ、その厚さは0.1~50μm程度であり、十分な接着性が得られる観点から1~30μmの範囲が好ましい。
接着層は、これら樹脂等からなる接着剤組成物を用いて、塗工法等の公知の形成法で形成することができる。
本発明の化粧シートは、必要に応じて、各層間密着性を向上させるために、各層間のいずれかにプライマー層、裏面プライマー層を有することができる。例えば、被着材と基材シートとの間で、基材シート側に裏面プライマー層としてプライマー層を設けることで、層間密着性に優れた化粧部材が得られる。また、表面保護層と他の層、例えば樹脂層を設ける場合は樹脂層との間に、プライマー層を設けることが、本発明の化粧シートの優れた耐傷性を得る観点から効果的である。
本発明の化粧シートは、少なくとも表面保護層に凹形状を有することが好ましい。本発明の化粧シートは凹形状を有することで、特に質感(触感)に優れたものとなる。この凹形状は、少なくとも表面保護層に存在していればよく、また基材シートに至るものがあってもよい。優れた質感(触感)を得る観点から、表面保護層内に留まるものだけでなく、樹脂層まで至るもの、装飾層まで至るもの、基材シートまで至るものが組み合わされていることが好ましい。
なお、本明細書において、上記表面保護層等が上記凹形状を有する場合、該表面保護層等の厚みは、上記凹形状を有さない箇所で測定した厚みを意味する。
なお、本明細書において、上記「明度」とは、本発明の化粧シートの表面側、すなわち、表面保護層側から測定した値である。
本発明の化粧シートの製造方法について、本発明の化粧シートとして好ましい態様の一つである、基材シート、装飾層、樹脂層、及び表面保護層を順に有する化粧シートを例にとって、その製造方法を説明する。本発明の化粧シートは、例えば、基材シート上に装飾層を設ける工程(1)、該装飾層上に樹脂層を設ける工程(2)、該樹脂層上に硬化性樹脂組成物を塗布し、硬化させて表面保護層を形成して化粧シートを作製する工程(3)を順に経ることにより製造することができる。
電子線源としては、特に制限はなく、例えばコックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、あるいは直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用いることができる。
また、電離放射線として紫外線を用いる場合には、波長190~380nmの紫外線を含むものを放射する。紫外線源としては特に制限はなく、例えば高圧水銀燈、低圧水銀燈、メタルハライドランプ、カーボンアーク燈等が用いられる。
図2に示されるように、本発明の化粧部材20は、被着材21と上記の本発明の化粧シート10とを、該被着材21と該化粧シート10の基材シート11とが対向するように備えるものである。なお、図2は、本発明の化粧部材の好ましい層構成の一例を示す断面模式図である。
被着材としては各種素材の平板、曲面板等の板材、立体形状物品、シート(或いはフィルム)等が挙げられる。例えば、木材単板、木材合板、パーティクルボード、MDF(中密度繊維板)等の木質繊維板等の板材や立体形状物品等として用いられる木質部材;鉄、アルミニウム等の板材や鋼板、立体形状物品、あるいはシート等として用いられる金属部材;ガラス、陶磁器等のセラミックス、石膏等の非セメント窯業系材料、ALC(軽量気泡コンクリート)板等の非陶磁器窯業系材料等の板材や立体形状物品等として用いられる窯業部材;アクリル樹脂、ポリエステル樹脂、ポリスチレン樹脂、ポリプロピレン等のポリオレフィン系樹脂、ABS(アクリロニトリル-ブタジエン-スチレン共重合体)樹脂、フェノール樹脂、塩化ビニル樹脂、セルロース系樹脂、ゴム等の板材、立体形状物品、あるいはシート等として用いられる樹脂部材等が挙げられる。また、これらの部材は、単独で、又は複数種を組み合わせて用いることができる。
図2に示したように、被着材21と化粧シート10とは、優れた接着性を得るため、接着剤層22を介して貼り合わせられることが好ましい。
上記接着剤層に用いられる接着剤としては、特に限定されず、公知の接着剤を使用することができ、例えば感熱接着剤や感圧接着剤等の接着剤が好ましく挙げられる。この接着剤層を構成する接着剤に用いられる樹脂としては、例えばアクリル系樹脂、ポリウレタン系樹脂、塩化ビニル系樹脂、酢酸ビニル系樹脂、塩化ビニル-酢酸ビニル系共重合樹脂、スチレン-アクリル系共重合樹脂、ポリエステル系樹脂、ポリアミド系樹脂等の中から選ばれる少なくとも1種の樹脂が使用される。また、イソシアネート等を硬化剤とする2液硬化型のポリウレタン系接着剤又はポリエステル系接着剤も適用し得る。
また、接着剤層には、粘着剤を用いることもできる。粘着剤としては、アクリル系、ウレタン系、シリコーン系、ゴム系等の粘着剤を適宜選択して用いることができる。
接着剤層の厚さは特に制限はないが、通常、1~100μmの範囲である。この範囲とすることで、優れた接着性が得られる。
本発明の化粧部材は、本発明の化粧シートを例えば上記の工程(1)~(3)により製造した化粧シートと、被着材とを、該化粧シートの基材シートと該被着材とを対向させて積層する工程(4)を経て製造することができる。
