WO2012002504A1 - 加飾シートの製造方法、加飾シート及びそれを用いてなる加飾成形品 - Google Patents
加飾シートの製造方法、加飾シート及びそれを用いてなる加飾成形品 Download PDFInfo
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- WO2012002504A1 WO2012002504A1 PCT/JP2011/065084 JP2011065084W WO2012002504A1 WO 2012002504 A1 WO2012002504 A1 WO 2012002504A1 JP 2011065084 W JP2011065084 W JP 2011065084W WO 2012002504 A1 WO2012002504 A1 WO 2012002504A1
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- decorative sheet
- layer
- decorative
- resin
- primer layer
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- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
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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
- 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
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- 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
- B05D3/06—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 exposure to radiation
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1725—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive using an intermediate support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/24—Pressing or stamping ornamental designs on surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0453—Ornamental plaques, e.g. decorative panels, decorative veneers produced by processes involving moulding
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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
- B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
- B29C2045/14237—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure the inserts being deformed or preformed outside the mould or mould cavity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14811—Multilayered articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/002—Coloured
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0087—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24628—Nonplanar uniform thickness material
- Y10T428/24736—Ornamental design or indicia
Definitions
- the present invention relates to a method for producing a decorative sheet used in decorative molded products for various uses such as for buildings, vehicles, and joinery, a decorative sheet, and a decorative molded product using the decorative sheet.
- a decorative molded product decorated by laminating a decorative sheet on the surface of the molded product is used in various applications such as building members and vehicle interior parts.
- a decorative sheet used for such a decorative molded product is usually manufactured by sequentially laminating a design layer and a surface protective layer on a substrate.
- the design layer is formed, unevenness is generated on the surface, and when the surface protective layer is laminated thereon, there is a concern that the smoothness of the surface protective layer surface is impaired.
- Patent Document 1 proposes a skin material for automobile interior including a thermoplastic resin base coat / transparent coat film bonded to the outer surface of a semi-rigid resin backing sheet capable of thermoplastic molding.
- the base coat and transparent coat film are coated on a matte carrier and dried, and then transferred to the backing sheet and laminated.
- the gloss of the transparent coat depends on the smoothness of the matte carrier, there arises a problem that fine adjustment of the smoothness becomes difficult.
- the decorative sheet is not smoothed at all as in the prior art, the smoothness and gloss of the decorative sheet surface and the smoothness and gloss of the decorative molded product after injection molding are significantly different. The design feeling of the decorative sheet and the design feeling of the decorative molded product sometimes differed greatly.
- smoothing treatment is performed by hot press processing or the like using a mirror-treated metal plate after laminating the surface protective layer.
- the unevenness of the design layer remains even if the surface of the surface protective layer is smoothed. Therefore, if the decorative sheet is heated in the simultaneous decoration of insert molding or injection molding, the surface protective layer is softened and the unevenness of the design layer May appear on the surface protective layer, and the smoothness and gloss of the surface of the decorative molded product may be impaired.
- the high smoothness and gloss of the decorative sheet are reduced after injection molding, and the smoothness and gloss of the decorative sheet surface are different from the smoothness and gloss of the decorative molded article surface after injection molding.
- the design feeling of the decorative design and the design feeling of the decorative molded product will be different.
- the present inventor is a high-gloss decorative sheet that retains surface smoothness and gloss even after three-dimensional molding such as insert molding and simultaneous injection molding, and maintains a sense of design.
- Japanese Patent Application No. 2009-088099 Japanese Patent Application No. 2009-088099
- both surfaces of the decorative sheet are smoothed by the process of making the surface of the design layer and primer layer smooth
- the roll of the decorative sheet has a problem that a small dust or dust is involved to form a dent or a scratch, and that the front and back surfaces of the decorative sheet are in close contact with each other, resulting in scratches and wrinkles.
- the present invention is a high gloss decorative sheet, the surface smoothness and gloss are maintained even after three-dimensional molding such as insert molding and injection molding simultaneous decoration, the design feeling is maintained, and To provide a method for producing a decorative sheet that is less likely to cause dents or scratches on the surface due to the inclusion of foreign matter even when wound on a roll, and is less likely to be scratched or wrinkled due to the close contact between the front and back surfaces. Is an issue.
- the present inventor can solve the above problems by smoothing the surface protective layer before laminating and roughening the back surface.
- the 10-point average roughness RzJIS of the back surface and the thickness of the base material, and the arithmetic average roughness Ra and the thickness of the base material each solve the above-mentioned problems by performing a roughening treatment so as to satisfy a specific formula. Found to get.
- the present invention has been completed based on such findings.
- the present invention [1] A step of forming a primer layer on a release film having a smooth surface, a step of forming a design layer on the primer layer, a step of transferring the primer layer and the design layer onto a substrate, A step of peeling the release film on the substrate, a step of laminating the ionizing radiation curable resin composition on the primer layer formed on the substrate, and crosslinking and curing the ionizing radiation curable resin composition.
- a step of forming a surface protective layer wherein the ten-point average roughness RzJIS and the thickness T of the substrate on the back surface of the decorative sheet are represented by the following formula (I):
- a method for producing a decorative sheet comprising a roughening treatment step in which the arithmetic average roughness Ra and the thickness T of the base material satisfy the following formula (II): T ⁇ 0.30 ⁇ RzJIS (I) T ⁇ 0.20 ⁇ Ra ⁇ T ⁇ 0.005 (II) [2]
- a step of forming a primer layer on a release film having a smooth surface a step of forming a design layer on the primer layer, a step of transferring the primer layer and the design layer onto a substrate, A step of peeling the release film on the substrate, a step of laminating the ionizing radiation curable resin composition on the primer layer formed on the substrate, and crosslinking and curing the ionizing radiation curable resin composition.
- a method for producing a decorative sheet comprising: [3] A decorative sheet having a design layer, a primer layer, and a surface protective layer formed by crosslinking and curing an ionizing radiation curable resin composition in this order on a substrate, wherein the surface of the surface protective layer is It is smooth, the ten-point average roughness RzJIS of the back surface of the decorative sheet and the base material thickness T satisfy the following formula (I), and the arithmetic average roughness Ra and the base material thickness T are A decorative sheet characterized by satisfying the following formula (II).
- a decorative sheet having, in this order, a design layer, a primer layer, and a surface protective layer obtained by crosslinking and curing an ionizing radiation curable resin composition on a substrate, the surface of the surface protective layer being A decorative sheet that is smooth and has an arithmetic average roughness Ra of 1.0 to 10.0 ⁇ m on the back surface of the decorative sheet; Is to provide.
- the surface smoothness and gloss are maintained even after three-dimensional molding such as insert molding and simultaneous injection molding, and the design feeling is maintained.
- a decorative sheet was obtained in which dents and scratches on the surface due to the inclusion of foreign matter are less likely to occur, and scratches and wrinkles are less likely to occur due to the close contact between the front and back surfaces. .
- this decorative sheet was actually produced, scratches and dents due to the inclusion of foreign matter were suppressed, and blocking between the decorative sheet surface and the back surface was suppressed.
- the method for producing a decorative sheet according to the present invention includes a step of forming a primer layer on a release film having a smooth surface, a step of forming a design layer on the primer layer, and the primer layer and the design layer as a base material.
- a step of transferring the film, a step of peeling off the release film on the substrate, a step of laminating an ionizing radiation curable resin composition on the primer layer formed on the substrate, and the ionizing radiation curing The step of forming a surface protective layer by crosslinking and curing the functional resin composition, the ten-point average roughness RzJIS of the back surface of the decorative sheet, and the thickness T of the base material satisfy the above formula (I), and arithmetic A roughening treatment step in which the average roughness Ra and the thickness T of the base material satisfy the above formula (II), or the arithmetic average roughness Ra of the back surface of the decorative sheet is 1.0 to 10.0 ⁇ m And a roughening treatment step.
- FIG.1 and FIG.2 is process drawing which shows the outline of the manufacturing method of the decorating sheet of this invention.
- the production method of the present invention is a method including at least the following steps (1) to (7).
- a primer layer 12 is formed by laminating a primer composition on a release film 11 having a smooth surface and then drying as necessary.
- the surface of a peeling film being smooth means that arithmetic mean roughness (Ra) is 0.5 micrometer or less, and it is preferable that it is 0.2 micrometer or less.
- the arithmetic average roughness (Ra) refers to the arithmetic average roughness Ra defined in JIS B 0601: 2001.
- the smoothness of the decorative sheet surface of the present invention is preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less, in terms of arithmetic average roughness Ra.
- the primer layer 12 As a method for laminating the primer layer 12, it can be formed by a coating method, and a transfer method can also be used.
- a coating method gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, silk screen solid coating, wire bar coating , Flow coat, comma coat, pouring coat, brush coating, spray coating and the like can be used.
- the transfer method is a method in which a coating film of a primer layer is once formed on a thin sheet (film base material) and then coated on the surface of the base material.
- a laminating method for adhering to a three-dimensional object a transferring method in which only a support sheet is peeled after adhering a transfer sheet once formed with a coating film and an adhesive layer on a releasable support sheet.
- the design layer 13 is formed by printing or coating the design ink on the primer layer 12 and then drying as necessary.
- the design layer 13 is composed of a pattern layer and / or a solid solid colored layer.
- primer layer 12 and design layer 13 formed on release film 11 are transferred onto substrate 14.
