WO2015147006A1 - Decorative sheet and decorative resin-molded article - Google Patents
Decorative sheet and decorative resin-molded article Download PDFInfo
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- WO2015147006A1 WO2015147006A1 PCT/JP2015/058970 JP2015058970W WO2015147006A1 WO 2015147006 A1 WO2015147006 A1 WO 2015147006A1 JP 2015058970 W JP2015058970 W JP 2015058970W WO 2015147006 A1 WO2015147006 A1 WO 2015147006A1
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- decorative sheet
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- surface protective
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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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
- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/12—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor of articles having inserts or reinforcements
-
- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/16—Lining or labelling
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- B29K2995/0037—Other properties
- B29K2995/007—Hardness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
Definitions
- the present invention relates to a decorative sheet having excellent formability. Furthermore, the present invention relates to a decorated resin molded article having excellent chemical resistance using the decorative sheet.
- a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product has been used for vehicle interior / exterior parts, building material interior materials, home appliance casings, and the like.
- a molding method or the like is used in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding.
- a decorative sheet is previously molded into a three-dimensional shape by a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold.
- the injection molding method that integrates the resin and the decorative sheet, and the injection molding that integrates the decorative sheet inserted into the mold during the injection molding with the molten resin injected into the cavity
- the decoration method is mentioned.
- decorative sheets used in the manufacture of decorative resin molded products are required to have the function of imparting stain resistance to various products used in daily life to decorative resin molded products. Yes.
- skin care products such as sunscreen cosmetics and insect repellents tend to be used frequently in recent years, and the frequency of contact of the skin applied with such skin care products with decorative resin molded products has increased.
- the decorative sheet is strongly required to have chemical resistance against skin care products.
- the surface protective layer is composed of a polyfunctional (meth) acrylate monomer having a molecular weight of 175 to 1000 and a weight.
- the mass of the polyfunctional (meth) acrylate monomer and the thermoplastic resin formed from an ionizing radiation curable resin composition containing a thermoplastic resin having an average molecular weight of 10,000 to less than 100,000. It is disclosed that by setting the ratio to 10:90 to 75:25, it is possible to provide stain resistance and moldability to sunscreen cream.
- Patent Document 1 Although the technique described in Patent Document 1 is useful in producing a decorative sheet having excellent moldability and chemical resistance, consumer demand for decorative resin molded products has recently been advanced and diversified. In order to follow this, it is necessary to create a new technique for providing a decorative sheet with excellent moldability and chemical resistance.
- the main object of the present invention is to provide a decorative sheet excellent in moldability and a decorative resin molded product excellent in chemical resistance using the decorative sheet.
- the present inventor has intensively studied to solve the above problems. As a result, at least the base material layer and the surface protective layer formed of the ionizing radiation curable resin composition are laminated, and the decorative sheet containing the blocked isocyanate is excellent in moldability. The present inventors have found that excellent chemical resistance can be imparted to decorative resin molded products. The present invention has been completed by further studies based on these findings.
- this invention provides the invention of the aspect hung up below.
- Item 1. At least, a base material layer and a surface protective layer formed of an ionizing radiation curable resin composition are laminated, The decorative sheet, wherein the surface protective layer contains a blocked isocyanate.
- Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer further comprises a catalyst that promotes the dissociation reaction of the blocked isocyanate.
- Item 3. Item 3.
- the decorative sheet according to Item 1 or 2 wherein the ionizing radiation curable resin composition contains polycarbonate (meth) acrylate.
- Item 4. Item 4. The decorative sheet according to Item 3, wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 5,000 or more.
- Item 5. The decorative sheet according to item 3 or 4, wherein the ionizing radiation curable resin composition of the surface protective layer further contains urethane (meth) acrylate.
- Item 6. The decorative sheet according to Item 5, wherein a mass ratio of the polycarbonate (meth) acrylate and the urethane (meth) acrylate is in the range of 50:50 to 99: 1.
- Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the surface protective layer has a thickness of 1 to 30 ⁇ m.
- Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, further comprising a primer layer between the base material layer and the surface protective layer.
- Item 9. Item 9.
- Item 10. Item 10. The decorative sheet according to Item 9, wherein the polyol resin is at least one selected from the group consisting of acrylic polyol, polyester polyol, and polycarbonate diol.
- Item 11. Item 11. The decorative sheet according to Item 9 or 10, wherein the polyol resin has a glass transition point (Tg) of 55 ° C or higher and a weight average molecular weight of 2,000 or higher.
- Tg glass transition point
- Item 12. The decorative sheet according to any one of Items 1 to 11, further comprising a pattern layer between the base material layer and the surface protective layer.
- Item 13. Item 12.
- Item 14. At least a molded resin layer, a base material layer, and a surface protective layer are laminated, A decorative resin molded product, wherein the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a blocked isocyanate.
- Item 15. Item 15. The decorated resin molded article according to Item 14, further comprising a primer layer between the base material layer and the surface protective layer.
- the decorative sheet according to any one of Items 1 to 13 is inserted into an injection mold, the injection mold is closed, and a resin in a fluid state is injected into the injection mold so that the resin, the decorative sheet, Integration process to integrate, A method for producing a decorated resin molded product.
- Item 17. The method for producing a decorated resin molded article according to Item 16, comprising a vacuum forming step of forming the decorative sheet into a three-dimensional shape in advance using a vacuum forming die before the integration step.
- the method for producing a decorated resin molded product according to Item 17, comprising a step of heating the decorative sheet in the vacuum forming step.
- a decorative sheet that is excellent in moldability and can impart excellent chemical resistance to a decorative resin molded product, and a decorative resin molded product using the decorative sheet. it can.
- Decorative sheet The decorative sheet of the present invention is such that at least a base material layer and a surface protective layer formed of an ionizing radiation curable resin composition are laminated, and the surface protective layer contains a blocked isocyanate.
- the surface protective layer formed of the ionizing radiation curable resin composition contains blocked isocyanate, thereby having high moldability and high chemical resistance to the decorative resin molded product. It can be set as the decorating sheet
- the surface protective layer formed by the ionizing radiation curable resin composition contains a blocked isocyanate
- the cross-linking density of the surface protective layer can be increased and hardened, and thus the decorative sheet obtained using the decorative sheet of the present invention
- the resin molded product is considered to exhibit excellent chemical resistance.
- the crosslinking density of the surface protective layer can be kept low without initiating the reaction with the blocked isocyanate until it is subjected to the molding of the decorative resin molded product.
- the decorative sheet of the present invention retains moderate flexibility and has excellent moldability.
- the decorative sheet of the present invention will be described in detail.
- the decorative sheet of the present invention has a laminated structure in which at least the base material layer 1 and the surface protective layer 2 are laminated in this order.
- the pattern layer 3 may be provided as necessary for the purpose of imparting decorativeness to the resin molded product.
- the base material layer 1 and the design layer are provided in the case where the design layer 3 is provided between the base material layer 1 and the surface protective layer 2. If necessary, a concealing layer 5 may be provided.