被着材と化粧シートとの積層する方法としては、例えば、接着剤を間に介して化粧シートを板状の被着材に加圧ローラーで加圧して積層するラミネート方法、接着剤を間に介して化粧シートを供給しつつ、複数の向きの異なるローラーにより、被着材を構成する複数の側面に順次化粧シートを加圧接着して積層してゆくラッピング加工、また、固定枠に固定した化粧シートが軟化する所定の温度になるまでシリコーンゴムシートを介してヒーターで加熱し、加熱され軟化した化粧シートに真空成形金型を押し付け、同時に真空成形金型から真空ポンプ等で空気を吸引し化粧シートを真空成形金型にしっかりと密着させる真空成形加工等が好ましく挙げられる。
(評価方法)
(1)明度(L*値)の測定
各実施例及び比較例で得られた化粧シートについて、分光測色計(「CM-3700d(型番)」,コニカミノルタホールディングス(株)製)を用いて、JIS Z 8730:2009に規定されるCIE(国際照明委員会)L*a*b*表色系におけるL*値を測定した。
(2)日射反射率の算出
各実施例及び比較例で得られた化粧シートについて、分光光度計(「UV-3100PC(型番)」,島津製作所(株)製)を用いて、表面保護層側から入射角10°にて分光反射率を測定し、得られたデータを用いて、JIS K 5602:2008に準拠した波長範囲780~2500nmでの日射反射率を算出し、下記の基準で評価した。
A:日射反射率が45%以上だった。
B:日射反射率が35%以上45%未満だった。
C:日射反射率が25%以上35%未満だった。
D:日射反射率が15%以上25%未満だった。
E:日射反射率が15%未満だった。
(3)耐候密着性の評価
各実施例及び比較例で得られた化粧シートを、次の耐候試験に供した。UVランプ(「M04-L21WB/SUV(型番)」,岩崎電気(株)製)、ランプジャケット(「WJ50-SUV(型番)」,岩崎電気(株)製)及び照度計(商品名「UVD-365PD」、岩崎電気(株)製)を備えた超促進耐候性試験装置(「アイ スーパー UVテスター SUV-W131(型番)」,岩崎電気(株)製)を使用した。化粧部材に対し、ブラックパネル温度63℃、照度60mW/cm2の条件で20時間照射を行った後、4時間結露を行うサイクルを繰り返した。
50時間後に、化粧シートの表面保護層の密着性について、室温(23℃)、相対湿度50%の条件下、25mm巾のサンプルの表面保護層面にセロハンテープを貼り付け、そのセロハンテープの一端を剥がし、その剥がした部分を、引張試験機(テンシロン試験機)を用いて、剥離スピード100mm/minにて剥離し、3回ずつ剥離強度を測定して、その平均値を下記の基準で評価した。
A:剥離強度が15N/25mm以上であった。
B:剥離強度が10N/25mm以上15N/25mm未満であった。
C:剥離強度が5N/25mm以上10N/25mm未満であった。
D:剥離強度が5N/25mm未満であった。
(4)耐候性外観評価
各実施例及び比較例で得られた化粧部材に対し、サンシャインウェザーメーターWEL-300(スガ試験機株式会社製)を用いて、ブラックパネル温度63℃で、120分中18分降雨の条件にて耐候性試験を行い、4000時間後目視にて観察し、表面保護層等の各層間の浮き、脱落などの外観異常の有無を検査し、以下の基準で評価した。
A:大きな外観変化は見られなかった。すなわち、外観変化は殆ど見られなかったレベルであった。
B:軽微な外観変化が見られた。
C:大きな外観変化が見られ、問題のあるレベルであった。
両面コロナ放電処理を施したポリプロピレン樹脂シート(白色の着色樹脂シート,厚さ:60μm,ポリプロピレン樹脂100質量部に対して、顔料としてカーボンブラックを0.01質量部含み、酸化チタンと合わせて10質量部)を基材シートとし、該基材シートの一方の面に2液硬化型アクリル-ウレタン樹脂をバインダーとし、複合酸化物(顔料A,マンガン元素、カルシウム元素及びチタン元素を含む複合酸化物,「MPT-370(商品名)」,石原産業(株)製)を固形分基準で70質量%含む印刷インキをグラビア印刷法で塗布して木目模様の装飾層(厚さ:1μm)を設け、他方の面に2液硬化型ウレタン-硝化綿混合樹脂組成物を塗布して裏面プライマー層(厚さ:2μm)を形成した。装飾層の上に、透明のポリウレタン樹脂系接着剤を塗布して接着層(乾燥後の厚さ:3μm)を形成し、透明なポリプロピレン樹脂をTダイ押出機により加熱溶融押出しして、透明な樹脂層(厚さ:80μm)を形成した。
次いで、樹脂層の表面にコロナ放電処理を施した後、2液硬化型アクリル-ウレタン樹脂組成物をグラビア印刷法で塗布してプライマー層(乾燥後の厚さ:1μm)を形成し、さらに透明の電子線硬化性樹脂組成物(電子線硬化性樹脂:3官能ウレタンアクリレート)をグラビアコート法により塗布(固形分:3g/m2)し、乾燥して未硬化樹脂層を形成し、酸素濃度200ppmの環境下で電子線(加圧電圧:125KeV、5Mrad)を照射して該未硬化樹脂層を硬化させて、表面保護層(厚さ:3μm)を得た。その後、表面保護層側からエンボス加工を施して、最大深さ30μmの凹形状を有する木目導管模様の凹凸模様を形成し、実施例1の化粧シートを得た。得られた化粧シートについて、上記の評価を行い、その評価結果を表1に示す。
実施例1において、装飾層の厚さ、明度、装飾層に含まれる複合酸化物の種類及び含有量(%、固形分基準)、並びに基材シートを表1に記載のように変更した以外は、実施例1と同様にして、実施例2~5、比較例1~3の化粧シートを作製した。得られた化粧シートについて、上記の評価を行い、その評価結果を表1に示す。