- a transfer method it is preferable to use hot pressing using a mirror plate or embossing using a mirror roll. Specifically, using a known hot press machine or embossing machine, the release film 11 and the base material 14 on which the primer layer 12 and the design layer 13 are laminated are heated and softened, and pressed and bonded together in a stacked state. As a result, a sheet as shown in FIG. 1A is obtained.
- the primer layer 12 is applied with a coating liquid comprising the ionizing radiation curable resin composition or an ionizing radiation curable resin composition. Laminate by coating on a smooth surface.
- the viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the primer layer 12 by a coating method described later.
- the prepared coating liquid is applied to the surface of the primer layer 12 so that the thickness after curing is 1 to 30 ⁇ m, such as gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer.
- the ionizing radiation curable resin has an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.
- an uncured resin layer made of the ionizing radiation curable resin composition is irradiated with ionizing radiation such as an electron beam or ultraviolet rays.
- ionizing radiation such as an electron beam or ultraviolet rays.
- the ionizing radiation curable resin composition is crosslinked and cured to form the surface protective layer 15.
- the decorating sheet 10 in which the surface protective layer 15 was formed can be obtained.
- 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 transmission capability increases as the acceleration voltage increases. Therefore, when using the base material 14 that deteriorates due to the electron beam, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal.
- the irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad).
- the electron beam source is not particularly limited.
- 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, a high frequency type, etc. Can be used.
- 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.
- the smoothness of the surface protective layer 13 is preferably 0.01 ⁇ m or more and less than 1.0 ⁇ m, more preferably 0.01 to 0.5 ⁇ m, and more preferably 0.05 to 0.2 ⁇ m as the arithmetic average roughness Ra. More preferably.
- the arithmetic average roughness Ra means the arithmetic average roughness Ra defined in JIS B 0601: 2001.
- the roughening treatment process on the back surface of the decoration sheet in the present invention is performed to the extent that the above-described formulas (I) and (II) are satisfied, and / or the above-mentioned.
- it will not specifically limit if it is a process which can roughen the back surface of a decorating sheet to such an extent that arithmetic average roughness Ra is satisfy
- filled For example, the design layer 13 of the base material 14, the back surface side of the decorating sheet 10, or specifically, Examples thereof include a method of roughening the surface not in contact with the primer layer 12 by hot pressing using a satin board, embossing using a satin roll, or sand blasting.
- the decorative sheet 10 is softened by heating it to a temperature not lower than the softening temperature of the base material constituting it and below the melting point or melting temperature.
- the back surface of the decorative sheet 10 is roughened by cooling and solidifying as shown in FIG.
- FIG.2 (d) the method of roughening the back surface of the decorating sheet 10 by providing the fine particle containing resin layer 16 is also mentioned.
- the back surface of the decorative sheet 10 is roughened by hot pressing or embossing
- a mirror plate is used on the front side of the base material 14 and a satin board is used on the back side.
- a hot press process is performed using a mirror plate on the release film 11 side and a satin board on the base material 14 side.
- the primer layer 12 and the design layer 13 are simultaneously transferred onto the substrate 14 by embossing using a mirror roll on the release film 11 side and a satin roll on the substrate 14 side.
- the back surface can also be roughened.
- Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting hot press temperature and embossing temperature, or adjusting the surface roughness of a satin board or a satin roll.
- the hot pressing temperature and embossing temperature may be appropriately selected depending on the base material. For example, when vinyl chloride is 30 to 70 ° C., polypropylene resin is 160 to 180 ° C., and acrylic resin is 150 to 260 ° C.
- the uneven shape of the roll can be shaped well.
- the arithmetic average roughness Ra of the satin board or satin roll is preferably 1.0 to 20.0 ⁇ m, more preferably 1.0 to 15.0 ⁇ m, and 1.0 to 10.0 ⁇ m. Further preferred.
- Sandblasting can be performed by spraying inorganic particles such as silica and titania onto the surface to be treated (the back surface of the decorative sheet 10) using compressed air. Since it is easy to maintain arithmetic mean roughness Ra of the back surface of the decorating sheet 10 when performing after the said process (3), it is preferable. Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting the particle diameter and spraying amount of an inorganic particle.
- Examples of the method for providing the fine particle-containing resin layer 16 on the back surface of the decorative sheet 10 include a method of laminating a resin composition containing a binder resin and fine particles by the above-described coating method or transfer method (FIG. 2 ( d)).
- the fine particle-containing resin layer 16 is provided on the back surface side of the decorative sheet 10, it can be performed before or after any of the steps (1) to (6), but after the step (3). This is preferable because the arithmetic average roughness Ra of the back surface of the decorative sheet 10 is easily maintained. Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting the compounding ratio of microparticles and binder resin, and the particle size of microparticles.
- the arithmetic average roughness Ra of the back surface is preferably 1.0 to 10.0 ⁇ m, more preferably 1.0 to 9.0 ⁇ m. 1.2 to 8.0 ⁇ m is particularly preferable.
- the arithmetic average roughness Ra means the arithmetic average roughness Ra specified in JIS B 0601: 2001.
- the 10-point average roughness Rz of the back surface is preferably 1.0 to 100.0 ⁇ m, and more preferably 5.0 to 50 ⁇ m.
- the ten-point average roughness Rz refers to the ten-point average roughness Rz defined in JIS B 0601: 2001.
- the effect of the present invention can be expressed, and when it is 10.0 ⁇ m or less, the roughness on the back surface side of the decorative sheet 10. Does not affect the surface, for example, when insert molding is performed using the decorative sheet 10, sufficient smoothness and surface gloss of the resulting molded product are obtained, and adhesion to the injection resin is also achieved. It will be enough.
- the back surface ten-point average roughness RzJIS and the thickness T of the base material preferably satisfy the following formula (I). It is more preferable to satisfy IA), and it is particularly preferable to satisfy the following formula (IB). T ⁇ 0.30 ⁇ RzJIS (I) T ⁇ 0.20 ⁇ RzJIS (IA) T ⁇ 0.18 ⁇ RzJIS (IB)
- the arithmetic average roughness Ra of the back surface and the thickness T of the base material satisfy the following formula (II). It is more preferable to satisfy ⁇ A), and it is particularly preferable to satisfy the following formula (II-B).
- the roughness on the back side also affects the surface.
- the surface smoothness and surface gloss of the resulting molded product are inferior. Problems such as poor adhesion to the resin occur.
- the arithmetic average roughness Ra is small, if the ten-point average roughness RzJIS exceeds the above range, there may be local irregularities, and friction occurs when the decorative sheets 10 are stacked. There is a risk of scratches and the like.
- the release film 11 used in the production method of the present invention is not particularly limited as long as it is a film that can be peeled off after contact with the primer layer 12. Examples thereof include films and papers made of polyethylene terephthalate, polyethylene, polypropylene, etc., or films and papers coated with a release agent such as silicone (release treatment).
- the release film 11 is preferably peeled and easy to peel off.
- the primer layer 12 formed on the release film 11 has a function of improving the adhesion between the design layer 13 and the surface protective layer 15 on the substrate 14. Furthermore, by smoothing the surface of the primer layer 12, it is possible to smooth the surface of the surface protective layer 15 without affecting the surface protective layer 15 by unevenness of the design layer 13.
- the primer composition constituting the primer layer 12 includes (meth) acrylic resin, urethane resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, Chlorinated polyethylene or the like is used.
- the thickness of the primer layer 12 is preferably about 0.1 to 10 ⁇ m. When the thickness is 0.1 ⁇ m or more, it is possible to sufficiently exert the effect of preventing the surface protective layer from being cracked, broken, whitened or the like. On the other hand, if the thickness of the primer layer is 10 ⁇ m or less, when the primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not fluctuate.
- the design layer 13 composed of the pattern layer and / or the entire solid colored layer shown in FIG. 1 gives decorativeness to the resin molded product.
- the pattern layer is formed by printing various patterns using ink and a printing machine.
- patterns there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth or cloth patterns, tiled patterns, brickwork patterns, etc.
- patterns such as marquetry and patchwork that combine these.
- These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.
- an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used.
- the binder is not particularly limited, and examples thereof include polyurethane resins (acrylic urethane copolymer resins, etc.), vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene.
- Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
- a concealing layer may be provided between the design layer 13 and the base material 14 as necessary.
- the concealing layer is provided for the purpose of preventing the pattern color of the decorative sheet 10 from being affected by a change or variation in the color of the surface of the base material 14.
- it is often formed with an opaque color, and a so-called solid printing layer having a thickness of about 1 to 20 ⁇ m is preferably used.
- the binder, colorant, and the like used are the same as those used for the design layer 13.
- the base material 14 in the production method of the present invention is selected in consideration of the suitability for vacuum forming and the suitability for simultaneous injection molding, and typically a resin sheet made of a thermoplastic resin is used.
- the thermoplastic resin generally includes acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter referred to as “ABS resins”), vinyl chloride resins, polyester resins, and the like. Is used.
- the base material 14 can be used as a single layer sheet
- the thickness of the base material 14 is selected according to the use, but is usually about 0.03 to 1.0 mm, and is generally about 0.03 to 0.5 mm in consideration of cost and the like.
- the surface can be subjected to a surface treatment such as an oxidation method if desired.
- a surface treatment such as an oxidation method
- the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method and the like. 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.
- a polymerizable monomer and a polymerizable oligomer and / or prepolymer as an ionizing radiation curable resin used in the ionizing radiation curable resin composition.
- oligomer / prepolymer a polymerizable monomer and a polymerizable oligomer and / or prepolymer
- an ionizing radiation curable resin used in the ionizing radiation curable resin composition is described below.