- the pattern layer 3 is provided between the base material layer 1 and the surface protective layer 2 for the purpose of improving the moldability of the decorative sheet and the adhesion of each layer, the pattern layer 3 and the surface protective layer.
- a primer layer 4 or the like may be provided between the two and the like as necessary.
- an adhesive layer 6 or the like may be provided under the base material layer 1.
- a laminated structure of the decorative sheet of the present invention a laminated structure in which a base material layer / surface protective layer are laminated in this order; a laminated structure in which a base material layer / picture layer / surface protective layer are laminated in this order; adhesive layer / base Laminated structure in which material layer / picture layer / surface protective layer are laminated in this order; laminated structure in which base material layer / hiding layer / design layer / surface protective layer are laminated in this order; base material layer / primer layer / surface protective layer Are laminated in this order; base material layer / pattern layer / primer layer / surface protective layer are laminated in this order; adhesive layer / base material layer / picture layer / primer layer / surface protective layer are in this order; Examples include a laminated structure.
- FIG. 1 the schematic sectional drawing of an example of the decorating sheet
- FIG. 2 the schematic sectional drawing of an example of the decorating sheet
- the base material layer 1 is formed of a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention.
- the resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molded resin layer, and the like, and preferably a thermoplastic resin.
- thermoplastic resin examples include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylate resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; Polycarbonate resin; Vinyl chloride resin; Polyethylene terephthalate (PET) resin.
- ABS resin is preferable from the viewpoint of three-dimensional moldability.
- ABS resin component which forms the base material layer 1 only 1 type may be used and 2 or more types may be mixed and used.
- the base material layer 1 may be formed with the single layer sheet
- the base material layer 1 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion between adjacent layers.
- Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method.
- a sandblasting method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.
- the base material layer 1 may be colored with a colorant or the like, painted for adjusting the color, formation of a pattern for imparting design properties, or the like.
- the thickness of the base material layer 1 is not particularly limited and is appropriately set according to the use of the decorative sheet, etc., but is usually about 50 to 800 ⁇ m, preferably about 100 to 600 ⁇ m, more preferably about 200 to 500 ⁇ m. It is done. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.
- the surface protective layer 2 is a layer provided in order to improve the chemical resistance and scratch resistance of the decorative sheet.
- the surface protective layer 2 is formed of an ionizing radiation curable resin composition.
- the surface protective layer 2 contains a blocked isocyanate.
- crosslinking with the blocked isocyanate is started in the process of forming the decorative resin molded product, and the ionizing radiation curable resin composition It is considered that the surface protection layer 2 formed of a product can be hardened by increasing the crosslink density, and the resulting decorative resin molded product is imparted with excellent chemical resistance.
- the crosslinking density of the surface protective layer can be kept low without initiating the reaction with the blocked isocyanate until it is subjected to the molding of the decorative resin molded product. It retains flexibility and has excellent moldability.
- the ionizing radiation curable resin used for forming the surface protective layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. A prepolymer, an oligomer, and / or a monomer appropriately mixed with each other.
- ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and ⁇ rays, and charged particle rays such as ⁇ rays and ion rays.
- UV ultraviolet
- EB electron beam
- electron beam curable resins can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics. Therefore, they are suitable for forming the surface protective layer 2. Used for.
- a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
- the polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule.
- polyfunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (me
- the oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule.
- a polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred.
- Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
- polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid.
- the polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton.
- the urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.
- the acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer.
- Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
- Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used.
- Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid.
- the polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
- Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer.
- Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain.
- These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.
- (meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning.
- ionizing radiation curable resins may be used alone or in combination of two or more.
- polycarbonate (meth) acrylate is preferably used from the viewpoint of further improving moldability. Further, from the viewpoint of improving scratch resistance, chemical resistance and other surface properties, it is more preferable to use urethane (meth) acrylate in addition to the above polycarbonate (meth) acrylate.
- the polycarbonate (meth) acrylate and the urethane (meth) acrylate that are suitably used as the ionizing radiation curable resin in the formation of the surface protective layer 2 will be described in detail.
- the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and (meth) acrylate at the terminal or side chain.
- urethane (meth) acrylate having a polycarbonate skeleton It may be.
- the (meth) acrylate is preferably 2 to 6 functional groups per molecule from the viewpoint of improving cross-linking and curing.
- the polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at the terminals or side chains.
- Polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.
- Polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl group of polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester).
- This esterification reaction can be performed by a normal esterification reaction.
- 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.
- the urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.
- Polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain.
- a typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.
- the diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R 1 —OH.
- R 1 is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond.
- R 1 is, for example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.
- diol compound examples include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2 -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.
- Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned.
- the trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide is added to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.
- the compound (C) used as a raw material of the polycarbonate polyol, which is a carbonyl component is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof.
- Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate.
- esters include esters. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
- Polycarbonate polyol is synthesized by subjecting the diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions.
- the charged molar ratio between the diol compound (A) and the polyhydric alcohol (B) may be set in the range of 50:50 to 99: 1, for example.
- the charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2-2 with respect to the hydroxyl group of the diol compound and the polyhydric alcohol. What is necessary is just to set to the range of an equivalent.
- the number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charge ratio is, for example, 3 or more on average per molecule, preferably 3 to 50, more preferably Includes 3 to 20.
- a necessary amount of (meth) acrylate groups are formed by an esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin.
- the terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.
- the method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726.
- the polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.
- the molecular weight of the polycarbonate (meth) acrylate is not particularly limited.
- the weight average molecular weight is 5,000 or more, preferably 10,000 or more.
- the upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is, for example, 100,000 or less, preferably 50,000 or less, from the viewpoint of controlling the viscosity not to be too high.
- the weight average molecular weight of the polycarbonate (meth) acrylate is preferably 10,000 to 50,000, and more preferably 10,000 to 2, from the viewpoint of further improving the expression effect of rich and low gloss with a texture and the moldability. Million.
- the weight average molecular weight of the polycarbonate (meth) acrylate in this specification is a value measured with polystyrene as a standard substance by gel permeation chromatography (GPC).
- the content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition used for forming the surface protective layer 2 is particularly limited to exhibit the effect of the present invention.
- limit From a viewpoint which improves the moldability of a decorating sheet more, Preferably it is 50 mass% or more, More preferably, it is 80 mass% or more, More preferably, 85 mass% or more is mentioned.
- the urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and a (meth) acrylate in the terminal or side chain.
- Such urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
- the urethane (meth) acrylate is preferably 2 to 12 functional groups per molecule from the viewpoint of improving cross-linking and curing.
- the urethane (meth) acrylate is preferably a polyfunctional urethane (meth) acrylate having two or more (meth) acrylates at the terminal or side chain.
- the ionizing radiation curable resin composition used for forming the surface protective layer 2 may further contain urethane (meth) acrylate.
- Urethane (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.