実施例1において、両面コロナ放電処理を施したポリプロピレン樹脂シートの酸化チタン量を増やして、顔料を30質量部とした以外は、実施例1と同様にして化粧シート及び化粧部材を作製した。得られた化粧シートについて、上記の評価を行い、その評価結果を表1に示す。
顔料B:ビスマス元素及びマンガン元素を含む複合酸化物(「Black 6301(商品名)」,アサヒ化成工業(株)製)
顔料C:ペリレンブラック(「NBD-0744(商品名)」,日弘ビックス(株)製)
一方、装飾層の厚さが0.5μmと薄く、明度が60と大きくなってしまった比較例1の化粧シートは、落ち着いた色調の意匠性は得られなかった。比較例2の化粧シートは装飾層の厚さが15μmと厚いため、明度は25となり落ち着いた色調の意匠性は得られたが、耐候密着性の点で十分な性能が得られなかった。比較例3の化粧シートは、顔料Cの隠蔽力や着色力が弱いために明度が60と大きくなってしまい、落ち着いた色調の意匠性は得られなかった。
11.基材シート
12.装飾層
13.樹脂層
14.表面保護層
20.化粧部材
21.被着材
22.接着剤層
Claims (12)
- 基材シート、装飾層、及び表面保護層を有する化粧シートであって、該装飾層が少なくともマンガン元素を含む複合酸化物を含有し、該装飾層の厚さが0.7~13μmである化粧シート。
- 明度が55以下である請求項1に記載の化粧シート。
- 複合酸化物が、さらにチタン元素、カルシウム元素及びビスマス元素から選ばれる少なくとも一種の元素を含むものである請求項1又は2に記載の化粧シート。
- 複合酸化物が、さらにチタン元素及びカルシウム元素から選ばれる少なくとも一種の元素とを含むものである請求項3に記載の化粧シート。
- 装飾層中の複合酸化物の含有量が、固形分基準で75質量%以下である請求項1~4のいずれかに記載の化粧シート。
- 基材シートが、カーボンブラックを含まないものである請求項1~5のいずれかに記載の化粧シート。
- 化粧シートが、カーボンブラックを含まないものである請求項1~6のいずれかに記載の化粧シート。
- 基材シートが、着色樹脂シートである請求項1~7のいずれかに記載の化粧シート。
- 表面保護層が、電離放射線硬化性樹脂組成物の硬化物である請求項1~8のいずれかに記載の化粧シート。
- 装飾層と表面保護層との間に、樹脂層を有する請求項1~9のいずれかに記載の化粧シート。
- 被着材と請求項1~10のいずれかに記載の化粧シートとを、該被着体と該化粧シートの基材シートとが対向するように備える化粧部材。
- 被着材が、木質部材、金属部材、及び樹脂部材から選ばれる少なくとも一種である請求項11に記載の化粧部材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016573443A JP6528785B2 (ja) | 2015-02-06 | 2016-02-05 | 化粧シート及び該化粧シートを備える化粧部材 |
US15/547,705 US20180022076A1 (en) | 2015-02-06 | 2016-02-05 | Decorative sheets and decorative members including the decorative sheets |
CN201680008405.7A CN107206744B (zh) | 2015-02-06 | 2016-02-05 | 装饰片和具备该装饰片的装饰部件 |
EP16746737.2A EP3254844B1 (en) | 2015-02-06 | 2016-02-05 | Decorative sheet and decorative member provided with decorative sheet |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-022589 | 2015-02-06 | ||
JP2015022589 | 2015-02-06 | ||
JP2015025787 | 2015-02-12 | ||
JP2015-025787 | 2015-02-12 | ||
JP2015189909 | 2015-09-28 | ||
JP2015-189909 | 2015-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016125907A1 true WO2016125907A1 (ja) | 2016-08-11 |
Family
ID=56564239
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/053590 WO2016125907A1 (ja) | 2015-02-06 | 2016-02-05 | 化粧シート及び該化粧シートを備える化粧部材 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20180022076A1 (ja) |
EP (1) | EP3254844B1 (ja) |
JP (1) | JP6528785B2 (ja) |
CN (1) | CN107206744B (ja) |