- the polymerizable monomer typically, 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”, and other similar ones have the same meaning.
- 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.
- Specific examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like.
- These polyfunctional (meth) acrylates may be used alone or in combination of two or more.
- a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the purpose of the present invention is not impaired, for the purpose of reducing the viscosity thereof.
- monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.
- an oligomer / prepolymer having a radical polymerizable unsaturated group in the molecule for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, Examples include polyether (meth) acrylates and polycarbonate (meth) acrylates.
- polymerizable oligomer / prepolymer other polybutadiene (meth) acrylate oligomer / prepolymer having a (meth) acrylate group in the side chain of the polybutadiene oligomer / prepolymer and a polysiloxane bond in the main chain Silicone (meth) acrylate oligomer / prepolymer with amino acid, aminoplast resin (meth) acrylate oligomer / prepolymer modified with aminoplast resin with many reactive groups in a small molecule, or novolak epoxy resin, bisphenol
- oligomers / prepolymers having cationically polymerizable functional groups in the molecule such as epoxy resin, aliphatic vinyl ether and aromatic vinyl ether.
- the ionizing radiation curable resin composition in the present invention when at least polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and a polyfunctional (meth) acrylate are used, excellent chemical resistance and Since scratch resistance and good three-dimensional formability are satisfied at the same time, it is preferable in that a decorative sheet that does not crack in the surface protective layer and can be easily three-dimensionally formed can be obtained.
- the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is preferably 98: 2 to 70:30, and more preferably 95: 5 to 80:20.
- the polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and has (meth) acrylate in the terminal or side chain.
- This (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing.
- the polycarbonate (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and more than 2,000. Is more preferable.
- the upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably more than 2,000 and not more than 50,000, and particularly preferably 5,000 to 20,000.
- the mass ratio of acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is preferred. Is from 50:50 to 95: 5, more preferably from 95: 5 to 80:20.
- the acrylic silicone (meth) acrylate used in the present invention is not particularly limited, and a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group.
- the acrylic silicone (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 1,000 or more, and more preferably 2,000 or more.
- the upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of establishing three-dimensional formability, chemical resistance, and scratch resistance, it is particularly preferably 2,000 to 100,000.
- the polyfunctional (meth) acrylate used for this invention should just be bifunctional or more (meth) acrylate, and there is no restriction
- bifunctional means having two ethylenically unsaturated bonds ⁇ (meth) acryloyl group ⁇ in the molecule.
- the polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.
- the polyfunctional (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and more than 2,000. More preferably.
- the upper limit of the weight average molecular weight of the polyfunctional (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably more than 2,000 and not more than 50,000, and particularly preferably 5,000 to 20,000.
- polyfunctional (meth) acrylate oligomer examples include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers.
- the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
- polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meta-methacrylate) having polysiloxane bonds in the main chain.
- the ionizing radiation curable resin When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin.
- the initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.
- the photosensitizer for example, p-dimethylbenzoic acid ester, tertiary amines, thiol sensitizers and the like can be used.
- an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.
- thermoplastic resin when it is desired to impart flexibility to the decorative sheet 10 obtained by the production method of the present invention, a thermoplastic resin can be added. On the other hand, when resistance to a solvent is required, it is preferable not to contain a thermoplastic resin.
- Thermoplastic resins include (meth) acrylic resins such as (meth) acrylic acid esters, polyvinyl acetals (butyral resin) such as polyvinyl butyral, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resins, urethane resins, Polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene and ⁇ -methylstyrene, acetal resins such as polyamide, polycarbonate and polyoxymethylene, fluororesins such as ethylene-tetrafluoroethylene copolymer, polyimide, polylactic acid, A polyvinyl acetal resin, liquid crystalline polyester resin, etc. are mentioned, These may be used individually by 1 type or in combination of 2 or more types. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.
- thermoplastic resins those having a (meth) acrylic resin as a main component are preferred in the present invention, and in particular, those obtained by polymerizing a monomer containing at least a (meth) acrylic acid ester as a monomer component. preferable. More specifically, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and other monomers Is preferred.
- the thermoplastic resin has a weight average molecular weight in the range of 90,000 to 120,000.
- the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a commonly used solvent can be appropriately selected, and examples thereof include tetrahydrofuran (THF) and N-methyl-2-pyrrolidinone (NMP).
- the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the thermoplastic resin is preferably in the range of 1.1 to 3.0. If the polydispersity is within this range, it is possible to obtain a high level of moldability, surface abrasion resistance, and scratch resistance after crosslinking and curing to form a surface protective layer. From the above points, the polydispersity of the (meth) acrylic resin is preferably in the range of 1.5 to 2.5.
- Examples of the additive used in the ionizing radiation curable resin composition include a weather resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, Examples include a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and an abrasion resistance improver.
- the surface protective layer 15 thus formed has various functions by adding various additives, for example, a so-called hard coat function, antifogging function, and antifouling function having high hardness and scratch resistance. Further, an antiglare function, an antireflection function, an ultraviolet shielding function, an infrared shielding function, and the like can be provided.
- the thickness of the surface protective layer 15 after curing is preferably 1 to 30 ⁇ m.
- the thickness of the surface protective layer 15 after curing is 1 ⁇ m or more, excellent design properties such as transparency and glossiness can be obtained, and further sufficient as a protective layer such as stain resistance, scratch resistance and weather resistance. Physical properties can be obtained.
- the thickness is 30 ⁇ m or less, there is no cracking or whitening of the protective layer at the time of molding, and the desired shape can be followed, and good design properties can be obtained even after three-dimensional molding.
- the thickness of the surface protective layer 15 after curing is preferably in the range of 2 to 20 ⁇ m, and more preferably in the range of 3 to 10 ⁇ m.
- binder resin used for the fine particle-containing resin layer 16 examples include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyurethane resins, acrylic resins, acrylic urethane resins, polycarbonate resins, and vinyl chloride / vinyl acetate copolymers.
- polyolefin resins such as polyethylene and polypropylene
- polyester resins polyurethane resins
- acrylic resins acrylic urethane resins
- polycarbonate resins polycarbonate resins
- vinyl chloride / vinyl acetate copolymers examples include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyurethane resins, acrylic resins, acrylic urethane resins, polycarbonate resins, and vinyl chloride / vinyl acetate copolymers.
- resins such as polyvinyl butyral resin and nitrocellulose resin (nitrified cotton)
- compounds such as alkyl titanate and ethyleneimine can also be used, and
- Examples of the fine particles used in the fine particle-containing resin layer 16 include silica, talc, calcium carbonate, precipitated barium sulfate, alumina, acidic clay, clay, magnesium carbonate, carbon black, tin oxide, titanium white, and urea powder resin.
- Inorganic fine particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, and organic polymers such as polyamide (nylon) are used.
- silica, acrylic beads, polyethylene wax and the like that are easy to handle and inexpensive are suitable.
- the average particle size of the fine particles is preferably 0.5 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and the addition amount is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. A range of 0.5 to 5 parts by mass is more preferable.
- the shape of the particles is a polyhedron, a sphere, a scale shape, or the like.
- the decorative sheet 10 obtained by the production method of the present invention can be used for various injection molding methods such as an insert molding method, an injection molding simultaneous decorating method, a blow molding method, and a gas injection molding method. It is suitably used for the injection molding simultaneous decoration method.
- the insert molding method in the vacuum forming step, the decorative sheet obtained by the manufacturing method of the present invention is vacuum-formed into a molded product surface shape in advance (off-line pre-molding) with a vacuum forming die, and then an extra portion is removed as necessary. Trimming to obtain a molded sheet.
- 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. To produce decorative resin molded products.
- thermoplastic resins such as polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins and vinyl chloride resins are typical.
- thermosetting resins such as urethane resins and epoxy resins can be used depending on applications.
- the decorative sheet of the present invention is placed in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) with this female mold ),
- the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated with the outer surface of the resin molding simultaneously with the injection molding, Manufactures decorative resin molded products.
- the decorative sheet receives heat pressure from the injection resin, and therefore, if the decorative sheet is close to a flat plate and the aperture of the decorative sheet is small, the decorative sheet may or may not be preheated.
- the same resin as described in the insert molding method can be used.
- the decorative resin molded product produced as described above is excellent in surface smoothness and gloss, and becomes a molded product with high design. Furthermore, in the production method of the present invention, the surface protective layer is completely cured at the production stage of the decorative sheet, and therefore a step of crosslinking and curing the surface protective layer after producing the decorative resin molded body is unnecessary.
- the decorative sheet was wound up in a roll shape in which the front surface side of one layer and the back surface side of the other layer were overlapped, and allowed to stand at 20 ° C. for 168 hours. Twenty decorative sheets were cut out from the roll, and the number of sheets with scratches and dents in the surface protective layer was confirmed. These scratches and dents are considered to be caused by foreign matters such as fine dust caught in the roll.
- ⁇ Decorative sheet with scratches and dents 0 sheets
- the decorative sheet was immersed in an oil bath at a predetermined temperature for 1 minute, and the embossing after dipping and the gloss were visually observed. Evaluation was performed in increments of 10 ° C., and the highest temperature was shown without any defogging and no change in gloss.
- Example 1 As the release film, a biaxially stretched polyethylene terephthalate film (thickness: 25 ⁇ m, arithmetic average roughness (Ra): 0.01 ⁇ m) having a silicone release layer on the surface layer was used. A polymer resin was applied to form a transparent primer layer having a thickness of 2 ⁇ m. Next, a woodgrain pattern design layer was formed on the primer layer by gravure printing using acrylic urethane copolymer resin ink.