- the molecular weight of urethane (meth) acrylate is not particularly limited, and examples include a weight average molecular weight of 100 or more, preferably 5 or more.
- the upper limit of the weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but is, for example, 100,000 or less, preferably 50,000 or less, from the viewpoint of controlling the viscosity not to be too high.
- the weight average molecular weight of urethane (meth) acrylate in this specification is a value measured with polystyrene as a standard substance by gel permeation chromatography (GPC).
- the mass ratio is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and still more preferably about 85:15 to 99: 1.
- the surface protective layer 2 further contains a blocked isocyanate in addition to the ionizing radiation curable resin.
- the blocked isocyanate is a compound in which the isocyanate group of the isocyanate compound is protected with a blocking agent, and is stable at normal temperature, but the blocking agent is dissociated by heating to regenerate an active isocyanate group. Since the blocked isocyanate functions as a crosslinking agent, the above isocyanate compound has two or more isocyanate groups in one molecule.
- a block isocyanate may be used individually by 1 type, and may be used in combination of 2 or more type.
- isocyanate compound examples include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); alicyclic diisocyanates such as isophorone diisocyanate (IPDI); xylylene diisocyanate (XDI) and the like.
- HMDI hexamethylene diisocyanate
- TMDI trimethylhexamethylene diisocyanate
- alicyclic diisocyanates such as isophorone diisocyanate (IPDI); xylylene diisocyanate (XDI) and the like.
- Aromatic aliphatic diisocyanates such as tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI); dimer acid diisocyanate (DDI), hydrogenated TDI (HTDI), hydrogenated Hydrogenated diisocyanates such as XDI (H6XDI), hydrogenated MDI (H12MDI); dimers, trimers, and higher molecular weight polymers of these diisocyanate compounds; Cyanates; and adduct of trimethylol propane such polyhydric alcohol or water or a low molecular weight polyester resin, and the like.
- the blocking agent include oximes such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime; phenols such as m-cresol and xylenol; methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanone Examples include alcohols such as hexanol and ethylene glycol monoethyl ether; lactams such as ⁇ -caprolactam; diketones such as diethyl malonate and acetoacetate; mercaptans such as thiophenol. Other examples include ureas such as thiourea; imidazoles; carbamic acids.
- oximes such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime
- Block isocyanate can be obtained by reacting the above isocyanate compound and blocking agent by a conventional method until free isocyanate groups disappear. Moreover, as a block isocyanate, a commercial item can also be used.
- the content of the blocked isocyanate in the surface protective layer 2 is preferably 0.5 mass with respect to 100 mass parts of the ionizing radiation curable resin. Part or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more.
- the content of the blocked isocyanate in the surface protective layer 2 is too large, the formability of the decorative sheet is lowered, so the content of the blocked isocyanate in the surface protective layer 2 is 100 parts by mass of ionizing radiation curable resin. Is preferably 100 parts by mass or less, more preferably 50 parts by mass or less.
- the surface protective layer 2 preferably contains a catalyst for promoting the dissociation reaction of the blocked isocyanate in addition to the above-mentioned blocked isocyanate.
- a catalyst for promoting the dissociation reaction of the blocked isocyanate in addition to the above-mentioned blocked isocyanate.
- catalysts include organotin compounds such as dibutyltin dilaurate, dibutyltin dioctate, and dibutyltin diacetate; aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (acetylacetonate), titanium bis Metals such as (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate) Examples include chelate compounds. Among these, tin-based catalysts are generally used.
- the content of the catalyst in the surface protective layer 2 is preferably 0.01 mass with respect to 100 mass parts of the ionizing radiation curable resin. Part or more, more preferably 0.2 part by weight or more.
- the content of the catalyst in the surface protective layer 2 is too large, the moldability of the decorative sheet is lowered, so the content of the catalyst in the surface protective layer 2 is 100 parts by mass of ionizing radiation curable resin.
- it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
- various additives can be blended according to desired physical properties to be provided in the surface protective layer 2.
- the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used.
- the ultraviolet absorber or light stabilizer a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.
- the thickness of the surface protective layer 2 after curing is not particularly limited, but is preferably 1 to 30 ⁇ m, more preferably about 1 to 10 ⁇ m. When the thickness within such a range is satisfied, the decorative sheet is excellent in moldability and sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Further, since the ionizing radiation curable resin composition forming the surface protective layer 2 can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous.
- the surface protective layer 2 is formed by, for example, preparing an ionizing radiation curable resin composition containing the above ionizing radiation curable resin, blocked isocyanate, and a catalyst added if necessary, and applying and curing the composition. Is done.
- the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form an uncured resin layer on the layer adjacent to the surface protective layer 2 with the below-mentioned application system.
- the prepared coating solution is a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating on the layer adjacent to the surface protective layer 2 so as to have the thickness described above. It is preferably applied by gravure coating to form an uncured resin layer.
- the uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 2.
- ionizing radiation such as electron beams and ultraviolet rays
- the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.
- the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protective layer 2, the electron beam transmission depth and the surface protection are used.
- the acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the surface protective layer 2 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.
- the irradiation dose is preferably such that the crosslinking density of the protective layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
- the electron beam source is not particularly limited.
- various electron beam accelerators such as a 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. Can be used.
- ultraviolet rays When ultraviolet rays are used as the ionizing radiation, it is sufficient to emit light including ultraviolet rays having a wavelength of 190 to 380 nm.
- the ultraviolet light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).
- the pattern layer 3 is a layer that gives decorativeness to the resin molded product, and is provided between the base material layer 1 and the surface protective layer 2 as necessary.
- the pattern layer 3 is formed by printing various patterns using ink and a printing machine.
- the pattern formed by the pattern layer 3 is not particularly limited.
- a grain pattern simulating the surface of a rock such as a grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth simulating a texture or a cloth-like pattern Patterns, tiled patterns, brickwork patterns, etc., and patterns such as marquetry and patchwork that combine these are also included.
- These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed.
- a binder and a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed.
- the binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, Examples thereof include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. These resins may be used alone or in combination of two or more.
- the colorant is not particularly limited.
- carbon black black
- iron black titanium white, antimony white, chrome yellow, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments
- quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue
- metallic pigments composed of scaly foils such as aluminum and brass
- pearl luster composed of scaly foils
- the thickness of the pattern layer 3 is not particularly limited, but for example, about 1 to 30 ⁇ m, preferably about 1 to 20 ⁇ m.
- the concealing layer 5 is provided with the base layer 1 and the pattern layer if the pattern layer 3 is provided between the base layer 1 and the surface protective layer 2 for the purpose of suppressing the color change and variation of the base layer 1.
- 3 is a layer provided as needed (not shown).
- the concealing layer 5 is provided in order to prevent the base material layer 1 from adversely affecting the color tone and design of the decorative sheet, it is generally formed as an opaque layer.
- the hiding layer 5 is formed by using an ink composition 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.
- the ink composition for forming the masking layer 5 is appropriately selected from those used for the pattern layer 3 described above.