WO (1) | WO2016125907A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018167495A (ja) * | 2017-03-30 | 2018-11-01 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
CN109421317A (zh) * | 2017-06-28 | 2019-03-05 | 菊水化学工业株式会社 | 壁面材以及用于壁面材的印刷用基材 |
WO2019065801A1 (ja) | 2017-09-27 | 2019-04-04 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
WO2019065800A1 (ja) | 2017-09-27 | 2019-04-04 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
WO2021049611A1 (ja) * | 2019-09-13 | 2021-03-18 | 大日本印刷株式会社 | 化粧材及び化粧部材 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020179517A (ja) * | 2019-04-23 | 2020-11-05 | 凸版印刷株式会社 | 加飾シート |
US20230033148A1 (en) * | 2019-12-27 | 2023-02-02 | Dai Nippon Printing Co., Ltd. | Metal tone decorative sheet and metal tone decorative molded body provided with metal tone decorative sheet |
IT202100028658A1 (it) * | 2021-11-11 | 2023-05-11 | Kompany S R L | Pellicola di rivestimento per serramenti |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01188334A (ja) * | 1988-01-23 | 1989-07-27 | Oike Ind Co Ltd | メタリック化粧シート |
JPH04214029A (ja) * | 1990-02-27 | 1992-08-05 | Engelhard Corp | 高赤外反射性褐色ルチル顔料組成物 |
JP2002532379A (ja) * | 1998-12-18 | 2002-10-02 | ディー エム シー ツー デグサ メタルズ キャタリスツ セルデック アクチェンゲゼルシャフト | ビスマスマンガンオキサイド顔料 |
JP2003246017A (ja) * | 2002-02-26 | 2003-09-02 | Toppan Printing Co Ltd | 化粧シート |
JP2004276345A (ja) * | 2003-03-14 | 2004-10-07 | Nippon Decor Inc | 赤外線反射機能を有する印刷フィルム |
JP2004322568A (ja) * | 2003-04-28 | 2004-11-18 | Toppan Printing Co Ltd | 化粧材及びその製造方法 |
JP2010202489A (ja) * | 2008-05-23 | 2010-09-16 | Ishihara Sangyo Kaisha Ltd | 赤外線反射材料及びその製造方法並びにそれを含有した塗料、樹脂組成物 |
JP2013086451A (ja) * | 2011-10-21 | 2013-05-13 | Toppan Cosmo Inc | 遮熱化粧シート |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59178252A (ja) * | 1983-03-30 | 1984-10-09 | 住友ベークライト株式会社 | 熱硬化性樹脂化粧板 |
CN1749032A (zh) * | 2004-09-16 | 2006-03-22 | 大日本印刷株式会社 | 装饰薄片和装饰材料 |
SE528890C2 (sv) * | 2005-02-17 | 2007-03-06 | Sandvik Intellectual Property | Metallsubstrat, artikel och förfarande |
JP2007254854A (ja) * | 2006-03-24 | 2007-10-04 | Citizen Tohoku Kk | 金属酸化物被膜及び金属酸化物被膜被覆部材 |
CN101445675A (zh) * | 2008-12-12 | 2009-06-03 | 温州亦柏化工有限公司 | 高色浓度的彩色铝颜料及其制备方法 |
JP5662651B2 (ja) * | 2009-05-01 | 2015-02-04 | スリーエム イノベイティブ プロパティズ カンパニー | 表面保護フィルム及びそれを備える多層フィルム |