- an electron beam curable resin composition made of bifunctional urethane acrylate (weight average molecular weight; 2,000) is cured to have a thickness of 6 ⁇ m. It was applied by gravure reverse.
- 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 electron beam curable resin composition to obtain a decorative sheet.
- the arithmetic average roughness Ra of the obtained decorative sheet was 0.1 ⁇ m on the front surface side and 2.0 ⁇ m on the back surface side.
- the obtained decorative sheet was heated with an infrared heater until the temperature of the sheet reached 170 ° C., softened, and then vacuum-formed.
- the decorative sheet was released from the mold and the back surface was confirmed, the emboss disappeared and became smooth.
- Unnecessary portions of the vacuum-formed decorative sheet were trimmed by pressing the die-cut mold with hydraulic pressure. Using this trimmed decorative sheet, it is inserted into an injection mold, then clamped, ABS resin is injected into the mold, and the decorative sheet is laminated and integrated on the surface of the molded product. A resin molded product was obtained.
- Example 2 Example 1 with the exception of using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 8.5 ⁇ m and a ten-point average roughness Rz JIS of 39 ⁇ m on the side having no design layer (back side) in the hot pressing step. Similarly, a decorative sheet and a decorative resin molded product were obtained.
- Example 3 As a base material, a sheet made of ABS resin having a thickness of 200 ⁇ m is used, and in the hot press process, the side having no design layer (the back side) has an arithmetic average roughness Ra of 6.9 ⁇ m and a ten-point average roughness RzJIS of 28 ⁇ m. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that a stainless steel metal plate with a handle was used.
- Example 4 A sheet of ABS resin having a thickness of 400 ⁇ m is used as a base material, and in the hot press process, the side having no design layer (the back side) has an arithmetic average roughness Ra4.0 and a ten-point average roughness RzJIS 23 ⁇ m.
- a decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that a stainless steel metal plate with a handle was used.
- Example 5 A sheet made of ABS resin having a thickness of 400 ⁇ m was used as a base material, and bifunctional polycarbonate acrylate (weight average molecular weight; 10,000) and hexafunctional urethane acrylate (weight average molecular weight; 6,000) were 94: A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that an electron beam curable resin mixed at a ratio of 6 was used.
- Example 6 A sheet made of an ABS resin having a thickness of 400 ⁇ m was used as a base material, and a bifunctional acrylic silicone acrylate (weight average molecular weight; 20,000) and a hexafunctional urethane acrylate (weight average molecular weight; 5,000) were 70. : A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that the electron beam curable resin mixed at a ratio of 30 was used.
- Comparative Example 1 In the hot press processing of Example 1, except that the hot press processing was performed at 140 ° C. using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 19 ⁇ m and a ten-point average roughness RzJIS 130 ⁇ m. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1.
- Comparative Example 2 As a base material, a sheet made of ABS resin having a thickness of 200 ⁇ m was used, and in the hot press processing of Example 1, instead of a stainless steel metal plate with a satin pattern on the back side, arithmetic average roughness Ra1. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that hot pressing was performed using a stainless steel specular plate with 8 ⁇ m and 10-point average roughness RzJIS 6 ⁇ m.
- Comparative Example 3 In Comparative Example 2, a sheet made of ABS resin having a thickness of 400 ⁇ m was used as a base material, and a composition comprising 100 parts by mass of acrylic resin and 10 parts by mass of silica (average particle size: 3.0 ⁇ m) on the surface side. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Comparative Example 1 except that gravure printing was performed at a coating amount of 1 g / m 2 to provide a fine particle-containing resin layer.
- Comparative Example 4 As a base material, a sheet made of ABS resin having a thickness of 100 ⁇ m was used, and in the hot press processing of Example 10, an arithmetic average roughness Ra28. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 5 except that hot pressing was performed using a stainless steel specular plate having a 2 ⁇ m, 10-point average roughness RzJIS of 97 ⁇ m.
- Example 7 As the release film, a biaxially stretched polyethylene terephthalate film (thickness: 25 ⁇ m, arithmetic average roughness (Ra): 0.01 ⁇ m) having a silicone release layer on the surface layer was used. A polymer resin was applied to form a transparent primer layer having a thickness of 2 ⁇ m. Next, a woodgrain pattern design layer was formed on the primer layer by gravure printing using acrylic urethane copolymer resin ink.
- the design layer side of the sheet on which the primer layer and the design layer are formed on the release film is brought into contact with the base material (sheet made of ABS resin, thickness: 400 ⁇ m), and then on the primer layer side (surface side)
- the base material sheet made of ABS resin, thickness: 400 ⁇ m
- the primer layer side surface side
- 150 Hot pressing was performed for 10 minutes under a pressure of 5 kgf / cm 2 at 5 ° C. After the hot pressing, the release film was peeled off, and the primer layer and the design layer were transferred to the substrate.
- an electron beam curable resin composition made of bifunctional urethane acrylate (weight average molecular weight; 2,000) is cured to have a thickness of 6 ⁇ m. It was applied by gravure reverse.
- 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 electron beam curable resin composition to obtain a decorative sheet.
- the arithmetic average roughness Ra of the obtained decorative sheet was 0.1 ⁇ m on the front surface side and 3.0 ⁇ m on the back surface side.
- the emboss fastness was 130 ° C.
- the obtained decorative sheet was heated with an infrared heater until the temperature of the sheet reached 170 ° C., softened, and then vacuum-formed.
- the decorative sheet was released from the mold and the back surface was confirmed, the embossing disappeared and became smooth. Unnecessary portions of the vacuum-formed decorative sheet were trimmed by pressing the die-cut mold with hydraulic pressure. Using this trimmed decorative sheet, it is inserted into an injection mold, then clamped, ABS resin is injected into the mold, and the decorative sheet is laminated and integrated on the surface of the molded product. A resin molded product was obtained.
- Example 8 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 7 except that the temperature of the hot press was changed to 140 ° C.
- Example 9 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 7 except that the temperature of the hot press was changed to 180 ° C.
- Example 10 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 7 except that the temperature of the hot press was changed to 230 ° C.
- Example 11 In the hot press processing of Example 7, instead of a stainless steel metal plate with a satin pattern on the back side, a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 ⁇ m was used, and the surface electron beam curable resin was used. After the composition is cured, a composition composed of 100 parts by mass of acrylic resin and 3 parts by mass of silica (average particle size: 1.5 ⁇ m) is applied to the back side by gravure printing at a coating amount of 1 g / m 2 to make a minute amount. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 7 except that the particle-containing resin layer was provided.
- Example 12 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that silica having an average particle diameter of 3.0 ⁇ m was used instead of silica having an average particle diameter of 1.5 ⁇ m.
- Example 13 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that silica having an average particle diameter of 5.0 ⁇ m was used instead of silica having an average particle diameter of 1.5 ⁇ m.
- Example 14 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that acrylic beads having an average particle diameter of 5.0 ⁇ m were used instead of silica having an average particle diameter of 1.5 ⁇ m.
- Example 15 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that polyethylene wax having an average particle diameter of 5.0 ⁇ m was used instead of silica having an average particle diameter of 1.5 ⁇ m.
- Example 16 Except for using an electron beam curable resin in which a bifunctional polycarbonate acrylate (weight average molecular weight; 10,000) and a hexafunctional urethane acrylate (weight average molecular weight; 6,000) were mixed at a ratio of 94: 6. In the same manner as in Example 7, a decorative sheet and a decorative resin molded product were obtained.
- a bifunctional polycarbonate acrylate weight average molecular weight; 10,000
- a hexafunctional urethane acrylate weight average molecular weight; 6,000
- Example 17 Implemented except that an electron beam curable resin in which a bifunctional acrylic silicone acrylate (weight average molecular weight; 20,000) and a hexafunctional urethane acrylate (weight average molecular weight; 5,000) were mixed at a ratio of 70:30 was used. In the same manner as in Example 7, a decorative sheet and a decorative resin molded product were obtained.
- a bifunctional acrylic silicone acrylate weight average molecular weight; 20,000
- a hexafunctional urethane acrylate weight average molecular weight; 5,000
- Example 7 In the hot press processing of Example 7, in place of the stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 ⁇ m instead of the stainless steel metal plate with a satin pattern on the back side, A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 7.
- Example 7 Comparative Example 6 In the hot press processing of Example 7, with the exception of performing the hot press processing at 140 ° C. using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 19 ⁇ m on the back side, Example 7 and Similarly, a decorative sheet and a decorative resin molded product were obtained.
- Comparative Example 7 In Comparative Example 5, a composition comprising 100 parts by mass of an acrylic resin and 10 parts by mass of silica (average particle size: 3.0 ⁇ m) on the surface side is subjected to gravure printing at a coating amount of 1 g / m 2 and a fine particle-containing resin. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Comparative Example 5 except that a layer was provided.
- Comparative Example 8 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that silica having an average particle diameter of 0.1 ⁇ m was used instead of silica having an average particle diameter of 1.5 ⁇ m.
- Comparative Example 9 A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 11 except that silica having an average particle size of 9.0 ⁇ m was used instead of silica having an average particle size of 1.5 ⁇ m.
- Comparative Example 10 In Comparative Example 5, a 10% isopropyl alcohol solution of a cationic surfactant (dimethyltrimethylammonium salt) as an antistatic agent was applied to the back side by gravure coating so that the coating thickness when dried was 0.5 g / m 3. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Comparative Example 5 except that.