- the concealing layer 5 is usually set to a thickness of about 1 to 20 ⁇ m and is desirably formed as a so-called solid printing layer.
- the decorative sheet of the present invention has a pattern layer 3 between the base material layer 1 and the surface protective layer 2 as desired for the purpose of making fine cracks and whitening difficult to occur in the stretched portion of the surface protective layer 2.
- a primer layer 4 may be provided between the pattern layer 3 and the surface protective layer 2.
- the primer layer 4 is preferably provided directly below the surface protective layer 2. That is, by providing the surface protective layer 2 and the primer layer 4 so as to be in contact with each other, the blocked isocyanate contained in the surface protective layer 2 constitutes the primer layer 4 in the process of molding the decorative resin molded product. By reacting with the primer composition, the surface protective layer 2 and the primer layer 4 are firmly bonded, and the chemical resistance of the resulting decorative resin molded product can be further enhanced.
- Primer compositions constituting the primer layer 4 include urethane resin, (meth) acrylic resin, (meth) acryl-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene. Those using chlorinated polyethylene as a binder resin are preferably used, and among these, urethane resins, (meth) acrylic resins, and (meth) acrylic-urethane copolymer resins are preferable.
- urethane resin polyurethane obtained by reacting polyol (polyhydric alcohol) and isocyanate can be used.
- polyol polyhydric alcohol
- isocyanate examples include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate.
- Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.
- (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers.
- Polymer specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer
- a (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.
- the (meth) acryl-urethane copolymer resin for example, an acryl-urethane (polyester urethane) block copolymer resin is preferable.
- the curing agent the above-mentioned various isocyanates are used.
- the acrylic-urethane (polyester urethane) block copolymer resin is adjusted to an acrylic / urethane ratio (mass ratio) of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.
- the primer composition constituting the primer layer 4 is preferably a polyol resin from the viewpoint of improving the chemical resistance and moldability of the decorative sheet.
- the content of the polyol resin is preferably 60% by mass or more, more preferably 80% by mass or more.
- the polyol resin examples include acrylic polyol; polyester polyol; polycarbonate diol; urethane polyol such as polyester urethane polyol and acrylic urethane polyol; polyolefin polyol such as polyethylene polyol, polypropylene polyol, polybutadiene polyol, and polyisoprene polyol; .
- acrylic polyol, polyester polyol, and polycarbonate diol are preferable from the viewpoint of improving the chemical resistance and moldability of the decorative sheet, and acrylic polyol is particularly preferable from the viewpoint of further improving the moldability.
- the acrylic polyol is not particularly limited as long as it is an acrylic resin having a plurality of hydroxyl groups.
- polyester polyol examples include a condensed polyester diol obtained by reacting a low-molecular diol and a dicarboxylic acid, a polylactone diol obtained by ring-opening polymerization of a lactone, and a polycarbonate diol.
- dicarboxylic acid examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid and fumaric acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.
- lactone for example, ⁇ -caprolactone is used.
- polyester polyol examples include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene adipate
- polyester polyol examples include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene adipate
- examples thereof include zetate, polyethylene sebacate, polybutylene azate, polybutylene sebacate, polyhexamethylene carbonate diol, and the like.
- Polycarbonate diol is a polycarbonate having hydroxyl groups at both ends in the molecule.
- the weight average molecular weight of the resin forming the primer layer 4 is not particularly limited, but is preferably 2,000 or more, more preferably 2,000 to 10 from the viewpoint of further improving the chemical resistance and moldability of the decorative sheet. About 10,000, more preferably about 2,000 to 50,000.
- the weight average molecular weight of the resin forming the primer layer 4 is less than 2,000, when the surface protective layer is formed on the primer layer, the primer layer dissolves and the primer layer is whitened. There is.
- the weight average molecular weight of the resin forming the primer layer 4 exceeds 100,000, the viscosity of the primer composition becomes too high, and printing failure may occur.
- the weight average molecular weight of the resin forming the primer layer 4 is a value measured by polystyrene as a standard substance by gel permeation chromatography (GPC).
- the glass transition point (Tg) of the polyol resin is not particularly limited, but is preferably 55 ° C. or higher, more preferably about 55 to 140 ° C. from the viewpoint of further improving the chemical resistance and moldability of the decorative sheet. More preferred is about 65 to 120 ° C, and particularly preferred is about 80 to 100 ° C. When the Tg of the polyol resin is less than 55 ° C., the primer layer 4 becomes soft and has adhesiveness.
- the decorative sheet of the present invention is produced on a roll-to-roll basis, for example, the above-mentioned pattern layer
- the primer layer 4 is printed on 3 or the like, it is easy to be damaged when it comes into contact with the guide roll, and there is a concern that blocking may occur when it is taken up by the paper discharge unit.
- the primer layer 4 is in a semi-molten state, and there is a possibility that, for example, the pattern layer 3 and the surface protective layer 2 may be misaligned, for example, at a high stretch portion in three-dimensional molding.
- the Tg of the polyol is 140 ° C.
- the resin of the primer layer 4 is sufficiently obtained by the heat (the drying step after the primer layer 4 is laminated, the drying step when the pattern layer 3 is laminated) applied to the decorative sheet manufacturing process. Since it softens, the adhesiveness with the surface protective layer 2 and the pattern layer 3 improves, for example.
- the resin used for forming the primer layer 4 may be used alone or in combination of two or more. Specifically, for example, an acrylic polyol and polyurethane can be used in combination.
- a crosslinking agent (curing agent) may be used together with the polyol resin forming the primer layer 4.
- a crosslinking agent By using a crosslinking agent, the adhesion between the surface protective layer 2 and the primer layer 4 can be enhanced.
- the content of the crosslinking agent is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyol resin forming the primer layer 4.
- the amount of the crosslinking agent in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the polyol resin constituting the primer layer 4, the amount of the crosslinking agent is reduced and the moldability of the decorative sheet is particularly enhanced. Is possible. Furthermore, by setting the amount of the crosslinking agent in such a specific range, even when the decorative sheet is exposed to a high temperature, the surface protective layer 2 is hardly peeled off and exhibits excellent heat-resistant adhesion. it can.
- the block isocyanate contained in the surface protective layer 2 can interact with the polyol resin of the primer layer 4 in the interface part of the surface protective layer 2 and the primer layer 4, the ratio of a crosslinking agent is Even in such a relatively small amount, excellent chemical resistance can be exhibited.
- the content of the crosslinking agent is set in such a range, and the content of the blocked isocyanate in the surface protective layer 2 is the resin 100 contained in the surface protective layer 2. It is preferably set in the range of 0.5 to 5 parts by mass with respect to parts by mass.