TW201231311A (en) * | 2011-01-31 | 2012-08-01 | Sipix Chemical Inc | Decoration film and decorated molded device |
JP2013237248A (ja) * | 2012-05-17 | 2013-11-28 | Toppan Cosmo Inc | 遮熱化粧シート |
JP6102469B2 (ja) * | 2013-01-17 | 2017-03-29 | 東洋インキScホールディングス株式会社 | 分散組成物、塗料組成物、塗膜、および着色物 |
-
2016
- 2016-02-05 CN CN201680008405.7A patent/CN107206744B/zh active Active
- 2016-02-05 EP EP16746737.2A patent/EP3254844B1/en active Active
- 2016-02-05 JP JP2016573443A patent/JP6528785B2/ja active Active
- 2016-02-05 WO PCT/JP2016/053590 patent/WO2016125907A1/ja active Application Filing
- 2016-02-05 US US15/547,705 patent/US20180022076A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01188334A (ja) * | 1988-01-23 | 1989-07-27 | Oike Ind Co Ltd | メタリック化粧シート |
JPH04214029A (ja) * | 1990-02-27 | 1992-08-05 | Engelhard Corp | 高赤外反射性褐色ルチル顔料組成物 |
JP2002532379A (ja) * | 1998-12-18 | 2002-10-02 | ディー エム シー ツー デグサ メタルズ キャタリスツ セルデック アクチェンゲゼルシャフト | ビスマスマンガンオキサイド顔料 |
JP2003246017A (ja) * | 2002-02-26 | 2003-09-02 | Toppan Printing Co Ltd | 化粧シート |
JP2004276345A (ja) * | 2003-03-14 | 2004-10-07 | Nippon Decor Inc | 赤外線反射機能を有する印刷フィルム |
JP2004322568A (ja) * | 2003-04-28 | 2004-11-18 | Toppan Printing Co Ltd | 化粧材及びその製造方法 |
JP2010202489A (ja) * | 2008-05-23 | 2010-09-16 | Ishihara Sangyo Kaisha Ltd | 赤外線反射材料及びその製造方法並びにそれを含有した塗料、樹脂組成物 |
JP2013086451A (ja) * | 2011-10-21 | 2013-05-13 | Toppan Cosmo Inc | 遮熱化粧シート |
Non-Patent Citations (1)
Title |
---|
See also references of EP3254844A4 * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018167495A (ja) * | 2017-03-30 | 2018-11-01 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
CN109421317A (zh) * | 2017-06-28 | 2019-03-05 | 菊水化学工业株式会社 | 壁面材以及用于壁面材的印刷用基材 |
KR20200059265A (ko) * | 2017-09-27 | 2020-05-28 | 다이니폰 인사츠 가부시키가이샤 | 화장 시트 및 이것을 이용한 화장재 |
WO2019065800A1 (ja) | 2017-09-27 | 2019-04-04 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
JP2019059178A (ja) * | 2017-09-27 | 2019-04-18 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
JP2019059180A (ja) * | 2017-09-27 | 2019-04-18 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
WO2019065801A1 (ja) | 2017-09-27 | 2019-04-04 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
KR20200059264A (ko) * | 2017-09-27 | 2020-05-28 | 다이니폰 인사츠 가부시키가이샤 | 화장 시트 및 이것을 이용한 화장재 |