- a cationic surfactant dimethyltrimethylammonium salt
- the arithmetic average roughness Ra and the ten-point average roughness Rz were measured for the front and back surfaces of the decorative sheets of Examples 7 to 17 and Comparative Examples 5 to 10, and the embossing fastness was measured for the back surface.
- the results are shown in Tables 3-5.
- blocking resistance of the decorative sheets of Examples 7 to 17 and Comparative Examples 5 to 10 obtained, scratches and dents due to foreign matters, and surface gloss, smoothness, haze and injection resin of the decorative resin molded product The adhesion was evaluated. The results are shown in Tables 3-5.
- the decorative sheets of Examples 1 to 6 were free from scratches or dents due to blocking or foreign matter inclusion even when wound on a roll.
- the smoothness of the surface of a decorative resin molded product was impaired.
- Comparative Example 2 in which Ra ⁇ T ⁇ 0.005, scratches or dents due to blocking or foreign matter entrainment occurred.
- the comparative example 3 which provided the microparticle containing resin layer in the decorating sheet surface side, the smoothness of the decorating resin molded product surface was impaired.
- Comparative Example 4 since Ra and RzJIS were too large, the surface gloss of the decorated resin molded product was remarkably lowered, and haze was generated.
- the decorative sheet obtained by the production method of the present invention is, for example, interior or exterior materials for vehicles such as automobiles, construction members such as baseboards and rims, joinery such as window frames and door frames, walls, floors, and ceilings. It is suitably used for decorative resin molded products such as interior materials for buildings, etc., housings of household electrical appliances such as television receivers and air conditioners, and containers.
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Abstract
Description
しかし、かかる製造方法においては、意匠層を形成した際に表面に凹凸が生じ、その上に表面保護層を積層した際に表面保護層表面の平滑性が損なわれることが懸念される。
また、従来のように加飾シートの平滑化処理を全く行わないと、加飾シート表面の平滑性及び艶と射出成形後の加飾成形品の平滑性及び艶とが著しく異なることにより、加飾シートの意匠感と加飾成形品の意匠感とが大きく相違することがあった。
[1]表面が平滑な剥離フィルム上にプライマー層を形成する工程と、該プライマー層上に意匠層を形成する工程と、該プライマー層及び該意匠層を基材上に転写する工程と、該基材上の該剥離フィルムを剥がす工程と、該基材上に形成された該プライマー層上に電離放射線硬化性樹脂組成物を積層する工程と、該電離放射線硬化性樹脂組成物を架橋硬化して表面保護層を形成する工程とを含む加飾シートの製造方法であって、さらに、該加飾シートの裏面の十点平均粗さRzJISと基材の厚さTとが下記式(I)を満たし、かつ、算術平均粗さRaと基材の厚さTとが下記式(II)を満たすようにする粗面化処理工程を含むことを特徴とする加飾シートの製造方法、
T×0.30≧RzJIS (I)
T×0.20≧Ra≧T×0.005 (II)
[2]表面が平滑な剥離フィルム上にプライマー層を形成する工程と、該プライマー層上に意匠層を形成する工程と、該プライマー層及び該意匠層を基材上に転写する工程と、該基材上の該剥離フィルムを剥がす工程と、該基材上に形成された該プライマー層上に電離放射線硬化性樹脂組成物を積層する工程と、該電離放射線硬化性樹脂組成物を架橋硬化して表面保護層を形成する工程とを含む加飾シートの製造方法であって、さらに該加飾シートの裏面の算術平均粗さRaを1.0~10.0μmとする粗面化処理工程を含むことを特徴とする加飾シートの製造方法、
[3]基材上に意匠層と、プライマー層と、電離放射線硬化性樹脂組成物を架橋硬化してなる表面保護層とをこの順に有する加飾シートであって、該表面保護層の表面が平滑であり、該加飾シートの裏面の十点平均粗さRzJISと基材の厚さTとが下記式(I)を満たし、かつ、算術平均粗さRaと基材の厚さTとが下記式(II)を満たすことを特徴とする加飾シート。
T×0.30≧RzJIS (I)
T×0.20≧Ra≧T×0.005 (II)
[4]基材上に意匠層と、プライマー層と、電離放射線硬化性樹脂組成物を架橋硬化してなる表面保護層とをこの順に有する加飾シートであって、該表面保護層の表面が平滑であり、該加飾シートの裏面の算術平均粗さRaが、1.0~10.0μmであることを特徴とする加飾シート、
を提供するものである。
11.剥離フィルム
12.プライマー層
13.意匠層
14.基材
15.表面保護層
16.微小粒子含有樹脂層
図1及び図2は本発明の加飾シートの製造方法の概略を示す工程図である。本発明の製造方法は、以下の(1)~(7)の工程を少なくとも含む方法である。
表面が平滑な剥離フィルム11上にプライマー組成物を積層した後必要に応じ乾燥することによりプライマー層12を形成する。
なお、本発明において、剥離フィルムの表面が平滑であるとは、算術平均粗さ(Ra)が0.5μm以下であることをいい、0.2μm以下であることが好ましい。ここで、算術平均粗さ(Ra)とは、JIS B 0601:2001に規定された算術平均粗さRaをいう。
また、本発明の加飾シート表面の平滑性は、算術平均粗さRaとして0.5μm以下であることが好ましく、0.2μm以下であることがより好ましい。
次に、プライマー層12上に意匠用インキを印刷又は塗工した後必要に応じ乾燥することにより意匠層13を形成する。意匠層13は、絵柄層及び/又は全面ベタ着色層からなる。
次いで、剥離フィルム11上に形成されたプライマー層12及び意匠層13を基材14に転写する。転写方法としては鏡面板を用いた熱プレス加工や鏡面ロールを用いたエンボス加工を用いることが好ましい。具体的には、公知の熱プレス機、エンボス加工機を用い、プライマー層12及び意匠層13を積層した剥離フィルム11と基材14を加熱軟化させ、重ねた状態で加圧し貼り合わせる。これにより、図1の(a)に示すようなシートが得られる。
転写後の基材14上の剥離フィルム11を剥がすことにより、図1の(b)に示すように基材14上に意匠層13とプライマー層12とがその順に積層されたシートが得られる。このとき、プライマー層12の表面は、前工程の剥離フィルム面を賦形し平滑面となっている。
次いで、電離放射線硬化性樹脂組成物からなる塗工液又は電離放射線硬化性樹脂組成物を含有する塗工液をプライマー層12の平滑面上に塗工することにより積層する。塗工液の粘度は、後述の塗工方式により、プライマー層12の表面に未硬化樹脂層を形成し得る粘度であれば良く、特に制限はない。
本発明の製造方法においては、調製された塗工液を、プライマー層12の表面に、硬化後の厚さが1~30μmになるように、グラビアコート、バーコート、ロールコート、リバースロールコート、コンマコート等の公知の方式、好ましくはグラビアコートにより塗工し、未硬化樹脂層を形成させる。
ここで、電離放射線硬化性樹脂とは、電磁波又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、紫外線又は電子線等を照射することにより、架橋、硬化する樹脂を指す。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。
次に、電離放射線硬化性樹脂組成物からなる未硬化樹脂層に電子線、紫外線等の電離放射線を照射することにより、電離放射線硬化性樹脂組成物を架橋硬化して表面保護層15を形成する。これにより、図1の(c)に示すように表面保護層15が形成された加飾シート10を得ることができる。
ここで、電離放射線として電子線を用いる場合、その加速電圧については、用いる樹脂や層の厚みに応じて適宜選定し得るが、通常加速電圧70~300kV程度で未硬化樹脂層を硬化させることが好ましい。
なお、電子線の照射においては、加速電圧が高いほど透過能力が増加するため、電子線により劣化する基材14を使用する場合には、電子線の透過深さと樹脂層の厚みが実質的に等しくなるように、加速電圧を選定することにより、基材14への余分な電子線の照射を抑制することができ、過剰電子線による基材の劣化を最小限にとどめることができる。
また、照射線量は、樹脂層の架橋密度が飽和する量が好ましく、通常5~300kGy(0.5~30Mrad)、好ましくは10~100kGy(1~10Mrad)の範囲で選定される。
さらに、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。