- the primer layer 4 since the blocked isocyanate contained in the surface protective layer 2 can interact with the polyol resin of the primer layer 4 at the interface portion between the surface protective layer 2 and the primer layer 4, the primer layer 4 is crosslinked. Even when the agent is not included, excellent chemical resistance can be exhibited while enhancing the adhesion between the surface protective layer 2 and the primer layer 4. Further, since the primer layer 2 does not substantially contain a cross-linking agent, the primer layer 4 becomes flexible and the moldability of the decorative sheet is enhanced, so when emphasizing the moldability of the decorative sheet, It is preferable that the primer layer 4 does not substantially contain a crosslinking agent.
- the crosslinking agent is not particularly limited as long as it can crosslink a polyol resin, and examples thereof include an isocyanate compound.
- examples of the isocyanate compound include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate (HMDI), isophorone diisocyanate, hydrogenated tolylene diisocyanate.
- An aliphatic (or alicyclic) isocyanate such as hydrogenated diphenylmethane diisocyanate is used.
- the primer layer 4 is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat with a silk screen, a wire bar coat, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating method.
- the transfer coating method is a method in which a primer layer or an adhesive layer is formed on a thin sheet (film substrate) and then the surface of the target layer in the decorative sheet is coated.
- the thickness of the primer layer 4 is not particularly limited, but preferably 0.1 ⁇ m or more. When it is 0.1 ⁇ m or more, the surface protective layer 2 has an effect of preventing cracking, breaking, whitening, and the like. On the other hand, if the thickness of the primer layer 4 is 10 ⁇ m or less, it is preferable that the three-dimensional formability does not fluctuate since the drying and curing of the coating film is stable when the primer layer 4 is applied.
- the adhesive layer 6 is a layer provided on the back surface of the base material layer 1 as necessary for the purpose of improving the adhesion and adhesion between the decorative sheet and the molding resin.
- the resin forming the adhesive layer 6 is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molding resin.
- a thermoplastic resin or a thermosetting resin may be used. Used.
- the thermoplastic resin include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. .
- thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- thermosetting resin include a urethane resin and an epoxy resin.
- thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- the adhesive layer 6 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decorating method by sticking on a resin molded body prepared in advance, such as a vacuum press-bonding method described later. Is preferably provided.
- a vacuum press-bonding method it is preferable to form the adhesive layer 7 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.
- the decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention is formed by laminating at least a molded resin layer and a surface protective layer, and the surface protective layer is formed of an ionizing radiation curable resin composition containing a blocked isocyanate. It is characterized by that.
- the decorative sheet may further be provided with at least one layer such as the above-described pattern layer 3, primer layer 4, and concealing layer 5.
- the decorative resin molded product of the present invention is produced, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention.
- various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention.
- the in the decorative sheet of the present invention the block contained in the surface protective layer in the process of heating the decorative sheet at the time of injection molding in these molding methods or at the time of preliminary molding (vacuum molding) prior to the molding, etc. It is considered that cross-linking with isocyanate is initiated, and the decorated resin molded product of the present invention obtained by such a molding method can exhibit excellent chemical resistance.
- these injection molding methods an insert molding method and an injection molding simultaneous decorating method are preferable.
- the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained.
- This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, a decorative resin molded product is manufactured.
- the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
- the decorative sheet may be heated and molded.
- the heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, when an ABS resin film is used as the base material layer If it exists, it can be normally about 120 to 200 ° C.
- the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.
- the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold.
- preliminary molding in-line preliminary molding
- the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding simultaneously with the injection molding
- a decorative resin molded product is manufactured.
- the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps. After the decorative sheet of the present invention is installed so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated, A pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold, After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.
- the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. If a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. In the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.
- the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made.
- the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine the decorative sheet is the first.
- the vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state.
- the resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down.
- the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface.
- the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.
- the vacuum pressure bonding method it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the moldability before the step of pressing the above-mentioned molded body against the decorative sheet.
- the vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method.
- the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, the temperature can be about 60 to 200 ° C.
- a crosslinking reaction with a blocked isocyanate can be started in the step of heating the decorative sheet.
- the reaction by the heating in the said process is inadequate, or when employ
- the molded resin layer may be formed by selecting a resin according to the application.
- the molding resin that forms the molding resin layer may be a thermoplastic resin or a thermosetting resin.
- thermoplastic resin examples include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate (PC) resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- thermosetting resin examples include urethane resin and epoxy resin. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- the decorative resin molded product of the present invention has excellent chemical resistance and high moldability of the decorative sheet, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames Interior materials for buildings such as walls, floors and ceilings; housings for home appliances such as television receivers and air conditioners; containers and the like.
- a pattern layer (thickness: 5 ⁇ m) was formed by gravure printing using an ink containing vinyl chloride-vinyl acetate-acrylic copolymer resin.
- a primer composition (acrylic polyol resin (weight average molecular weight 8000) 89.9 parts by mass, polyurethane resin (weight average molecular weight 6000) 10.1 parts by mass, hexamethylene diisocyanate 7 parts by mass) is used on the pattern layer.
- a primer layer (thickness 3 ⁇ m) was provided by gravure printing.
- the electron beam curable resin described in Table 1 and Table 2 is applied by bar coating so that the cured thickness of the resin composition is 10 ⁇ m, and the surface is made of an uncured electron beam curable resin.
- a protective layer was formed.
- the uncured surface protective layer is 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, and the base layer / pattern layer / primer layer / A decorative sheet in which the surface protective layers were laminated in this order was obtained.
- the moldability, chemical resistance, and heat-resistant adhesion of the obtained decorative sheet were evaluated as follows. The results are shown in Tables 1 and 2.
- the amount of hexamethylene diisocyanate used as a crosslinking agent (curing agent) for the primer layer was 3 parts by mass.
- Examples 13 to 18 A decorative sheet was obtained in the same manner as in Examples 1 to 12 and Comparative Examples 1 and 2, except that hexamethylene diisocyanate was not added to the primer composition. Moreover, the moldability and chemical resistance of the obtained decorative sheet were evaluated as follows. The results are shown in Tables 1 and 2.
- Formability evaluation In vacuum forming, the decorative sheet is heated to 180 ° C., a mold having a part with a stretching ratio of 100 to 250%, a mold having a part with a stretching ratio of 100 to 300%, and a stretching ratio of 100 to 350 Molding was performed using a mold having a portion that is%. The surface state of the decorative sheet after molding was visually observed, and the moldability was evaluated according to the following criteria.
- the decorative sheet was heated to 180 ° C., and the following test was performed on the decorative resin molded product obtained by injection molding using ABS resin as a molding resin.
- the temperature of the molding resin at the time of injection molding was 240 ° C.
- Sunscreen cosmetics Commercially available sunscreen cosmetics were dropped on the surface of the decorative sheet, gauze was stacked from above, and left in an oven at 80 ° C. for 1 hour. After the decorative sheet was taken out and the surface was washed away with a cleaning solution, the state of the dripping portion was visually observed, and the chemical resistance of the sunscreen cosmetic was evaluated according to the following criteria. Sunscreen cosmetics are those of commercially available SPF 50.