EP3689598A4 (en) * | 2017-09-27 | 2021-07-14 | Dai Nippon Printing Co., Ltd. | DECORATIVE FILM AND DECORATIVE MATERIAL WITH IT |
US11731409B2 (en) | 2017-09-27 | 2023-08-22 | Dai Nippon Printing Co., Ltd. | Decorative sheet and decorative material using same |
KR102584824B1 (ko) | 2017-09-27 | 2023-10-05 | 다이니폰 인사츠 가부시키가이샤 | 화장 시트 및 이것을 이용한 화장재 |
KR102584821B1 (ko) | 2017-09-27 | 2023-10-05 | 다이니폰 인사츠 가부시키가이샤 | 화장 시트 및 이것을 이용한 화장재 |
WO2021049611A1 (ja) * | 2019-09-13 | 2021-03-18 | 大日本印刷株式会社 | 化粧材及び化粧部材 |
JPWO2021049611A1 (ja) * | 2019-09-13 | 2021-09-27 | 大日本印刷株式会社 | 化粧材及び化粧部材 |
JP7001196B2 (ja) | 2019-09-13 | 2022-01-19 | 大日本印刷株式会社 | 化粧材及び化粧部材 |
Also Published As
Publication number | Publication date |
---|---|
EP3254844A1 (en) | 2017-12-13 |
EP3254844A4 (en) | 2018-07-11 |
EP3254844B1 (en) | 2021-01-20 |
JPWO2016125907A1 (ja) | 2017-10-19 |
US20180022076A1 (en) | 2018-01-25 |
CN107206744A (zh) | 2017-09-26 |
JP6528785B2 (ja) | 2019-06-12 |
CN107206744B (zh) | 2021-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016125907A1 (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
JP6760459B2 (ja) | 化粧シート | |
JP5839066B2 (ja) | 化粧シート、及びこれを用いた化粧部材 | |
WO2018062299A1 (ja) | 化粧シート及びこれを用いた化粧材 | |
JP6819419B2 (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
JP6115247B2 (ja) | 化粧シート及びそれを用いた化粧材 | |
JP6774650B2 (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
JP6962109B2 (ja) | 化粧シート及びこれを用いた化粧材 | |
JP6772859B2 (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
JP2019038195A (ja) | 暗色絵柄化粧シート及びこれを用いた化粧部材 | |
JP2018167495A (ja) | 化粧シート及びこれを用いた化粧材 | |
JP2019064139A (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
WO2019065800A1 (ja) | 化粧シート及びこれを用いた化粧材 | |
JP6977294B2 (ja) | 化粧シート及びこれを用いた化粧材 | |
JP6955687B2 (ja) | 化粧シート及び該化粧シートを備える化粧部材 | |
JP2019038194A (ja) | 化粧シート及びこれを用いた化粧材 | |
JP2019126984A (ja) | 遮熱性化粧シート及びこれを用いた化粧部材 | |
JP7001196B2 (ja) | 化粧材及び化粧部材 | |
JP7415403B2 (ja) | 化粧シート及び化粧材 | |
JP2020163767A (ja) | 化粧材 | |
JP5625702B2 (ja) | 真空成形用化粧シート | |
JP2020124860A (ja) | 化粧シート及びこれを用いた化粧部材 | |
JP2020151902A (ja) | 化粧シート及びこれを用いた化粧材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16746737 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016573443 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15547705 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2016746737 Country of ref document: EP |