本発明における加飾シート裏面の粗面化処理工程は、上述の式(I)及び式(II)を満たす程度に、及び/又は上述の算術平均粗さRaを満たす程度に加飾シートの裏面を粗面化し得る工程であれば特に限定されないが、例えば、加飾シート10の裏面側、具体的には基材14の意匠層13やプライマー層12と接しない面を、梨地板を用いた熱プレスや梨地ロールを用いたエンボス加工やサンドブラスト処理により粗面化する方法が挙げられる。熱プレス加工、エンボス加工としては、公知の方法を用いることができ、加飾シート10を、構成する基材の軟化温度以上、融点或いは溶融温度未満の温度に加熱して軟化させ、該加飾シート10の裏面側を加圧、賦形した後、冷却、固化することにより、図1に示すように加飾シート10の裏面は粗面化される。
また、本発明における粗面化処理としては、図2(d)に示すように、加飾シート10の裏面を、微小粒子含有樹脂層16を設けることにより、粗面化する方法も挙げられる。
被処理面のRzJIS及びRaの調整は、熱プレス温度やエンボス温度を調整したり、梨地板や梨地ロールの表面粗さを調整することで行うことができる。熱プレス温度やエンボス温度は、基材により適宜選定すればよく、例えば、塩化ビニルは30~70℃、ポリプロピレン樹脂は160~180℃、アクリル系樹脂は150~260℃とすると、梨地板や梨地ロールの凹凸形状を良好に賦形することができる。また、梨地板や梨地ロールの算術平均粗さRaは、1.0~20.0μmであると好ましく、1.0~15.0μmであるとより好ましく、1.0~10.0μmであるとさらに好ましい。
加飾シート10の裏面側に、微小粒子含有樹脂層16を設ける場合には、上記(1)~(6)のいずれかの工程の前後で行うことができるが、上記工程(3)以降に行うと、加飾シート10の裏面の算術平均粗さRaを高く維持しやすいため好ましい。被処理面のRzJIS及びRaの調整は、微小粒子とバインダー樹脂との配合比や、微小粒子の粒径を調整することで行うことができる。
また、上記粗面化処理は、裏面の十点平均粗さRzを1.0~100.0μmとすることが好ましく、5.0~50μmとすることが好ましい。ここで、十点平均粗さRzとは、JIS B 0601:2001に規定された十点平均粗さRzをいう。
加飾シート10の裏面の算術平均粗さRaが1.0μm以上であると、本発明の効果を発現させることができ、10.0μm以下であると、加飾シート10の裏面側の粗さが表面に影響することがないため、例えば加飾シート10を用いてインサート成形を行った場合に、得られる成形品の表面の平滑性や表面艶が十分得られ、射出樹脂との密着性も十分なものとなる。
T×0.30≧RzJIS (I)
T×0.20≧RzJIS (I-A)
T×0.18≧RzJIS (I-B)
T×0.20≧Ra≧T×0.005 (II)
T×0.18≧Ra≧T×0.02 (II-A)
T×0.15≧Ra≧T×0.03 (II-B)
加飾シート10の裏面の算術平均粗さRaが上記範囲未満であると、異物を巻き込むことによる表面の凹みや傷が生じたり、表面と裏面が互いに密着することによる擦り傷やシワが生じるおそれがある。一方、加飾シート10の裏面の算術平均粗さRaが上記範囲を超えると、基材の厚さに対して加飾シート10の裏面の算術平均粗さRaが大きすぎるため、加飾シート10が軟化した際に裏面側の粗さが表面にも影響し、例えば加飾シート10を用いてインサート成形を行った場合に、得られる成形品の表面の平滑性や表面艶が劣ったり、射出樹脂との密着性が劣るなどの問題が発生する。
また、算術平均粗さRaが小さくとも、十点平均粗さRzJISが上記範囲を超える場合、局所的に凹凸が生じている可能性があり、加飾シート10同士を重ねた際に摩擦が生じ、擦り傷等が発生する恐れが生じる。
プライマー層12を構成するプライマー組成物は、(メタ)アクリル樹脂、ウレタン樹脂、(メタ)アクリル・ウレタン共重合体樹脂、塩化ビニル-酢酸ビニル共重合体、ポリエステル樹脂、ブチラール樹脂、塩素化ポリプロピレン、塩素化ポリエチレン等が用いられる。
0.1μm以上であると、表面保護層の割れ、破断、白化等を防ぐ効果を十分に発揮させることも可能となる。一方、プライマー層の厚さが10μm以下であれば、プライマー層を塗工した際、塗膜の乾燥、硬化が安定であるので成形性が変動することが無く好ましい。
着色剤としては、カーボンブラック(墨)、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)顔料等が用いられる。
基材14の厚さは、用途に応じて選定されるが、通常、0.03~1.0mm程度であり、コスト等を考慮すると0.03~0.5mm程度が一般的である。
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。
重合性モノマーとしては、代表的には、分子中にラジカル重合性不飽和基を持つ(メタ)アクリレート系モノマーが好適であり、中でも多官能性(メタ)アクリレートが好ましい。なお、ここで「(メタ)アクリレート」とは「アクリレート又はメタクリレート」を意味し、他の類似するものも同様の意である。多官能性(メタ)アクリレートとしては、分子内にエチレン性不飽和結合を2個以上有する(メタ)アクリレートであれば良く、特に制限はない。具体的にはエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート等が挙げられる。これらの多官能性(メタ)アクリレートは1種を単独で用いても良いし、2種以上を組み合わせて用いても良い。
本発明に用いられるポリカーボネート(メタ)アクリレートは、特に限定されず、ポリマー主鎖にカーボネート結合を有し、且つ末端あるいは側鎖に(メタ)アクリレートを有するものであれば良い。この(メタ)アクリレートは、架橋、硬化する観点から、2官能以上有することが好ましい。
ポリカーボネート(メタ)アクリレートは、GPC分析によって測定され、かつ標準ポリスチレンで換算された重量平均分子量が、500以上であることが好ましく、1,000以上であることがより好ましく、2,000を超えることがさらに好ましい。ポリカーボネート(メタ)アクリレートの重量平均分子量の上限は特に制限されないが、粘度が高くなり過ぎないように制御する観点から100,000以下が好ましく、50,000以下がより好ましい。耐傷付き性と三次元成形性とを両立させる観点から、さらに好ましくは、2,000を超え50,000以下であり、特に好ましくは、5,000~20,000である。
本発明に用いられるアクリルシリコーン(メタ)アクリレートは、特に限定されず、1分子中に、アクリル樹脂の構造の一部がシロキサン結合(Si-O)に置換しており、かつ官能基としてアクリル樹脂の側鎖及び/又は主鎖末端に(メタ)アクリロイルオキシ基(アクリロイルオキシ基又はメタアクリロイルオキシ基)を2個以上有しているものであれば良い。
アクリルシリコーン(メタ)アクリレートは、GPC分析によって測定され、かつ標準ポリスチレンで換算された重量平均分子量が、1,000以上であることが好ましく、2,000以上であることがより好ましい。アクリルシリコーン(メタ)アクリレートの重量平均分子量の上限は特に制限されないが、粘度が高くなり過ぎないように制御する観点から150,000以下が好ましく、100,000以下がより好ましい。三次元成形性と耐薬品性と耐傷付き性とを鼎立させる観点から、2,000~100,000であることが特に好ましい。
また、多官能(メタ)アクリレートは、オリゴマー及びモノマーのいずれでも良いが、三次元成形性向上の観点から多官能(メタ)アクリレートオリゴマーが好ましい。
多官能(メタ)アクリレートは、GPC分析によって測定され、かつ標準ポリスチレンで換算された重量平均分子量が、500以上であることが好ましく、1,000以上であることがより好ましく、2,000を超えることがさらに好ましい。多官能(メタ)アクリレートの重量平均分子量の上限は特に制限されないが、粘度が高くなり過ぎないように制御する観点から100,000以下が好ましく、50,000以下がより好ましい。耐傷付き性と三次元成形性とを両立させる観点から、さらに好ましくは、2,000を超え50,000以下であり、特に好ましくは、5,000~20,000である。
また、光増感剤として、例えばp-ジメチル安息香酸エステル、第三級アミン類、チオール系増感剤等を用いることができる。
熱可塑性樹脂としては、(メタ)アクリル酸エステル等の(メタ)アクリル系樹脂、ポリビニルブチラール等のポリビニルアセタール(ブチラール樹脂)、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等のポリエステル樹脂、塩化ビニル樹脂、ウレタン樹脂、ポリエチレン,ポリプロピレン等のポリオレフィン、ポリスチレン,α-メチルスチレン等のスチレン系樹脂、ポリアミド、ポリカーボネート、ポリオキシメチレン等のアセタール樹脂、エチレン-4フッ化エチレン共重合体等のフッ素樹脂、ポリイミド、ポリ乳酸、ポリビニルアセタール樹脂、液晶性ポリエステル樹脂等が挙げられ、これらは1種単独でも又は2種以上を組み合わせて用いても良い。2種以上組み合わせる場合は、これらの樹脂を構成するモノマーの共重合体でも良いし、それぞれの樹脂を混合して用いても良い。
より具体的には、(メタ)アクリル酸エステルの単独重合体、2種以上の異なる(メタ)アクリル酸エステルモノマーの共重合体、又は(メタ)アクリル酸エステルと他のモノマーとの共重合体が好ましい。
なお、ここで重量平均分子量とは、ゲルパーミエションクロマトグラフィー(GPC)により測定したポリスチレン換算のものである。ここで用いる溶媒としては通常用いられるものを適宜選択して行うことができ、例えば、テトラヒドロフラン(THF)又はN-メチル-2-ピロリジノン(NMP)等が挙げられる。
微小粒子の平均粒径は好ましくは0.5~20μm、より好ましくは0.5~10μmであり、添加量は、バインダー樹脂100質量部に対して、0.1~10質量部の範囲が好ましく、0.5~5質量部の範囲がさらに好ましい。なお、粒子の形状は、多面体、球形、鱗片状などである。
インサート成形法では、真空成形工程において、本発明の製造方法により得られる加飾シートを真空成形型により予め成形品表面形状に真空成形(オフライン予備成形)し、次いで必要に応じて余分な部分をトリミングして成形シートを得る。この成形シートを射出成形型に挿入し、射出成形型を型締めし、流動状態の樹脂を型内に射出し、固化させて、射出成形と同時に樹脂成形物の外表面に加飾シートを一体化させ、加飾樹脂成形品を製造する。
なお、射出成形同時加飾法では、射出樹脂による熱圧を加飾シートが受けるため、平板に近く、加飾シートの絞りが小さい場合には、加飾シートは予熱してもしなくても良い。
また、ここで用いる射出樹脂としてはインサート成形法で説明したものと同様のものを用いることができる。
なお、各評価方法・測定方法の詳細を以下に示す。
株式会社東京精密製表面粗さ測定器、商品名「ハンディサーフE-35A」を使用し、JIS B 0601:2001に準拠し、長さLの粗さ曲線を中心線から折り返し、それぞれの粗さ曲線と中心線によって得られた全面積を長さLで割った値をマイクロメートル(μm)で表わした。