- Insect repellent A commercially available insect repellent was dropped on the surface of the decorative sheet, gauze was piled up, and left in an oven at 80 ° C. for 1 hour. After the decorative sheet was taken out and the surface was washed away with a cleaning solution, the state of the dripping portion was visually observed, and the chemical resistance of the insect repellent was evaluated according to the following criteria. Insect repellents are commercially available and contain 25% diet (N, N-diethyl-m-toluamide) and 75% other ingredients.
- the surface of the decorative sheet was rubbed while applying a load of 500 g to the decorative sheet using gauze containing ethanol ethanol (purity 99.5%).
- A Even when rubbing 100 times or more, the surface protective layer is not peeled off, and the chemical resistance is very high.
- ⁇ The rubbing of 50 times or more does not peel off the protective layer, and the chemical resistance is high.
- Protective layer is not peeled off by rubbing and chemical resistance is not a problem for practical use
- XX The protective layer is peeled off by rubbing less than 30 times, and chemical resistance is practically problematic
- the ionizing radiation curable resin and the blocked isocyanate are as follows. Dibutyltin dilaurate was used as the catalyst.
- Ionizing radiation curable resin (EB1) Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 64.7 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 32.3 parts by mass tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) 3 masses Department (EB2) Bifunctional polycarbonate acrylate (weight average molecular weight: 8,000) 48.5 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 48.5 parts by mass Tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) 3 masses Part Block isocyanate A: Block of hexamethylene diisocyanate (reaction initiation temperature 90 ° C.) B: Block of hexamethylene diisocyanate (reaction
- Examples 1 to 19 in which blocked isocyanate was blended with the ionizing radiation curable resin composition were excellent in chemical resistance and moldability or had no practical problem. Further, from comparison between Examples 6 to 7 and 9 to 12 and Examples 13 to 18, it can be seen that Examples 13 to 18 in which hexamethylene diisocyanate was not blended have improved moldability. Furthermore, the decorative sheets of Examples 13 to 18 that did not contain hexamethylene diisocyanate also had high adhesion after molding. On the other hand, in Comparative Examples 1 and 2 in which no blocked isocyanate was blended, although the moldability was excellent, the chemical resistance was low and it was not practically usable.
- Example 19 in which the amount of blocked isocyanate in the surface protective layer was set to 1 part by mass and the amount of the crosslinking agent in the primer layer was set to 3 parts by mass, extremely severe using a mold having a part with a maximum draw ratio of 350% Even under the molding conditions, the coating film was not cracked at an elongation of 350%, and the moldability was particularly high. Furthermore, as shown in Table 2, in Example 11 and Example 19, the heat-resistant adhesion was particularly excellent.
- the resin composition was cured to form a surface protective layer.
- the electron beam curable resin is cured by irradiating an uncured surface protective layer with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad). I let you.
- a thermosetting resin it hardened
- a thermoplastic resin nothing was done after coating.
- the moldability, adhesion, chemical resistance, and heat-resistant adhesion of the obtained decorative sheet were evaluated as follows. The results are shown in Tables 3 and 4.
- Formability evaluation In vacuum forming, the decorative sheet is heated to 180 ° C., a mold having a part with a stretching ratio of 100 to 250%, a mold having a part with a stretching ratio of 100 to 300%, and a stretching ratio of 100 to 350 Molding was performed using a mold having a portion that is%. The surface state of the decorative sheet after molding was visually observed, and the moldability was evaluated according to the following criteria.
- Ethanol aqueous solution Three gauze layers (20 mm long x 20 mm wide x about 1 mm thick) are placed on the surface of each decorative sheet after the above-described evaluation of moldability, and ethanol (purity 99.5%) is placed on the gauze. An ethanol aqueous solution was dropped until the entire surface was immersed (the amount dropped was 3 to 5 ml), and covered with a watch glass from above. After leaving this at room temperature (25 ° C.) for 1 hour, the watch glass and gauze were removed, and the state of the decorative sheet on which the gauze was placed (test surface) was visually observed.
- the evaluation criteria are as follows.
- Sunscreen Cosmetics 0.5 g of commercially available sunscreen cosmetics were uniformly applied to the surface of each decorative sheet after the above-described evaluation of moldability was performed on a portion of 50 mm length ⁇ 50 mm width. This was left in an oven at 80 ° C. for 1 hour. After taking out the decorative sheet and rinsing the surface with a cleaning solution, the state of the part where the sunscreen cosmetic was applied (test surface) was visually observed, and the chemical resistance of the sunscreen cosmetic was evaluated according to the following criteria. . Sunscreen cosmetics are those of commercially available SPF 50.
- the resins and curing agents used for the surface protective layer are as follows. Dibutyltin dilaurate was used as the catalyst.
- Resin A Thermosetting resin Acrylic polyol (Hydroxyl value: 55, Weight average molecular weight: 8,000)
- B Electron curable resin Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 65 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 32 parts by mass Tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) ) 3 parts by mass
- C thermoplastic resin acrylic resin (PMMA, weight average molecular weight 10,000)
- Curing agent a Block of hexamethylene diisocyanate trimer (reaction start temperature 110 ° C.)
- b Hexamethylene diisocyanate (HMDI)
- Examples 20 to 22 and Reference Examples 1 to 5 in which blocked isocyanate is blended in the surface protective layer and a primer layer is provided are excellent in moldability, adhesion, and chemical resistance. There was no problem in practical use. Moreover, in Reference Example 4 and Example 21 in which no curing agent was blended in the primer layer, the moldability was particularly high. Furthermore, from the comparison between Example 21 and Comparative Example 7, Example 21 in which blocked isocyanate is blended in the surface protective layer may have high adhesion even though the curing agent is not blended in the primer layer. I understand. On the other hand, in the comparative example 3 using the isocyanate which is not blocked by the surface protective layer, the moldability was poor and was not practical.
- Example 22 in which the mass ratio of the resin / curing agent of the surface protective layer was 100/1 and the mass ratio of the resin / curing agent of the primer layer was 100/3, the maximum draw ratio was 350%. Even under extremely severe molding conditions using a mold having a portion, the coating film was not cracked at a portion having an elongation of 350%, and the moldability was particularly high. Furthermore, as shown in Table 4, in Example 22, the heat-resistant adhesion was particularly excellent.
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Abstract
Description
項1. 少なくとも、基材層と、電離放射線硬化性樹脂組成物により形成された表面保護層とが積層されており、
前記表面保護層が、ブロックイソシアネートを含む、加飾シート。
項2. 前記表面保護層が、前記ブロックイソシアネートの解離反応を促進する触媒をさらに含む、項1に記載の加飾シート。
項3. 前記電離放射線硬化性樹脂組成物が、ポリカーボネート(メタ)アクリレートを含む、項1または2に記載の加飾シート。
項4. 前記ポリカーボネート(メタ)アクリレートの重量平均分子量が、5千以上である、項3に記載の加飾シート。
項5. 前記表面保護層の電離放射線硬化性樹脂組成物が、ウレタン(メタ)アクリレートをさらに含む、項3または4に記載の加飾シート。
項6. 前記ポリカーボネート(メタ)アクリレートと、前記ウレタン(メタ)アクリレートとの質量比が、50:50~99:1の範囲にある、項5に記載の加飾シート。
項7. 前記表面保護層の厚みが、1~30μmである、項1~6のいずれかに記載の加飾シート。
項8. 前記基材層と前記表面保護層との間に、プライマー層をさらに有する、項1~7のいずれかに記載の加飾シート。
項9. 前記プライマー層が、ポリオール樹脂を含む樹脂組成物により形成されている、項8に記載の加飾シート。
項10. 前記ポリオール樹脂が、アクリルポリオール、ポリエステルポリオール、及びポリカーボネートジオールからなる群から選択された少なくとも1種である、項9に記載の加飾シート。
項11. 前記ポリオール樹脂のガラス転移点(Tg)が55℃以上であり、重量平均分子量が2千以上である、項9または10に記載の加飾シート。
項12. 前記基材層と前記表面保護層との間に、絵柄層をさらに有する、項1~11のいずれかに記載の加飾シート。
項13. 前記基材層と前記プライマー層との間に、絵柄層をさらに有する、項8~11のいずれかに記載の加飾シート。
項14. 少なくとも、成形樹脂層と、基材層と、表面保護層とが積層されており、
前記表面保護層が、ブロックイソシアネートを含む電離放射線硬化性樹脂組成物の硬化物により形成されてなる、加飾樹脂成形品。
項15. 前記基材層と前記表面保護層との間に、プライマー層をさらに有する、項14に記載の加飾樹脂成形品。
項16. 項1~13のいずれかに記載の加飾シートを射出成形型に挿入し、前記射出成形型を 閉じ、流動状態の樹脂を前記射出成形型内に射出して前記樹脂と前記加飾シートとを一体化する一体化工程、
を備える、加飾樹脂成形品の製造方法。
項17. 前記加飾シートを真空成形型により予め立体形状に成形する真空成形工程を前記一体化工程の前に備える、項16に記載の加飾樹脂成形品の製造方法。
項18. 前記真空成形工程において前記加飾シートを加熱する工程を含む、項17に記載の加飾樹脂成形品の製造方法。 That is, this invention provides the invention of the aspect hung up below.
The decorative sheet, wherein the surface protective layer contains a blocked isocyanate.
Item 3. Item 3. The decorative sheet according to
Item 4. Item 4. The decorative sheet according to Item 3, wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 5,000 or more.
Item 5. Item 5. The decorative sheet according to item 3 or 4, wherein the ionizing radiation curable resin composition of the surface protective layer further contains urethane (meth) acrylate.
Item 6. Item 6. The decorative sheet according to Item 5, wherein a mass ratio of the polycarbonate (meth) acrylate and the urethane (meth) acrylate is in the range of 50:50 to 99: 1.
Item 7. Item 7. The decorative sheet according to any one of
Item 8. Item 8. The decorative sheet according to any one of
Item 9. Item 9. The decorative sheet according to Item 8, wherein the primer layer is formed of a resin composition containing a polyol resin.
Item 10. Item 10. The decorative sheet according to Item 9, wherein the polyol resin is at least one selected from the group consisting of acrylic polyol, polyester polyol, and polycarbonate diol.
Item 11. Item 11. The decorative sheet according to Item 9 or 10, wherein the polyol resin has a glass transition point (Tg) of 55 ° C or higher and a weight average molecular weight of 2,000 or higher.
Item 12. Item 12. The decorative sheet according to any one of
Item 13. Item 12. The decorative sheet according to any one of Items 8 to 11, further comprising a pattern layer between the base material layer and the primer layer.
Item 14. At least a molded resin layer, a base material layer, and a surface protective layer are laminated,
A decorative resin molded product, wherein the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a blocked isocyanate.
Item 15. Item 15. The decorated resin molded article according to Item 14, further comprising a primer layer between the base material layer and the surface protective layer.
Item 16. Item 14. The decorative sheet according to any one of
A method for producing a decorated resin molded product.
Item 17. Item 17. The method for producing a decorated resin molded article according to Item 16, comprising a vacuum forming step of forming the decorative sheet into a three-dimensional shape in advance using a vacuum forming die before the integration step.
Item 18. Item 18. The method for producing a decorated resin molded product according to Item 17, comprising a step of heating the decorative sheet in the vacuum forming step.
本発明の加飾シートは、少なくとも、基材層と、電離放射線硬化性樹脂組成物により形成された表面保護層とが積層されており、表面保護層が、ブロックイソシアネートを含むことを特徴とする。本発明の加飾シートにおいては、電離放射線硬化性樹脂組成物により形成された表面保護層が、ブロックイソシアネートを含むことにより、高い成形性を有すると共に、加飾樹脂成形品に高い耐薬品性を付与する機能を有する加飾シートとすることができる。本発明の加飾シートによって加飾樹脂成形品に高い耐薬品性を付与できる詳細な機構は必ずしも明確でないが、電離放射線硬化性樹脂組成物により形成された表面保護層がブロックイソシアネートを含むため、加飾樹脂成形品を成形する過程でブロックイソシアネートによる架橋が開始し、表面保護層の架橋密度を高めて硬く形成することができ、このため、本発明の加飾シートを用いて得られる加飾樹脂成形品は、優れた耐薬品性を発現するものと考えられる。さらに、本発明の加飾シートにおいては、加飾樹脂成形品の成形に供する前まではブロックイソシアネートによる反応を開始させることなく、表面保護層の架橋密度を低く維持することができるので、成形時における本発明の加飾シートは、適度な柔軟性を保持しており、優れた成形性も備えている。以下、本発明の加飾シートについて詳述する。 1. Decorative sheet The decorative sheet of the present invention is such that at least a base material layer and a surface protective layer formed of an ionizing radiation curable resin composition are laminated, and the surface protective layer contains a blocked isocyanate. Features. In the decorative sheet of the present invention, the surface protective layer formed of the ionizing radiation curable resin composition contains blocked isocyanate, thereby having high moldability and high chemical resistance to the decorative resin molded product. It can be set as the decorating sheet | seat which has the function to provide. Although the detailed mechanism that can impart high chemical resistance to the decorative resin molded article by the decorative sheet of the present invention is not necessarily clear, the surface protective layer formed by the ionizing radiation curable resin composition contains a blocked isocyanate, In the process of molding a decorative resin molded article, cross-linking with a blocked isocyanate starts, and the cross-linking density of the surface protective layer can be increased and hardened, and thus the decorative sheet obtained using the decorative sheet of the present invention The resin molded product is considered to exhibit excellent chemical resistance. Furthermore, in the decorative sheet of the present invention, the crosslinking density of the surface protective layer can be kept low without initiating the reaction with the blocked isocyanate until it is subjected to the molding of the decorative resin molded product. The decorative sheet of the present invention retains moderate flexibility and has excellent moldability. Hereinafter, the decorative sheet of the present invention will be described in detail.