(十点平均粗さRzJIS)
十点平均粗さRzJISを、JIS B 0601:2001に準拠して、測定長4mm、カットオフ値0.8mmで測定した。
加飾シートを2枚用い、一方の表面側と他方の裏面側とを重ね合わせてブロッキング・テスターにより2.94MPaの荷重をかけ、40℃で72時間放置した後、接している面同士の付着・接合程度を以下の指標により評価した。
○:重ねた加飾シートを剥がす際、全く抵抗が無い状態である。
×:重ねた加飾シートを剥がす際に抵抗が有り、加飾シートの表面側にブロッキングに由来する擦り傷やシワが確認された。
加飾シートを、一層の表面側と他層の裏面側とを重ね合わせたロール状に巻き取り、20℃で168時間放置した。ロールから20枚の加飾シートを切り出し、表面保護層に傷、凹みが有るものの枚数を確認した。尚、これらの傷や凹みは、ロールに巻き込まれた微細な塵埃等の異物に起因するものと考えられる。
○:傷、凹みが生じた加飾シート 0枚
△:傷、凹みが生じた加飾シート 10枚未満
×:傷、凹みが生じた加飾シート 10枚以上
グロスメーター(ビックガードナー社製マイクロ-トリ-グロス)を用い、入射角60°の条件で、グロス値を測定した。数値が高いほど艶が高いことを示す。
(平滑性)
加飾シートをインサート成形した成形品表面を目視にて評価した。
○;表面の平滑性に優れ、成形品表面に鮮鋭な像が映り込んだ。
×;表面の平滑性に乏しく、成形品表面に映り込んだ像が歪んだ。
(ヘイズ)
ASTM D4039に定義されたヘイズ値にて評価した。グロスメーター(ビックガードナー社製マイクロ-トリ-グロス)を用い、入射角60°、20°の条件で、それぞれのグロス値を測定し、下式にてヘイズ値を求めた。
ヘイズ値=グロス値(60°)-グロス値(20°)
ヘイズ値が小さいほど光沢感、透明感が高いことを示し、ヘイズ値が大きいほど曇り透明性が低いことを示す。
インサート成形後にシート表面にカッターナイフを用いて2mm間隔に縦10本、横10本の碁盤目状の切れ込みを入れた後、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。
◎:剥離はなかった。
○:碁盤目の切れ込みに沿って極軽微な剥離が見られた。
×:シートと射出樹脂の間で剥離が見られた。
加飾シートを所定温度のオイルバスに1分間浸漬し、浸漬後のエンボスのしぼ戻り及び艶を目視した。10℃刻みで評価を行い、しぼ戻りがなく、艶の変化もない最も高い温度を示した。
剥離フィルムとして表層にシリコーン系の離型層を有する2軸延伸ポリエチレンテレフタレートフィルム(厚さ:25μm、算術平均粗さ(Ra):0.01μm)を用い、この剥離フィルム上にアクリル/ウレタンブロック共重合樹脂を塗工して、厚さ2μmの透明なプライマー層を形成した。
次いで、このプライマー層上にアクリルウレタン共重合樹脂インキを用い、グラビア印刷により木目柄の意匠層を形成した。その後、剥離フィルム上にプライマー層と意匠層とが形成されたシートの意匠層側を基材(ABS樹脂からなるシート、厚さ;300μm)に接触させた後、プライマー層側(表面側)に算術平均粗さRa0.05μmのステンレス製鏡面板を、基材側(裏面側)に算術平均粗さRa4.0μm、十点平均粗さRzJIS16μmの梨地柄の入ったステンレス製金属板を用いた熱プレス機を用いて、150℃、5kgf/cm2の加圧下、10分間熱プレス加工を行った。熱プレス加工後、剥離フィルムを剥離し、プライマー層、意匠層を基材に転写した。
次に、剥離フィルムを剥離した後のプライマー層表面に、2官能のウレタンアクリレート(重量平均分子量;2,000)からなる電子線硬化性樹脂組成物を硬化後の厚さが6μmとなるようにグラビアリバースにて塗布した。この未硬化樹脂層に加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、電子線硬化性樹脂組成物を硬化させ加飾シートを得た。
得られた加飾シートの算術平均粗さRaは、表面側が0.1μmであり、裏面側が2.0μmであった。
次に、得られた加飾シートを、シートの温度が170℃になるまで赤外線ヒーターで加熱し、軟化させた後、真空成形した。型より加飾シートを離型し、裏面を確認したところエンボスは消失し、平滑になっていた。真空成形した加飾シートの不要部分を、ダイカット型を油圧により押し当ててトリミングした。このトリミングした加飾シートを用いて、射出成形型に挿入した後、型締めして、型内にABS樹脂を射出して、成形品表面に加飾シートが積層一体化し、インサート成形による加飾樹脂成形品を得た。
熱プレス工程において、意匠層を有しない側(裏面側)に算術平均粗さRa8.5μm、十点平均粗さRzJIS39μmの梨地柄の入ったステンレス製金属板を用いた以外は、実施例1と同様にして加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ200μmのABS樹脂からなるシートを用い、かつ、熱プレス工程において、意匠層を有しない側(裏面側)に算術平均粗さRa6.9μm、十点平均粗さRzJIS28μmの梨地柄の入ったステンレス製金属板を用いた以外は、実施例1と同様にして加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ400μmのABS樹脂からなるシートを用い、かつ、熱プレス工程において、意匠層を有しない側(裏面側)に算術平均粗さRa4.0、十点平均粗さRzJIS23μmの梨地柄の入ったステンレス製金属板を用いた以外は、実施例1と同様にして加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ400μmのABS樹脂からなるシートを用い、かつ、2官能のポリカーボネートアクリレート(重量平均分子量;10,000)と6官能のウレタンアクリレート(重量平均分子量;6,000)を94:6の比で混合した電子線硬化性樹脂を用いた以外は実施例1と同様にして加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ400μmのABS樹脂からなるシートを用い、かつ、2官能のアクリルシリコーンアクリレート(重量平均分子量;20,000)と6官能のウレタンアクリレート(重量平均分子量;5,000)を70:30の比で混合した電子線硬化性樹脂を用いた以外は実施例1と同様にして加飾シート及び加飾樹脂成形品を得た。
実施例1の熱プレス加工において、算術平均粗さRaが19μm、十点平均粗さRzJIS130μmの梨地柄の入ったステンレス製金属板を用いて、140℃で熱プレス加工を行った以外は、実施例1と同様に加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ200μmのABS樹脂からなるシートを用い、かつ、実施例1の熱プレス加工において、裏面側に、梨地柄の入ったステンレス製金属板に代えて、算術平均粗さRa1.8μm、十点平均粗さRzJIS6μmのステンレス製鏡面板を用いて熱プレス加工を行った以外は、実施例1と同様に加飾シート及び加飾樹脂成形品を得た。
比較例2において、基材として、厚さ400μmのABS樹脂からなるシートを用い、かつ、表面側にアクリル系樹脂100質量部及びシリカ(平均粒径:3.0μm)10質量部からなる組成物を塗工量1g/m2でグラビア印刷を施して微小粒子含有樹脂層を設けた以外は比較例1と同様にして加飾シート及び加飾樹脂成形品を得た。
基材として、厚さ100μmのABS樹脂からなるシートを用い、かつ、実施例10の熱プレス加工において、裏面側に、梨地柄の入ったステンレス製金属板に代えて、算術平均粗さRa28.2μm、十点平均粗さRzJIS97μmのステンレス製鏡面板を用いて熱プレス加工を行った以外は、実施例5と同様に加飾シート及び加飾樹脂成形品を得た。
剥離フィルムとして表層にシリコーン系の離型層を有する2軸延伸ポリエチレンテレフタレートフィルム(厚さ:25μm、算術平均粗さ(Ra):0.01μm)を用い、この剥離フィルム上にアクリル/ウレタンブロック共重合樹脂を塗工して、厚さ2μmの透明なプライマー層を形成した。
次いで、このプライマー層上にアクリルウレタン共重合樹脂インキを用い、グラビア印刷により木目柄の意匠層を形成した。その後、剥離フィルム上にプライマー層と意匠層とが形成されたシートの意匠層側を基材(ABS樹脂からなるシート、厚さ;400μm)に接触させた後、プライマー層側(表面側)に算術平均粗さRa0.05μmのステンレス製鏡面板を、基材側(裏面側)に算術平均粗さRa8.0μmの梨地柄の入ったステンレス製金属板を用いた熱プレス機を用いて、150℃、5kgf/cm2の加圧下、10分間熱プレス加工を行った。熱プレス加工後、剥離フィルムを剥離し、プライマー層、意匠層を基材に転写した。
次に、剥離フィルムを剥離した後のプライマー層表面に、2官能のウレタンアクリレート(重量平均分子量;2,000)からなる電子線硬化性樹脂組成物を硬化後の厚さが6μmとなるようにグラビアリバースにて塗布した。この未硬化樹脂層に加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、電子線硬化性樹脂組成物を硬化させ加飾シートを得た。
得られた加飾シートの算術平均粗さRaは、表面側が0.1μmであり、裏面側が3.0μmであった。また、エンボス堅牢度は130℃であった。
次に、得られた加飾シートを、シートの温度が170℃になるまで赤外線ヒーターで加熱し、軟化させた後、真空成形した。型より加飾シートを離型し、裏面を確認したところエンボスは消失し、平滑になっていた。真空成形した加飾シートの不要部分を、ダイカット型を油圧により押し当ててトリミングした。このトリミングした加飾シートを用いて、射出成形型に挿入した後、型締めして、型内にABS樹脂を射出して、成形品表面に加飾シートが積層一体化し、インサート成形による加飾樹脂成形品を得た。
熱プレスの温度を140℃に変更した以外は、実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
熱プレスの温度を180℃に変更した以外は、実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
熱プレスの温度を230℃に変更した以外は、実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
実施例7の熱プレス加工において、裏面側に、梨地柄の入ったステンレス製金属板に代えて、算術平均粗さRa0.05μmのステンレス製鏡面板を用い、また、表面の電子線硬化性樹脂組成物を硬化させた後、裏面側にアクリル系樹脂100質量部及びシリカ(平均粒径:1.5μm)3質量部からなる組成物を塗工量1g/m2でグラビア印刷を施して微小粒子含有樹脂層を設けた以外は実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径3.0μmのシリカを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径5.0μmのシリカを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径5.0μmのアクリルビーズを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径5.0μmのポリエチレンワックスを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
2官能のポリカーボネートアクリレート(重量平均分子量;10,000)と6官能のウレタンアクリレート(重量平均分子量;6,000)を94:6の比で混合した電子線硬化性樹脂を用いた以外は実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
2官能のアクリルシリコーンアクリレート(重量平均分子量;20,000)と6官能のウレタンアクリレート(重量平均分子量;5,000)を70:30の比で混合した電子線硬化性樹脂を用いた以外は実施例7と同様にして加飾シート及び加飾樹脂成形品を得た。
実施例7の熱プレス加工において、裏面側に、梨地柄の入ったステンレス製金属板に代えて、算術平均粗さRa0.05μmのステンレス製鏡面板を用いて熱プレス加工を行った以外は、実施例7と同様に加飾シート及び加飾樹脂成形品を得た。
実施例7の熱プレス加工において、裏面側に、算術平均粗さRaが19μmの梨地柄の入ったステンレス製金属板を用いて、140℃で熱プレス加工を行った以外は、実施例7と同様に加飾シート及び加飾樹脂成形品を得た。
比較例5において、表面側にアクリル系樹脂100質量部及びシリカ(平均粒径:3.0μm)10質量部からなる組成物を塗工量1g/m2でグラビア印刷を施して微小粒子含有樹脂層を設けた以外は比較例5と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径0.1μmのシリカを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
平均粒径1.5μmのシリカに代えて、平均粒径9.0μmのシリカを用いた以外は実施例11と同様にして加飾シート及び加飾樹脂成形品を得た。
比較例5において、裏面側に帯電防止剤としてカチオン系界面活性剤(ジメチル硫酸トリメチルアンモニウム塩)のイソプロピルアルコール10%溶液を乾燥時塗布厚が0.5g/m3となるようにグラビアコーティングにより塗布した以外は比較例5と同様にして加飾シート及び加飾樹脂成形品を得た。
また、加飾シート表面側に微小粒子含有樹脂層を設けた比較例3では、加飾樹脂成形品表面の平滑性が損なわれた。
比較例4では、Ra及びRzJISが大きすぎるため、加飾樹脂成形品の表面艶が著しく低下し、ヘイズが生じた。
また、加飾シート表面側に微小粒子含有樹脂層を設けた比較例7では、加飾シート表面の平滑性が損なわれた。
比較例10では、加飾シートの裏面に界面活性剤を塗布することでブロッキングが抑止されたが、加飾シートの両面が共に平滑であるため、異物の巻き込みによる傷や凹みは完全には防止できず、また、射出樹脂との密着性が低下してしまった。
Claims (8)
- 表面が平滑な剥離フィルム上にプライマー層を形成する工程と、該プライマー層上に意匠層を形成する工程と、該プライマー層及び該意匠層を基材上に転写する工程と、該基材上の該剥離フィルムを剥がす工程と、該基材上に形成された該プライマー層上に電離放射線硬化性樹脂組成物を積層する工程と、該電離放射線硬化性樹脂組成物を架橋硬化して表面保護層を形成する工程とを含む加飾シートの製造方法であって、さらに、該加飾シートの裏面の十点平均粗さRzJISと基材の厚さTとが下記式(I)を満たし、かつ、算術平均粗さRaと基材の厚さTとが下記式(II)を満たすようにする粗面化処理工程を含むことを特徴とする加飾シートの製造方法。
T×0.30≧RzJIS (I)
T×0.20≧Ra≧T×0.005 (II) - 表面が平滑な剥離フィルム上にプライマー層を形成する工程と、該プライマー層上に意匠層を形成する工程と、該プライマー層及び該意匠層を基材上に転写する工程と、該基材上の該剥離フィルムを剥がす工程と、該基材上に形成された該プライマー層上に電離放射線硬化性樹脂組成物を積層する工程と、該電離放射線硬化性樹脂組成物を架橋硬化して表面保護層を形成する工程とを含む加飾シートの製造方法であって、さらに該加飾シートの裏面の算術平均粗さRaを1.0~10.0μmとする粗面化処理工程を含むことを特徴とする加飾シートの製造方法。
- 前記粗面化処理が、前記基材に梨地板を用いた熱プレス加工又は梨地ロールを用いたエンボス加工を施すことにより行われる請求項1又は2に記載の加飾シートの製造方法。
- 前記粗面化処理が、前記基材の裏面側に微小粒子を含有する樹脂層を設けることにより行われる請求項1又は2に記載の加飾シートの製造方法。
- 基材上に意匠層と、プライマー層と、電離放射線硬化性樹脂組成物を架橋硬化してなる表面保護層とをこの順に有する加飾シートであって、該表面保護層の表面が平滑であり、該加飾シートの裏面の十点平均粗さRzJISと基材の厚さTとが下記式(I)を満たし、かつ、算術平均粗さRaと基材の厚さTとが下記式(II)を満たすことを特徴とする加飾シート。
T×0.30≧RzJIS (I)
T×0.20≧Ra≧T×0.005 (II) - 基材上に意匠層と、プライマー層と、電離放射線硬化性樹脂組成物を架橋硬化してなる表面保護層とをこの順に有する加飾シートであって、該表面保護層の表面が平滑であり、該加飾シートの裏面の算術平均粗さRaが、1.0~10.0μmであることを特徴とする加飾シート。
- 前記表面保護層の表面の算術平均粗さRaが、0.01μm以上1.0μm未満である請求項5又は6に記載の加飾シート。
- 請求項5~7のいずれかに記載の加飾シートを用いてなる加飾成形品。
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EP11800966.1A EP2589440B1 (en) | 2010-06-30 | 2011-06-30 | Process for producing decorative sheet, decorative sheet, and process for producing a decorative molded article using said decorative sheet. |
US13/807,081 US8801888B2 (en) | 2010-06-30 | 2011-06-30 | Process for producing decorative sheet, decorative sheet, and decorative molded article obtained using same |
KR1020127033976A KR101798683B1 (ko) | 2010-06-30 | 2011-06-30 | 장식 시트의 제조 방법, 장식 시트 및 그것을 사용하여 이루어지는 장식 성형품 |
CN201180032774.7A CN103108704B (zh) | 2010-06-30 | 2011-06-30 | 装饰片的制造方法、装饰片、以及使用该装饰片得到的装饰成形品 |
US14/291,258 US20140272293A1 (en) | 2010-06-30 | 2014-05-30 | Process For Producing Decorative Sheet, Decorative Sheet, And Decorative Molded Article Obtained Using Same |
US15/901,163 US11123969B2 (en) | 2010-06-30 | 2018-02-21 | Process for producing decorative sheet, decorative sheet, production process for a decorated resin molded article, and decorative molded article obtained using same |
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US14/291,258 Division US20140272293A1 (en) | 2010-06-30 | 2014-05-30 | Process For Producing Decorative Sheet, Decorative Sheet, And Decorative Molded Article Obtained Using Same |
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US20170106632A1 (en) * | 2014-03-26 | 2017-04-20 | Dai Nippon Printing Co., Ltd. | Transfer film for three-dimensional molding |
DE102014104760A1 (de) * | 2014-04-03 | 2015-10-08 | Fritz Egger Gmbh & Co. Og | Schichtstoff und Verfahren zu dessen Herstellung |
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JP6919836B2 (ja) * | 2017-09-29 | 2021-08-18 | 大日本印刷株式会社 | 転写シート及び該転写シートを使用したメラミン化粧板の製造方法 |
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CN103108704A (zh) | 2013-05-15 |
JP2012011321A (ja) | 2012-01-19 |
US20130101793A1 (en) | 2013-04-25 |
KR101798683B1 (ko) | 2017-11-16 |
EP2589440A1 (en) | 2013-05-08 |
KR20130115107A (ko) | 2013-10-21 |
US20180178497A1 (en) | 2018-06-28 |
EP2589440A4 (en) | 2015-01-07 |
EP2589440B1 (en) | 2019-08-07 |
JP5609324B2 (ja) | 2014-10-22 |
US11123969B2 (en) | 2021-09-21 |
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US20140272293A1 (en) | 2014-09-18 |
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