本発明の加飾シートは、少なくとも、基材層1と、表面保護層2とがこの順に積層された積層構造を有する。本発明の加飾シートにおいて、樹脂成形品に装飾性を付与することなどを目的として、必要に応じて、絵柄層3を設けてもよい。また、基材層1の色の変化やバラツキを抑制することなどを目的として、基材層1と表面保護層2との間、絵柄層3を設ける場合であれば基材層1と絵柄層3との間などに、必要に応じて、隠蔽層5を設けてもよい。さらに、加飾シートの成形性や各層の密着性を高めることなどを目的として、基材層1と表面保護層2との間、絵柄層3を設ける場合であれば絵柄層3と表面保護層2との間などに、必要に応じて、プライマー層4などを設けてもよい。さらに、基材層1の下に、接着層6などを設けてもよい。 Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least the
[基材層1]
基材層1は、本発明の加飾シートにおいて支持体としての役割を果たす樹脂シート(樹脂フィルム)により形成されている。基材層1に使用される樹脂成分については、特に制限されず、三次元成形性や成形樹脂層との相性等に応じて適宜選定すればよいが、好ましくは、熱可塑性樹脂が挙げられる。熱可塑性樹脂としては、具体的には、アクリロニトリル-ブタジエン-スチレン樹脂(以下「ABS樹脂」と表記することもある);アクリロニトリル-スチレン-アクリル酸エステル樹脂;アクリル樹脂;ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂;ポリカーボネート樹脂;塩化ビニル系樹脂;ポリエチレンテレフタラート(PET)樹脂等が挙げられる。これらの中でも、ABS樹脂が三次元成形性の観点から好ましい。基材層1を形成する樹脂成分としては、1種類のみを用いてもよいし、2種類以上を混合して用いてもよい。また、基材層1は、これら樹脂の単層シートで形成されていてもよく、また同種又は異種樹脂による複層シートで形成されていてもよい。 Composition of each layer forming the decorative sheet [base material layer 1]
The
表面保護層2は、加飾シートの耐薬品性、耐傷付き性などを高めるために設けられる層である。表面保護層2は、電離放射線硬化性樹脂組成物により形成されてなる。さらに、表面保護層2は、ブロックイソシアネートを含む。上述の通り、本発明の加飾シートにおいては、表面保護層2がブロックイソシアネートを含んでいるため、加飾樹脂成形品を成形する過程でブロックイソシアネートによる架橋を開始させ、電離放射線硬化性樹脂組成物により形成された表面保護層2の架橋密度を高めて硬く形成することができ、得られる加飾樹脂成形品に優れた耐薬品性を付与しているものと考えられる。さらに、本発明の加飾シートにおいては、加飾樹脂成形品の成形に供する前まではブロックイソシアネートによる反応を開始させることなく、表面保護層の架橋密度を低く維持することができるので、適度な柔軟性を保持しており、優れた成形性も備えている。 [Surface protective layer 2]
The surface
表面保護層2の形成に使用される電離放射線硬化性樹脂とは、電離放射線を照射することにより、架橋、硬化する樹脂であり、具体的には、分子中に重合性不飽和結合又はエポキシ基を有するプレポリマー、オリゴマー、及び/又はモノマーを適宜混合したものが挙げられる。ここで電離放射線とは、電磁波又は荷電粒子線のうち、分子を重合あるいは架橋しうるエネルギー量子を有するものを意味し、通常紫外線(UV)又は電子線(EB)が用いられるが、その他、X線、γ線等の電磁波、α線、イオン線等の荷電粒子線も含むものである。電離放射線硬化性樹脂の中でも、電子線硬化性樹脂は、無溶剤化が可能であり、光重合用開始剤を必要とせず、安定な硬化特性が得られるため、表面保護層2の形成において好適に使用される。 (Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface
ポリカーボネート(メタ)アクリレートは、ポリマー主鎖にカーボネート結合を有し、か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、特に制限されず、例えば、ポリカーボネート骨格を有するウレタン(メタ)アクリレートなどであってもよい。また、当該(メタ)アクリレートは、架橋、硬化を良好にするという観点から、1分子当たりの官能基の数として、好ましくは2~6個が挙げられる。ポリカーボネート(メタ)アクリレートは、末端あるいは側鎖に(メタ)アクリレートを2個以上有する多官能ポリカーボネート(メタ)アクリレートであることが好ましい。ポリカーボネート(メタ)アクリレートは、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。 <Polycarbonate (meth) acrylate>
The polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and (meth) acrylate at the terminal or side chain. For example, urethane (meth) acrylate having a polycarbonate skeleton It may be. The (meth) acrylate is preferably 2 to 6 functional groups per molecule from the viewpoint of improving cross-linking and curing. The polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at the terminals or side chains. Polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.
ウレタン(メタ)アクリレートは、ポリマー主鎖にウレタン結合を有し、か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、特に制限されない。このようなウレタン(メタ)アクリレートは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアネートの反応によって得られるポリウレタンオリゴマーを、(メタ)アクリル酸でエステル化することにより得ることができる。また、ウレタン(メタ)アクリレートは、架橋、硬化を良好にするという観点から、1分子当たりの官能基の数として、好ましくは2~12個が挙げられる。ウレタン(メタ)アクリレートは、末端あるいは側鎖に(メタ)アクリレートを2個以上有する多官能ウレタン(メタ)アクリレートであることが好ましい。表面保護層2の形成に使用される電離放射線硬化性樹脂組成物に、上記のポリカーボネート(メタ)アクリレートに加えて、ウレタン(メタ)アクリレートをさらに含んでいてもよい。ウレタン(メタ)アクリレートは、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。 <Urethane (meth) acrylate>
The urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Such urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The urethane (meth) acrylate is preferably 2 to 12 functional groups per molecule from the viewpoint of improving cross-linking and curing. The urethane (meth) acrylate is preferably a polyfunctional urethane (meth) acrylate having two or more (meth) acrylates at the terminal or side chain. In addition to the polycarbonate (meth) acrylate, the ionizing radiation curable resin composition used for forming the surface
絵柄層3は、樹脂成形品に装飾性を与える層であり、基材層1と表面保護層2との間などに必要に応じて設けられる。絵柄層3は、種々の模様をインキと印刷機を使用して印刷することにより形成される。絵柄層3によって形成される模様は、特に制限されず、例えば、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、煉瓦積模様など挙げられ、これらを複合した寄木、パッチワーク等の模様も挙げられる。これらの模様は、通常の黄色、赤色、青色、及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。 [Picture layer 3]
The pattern layer 3 is a layer that gives decorativeness to the resin molded product, and is provided between the
隠蔽層5は、基材層1の色の変化やバラツキを抑制する目的で、基材層1と表面保護層2との間、絵柄層3を設ける場合であれば基材層1と絵柄層3との間などに、必要に応じて設けられる層である(図示していない)。 [Hidden layer 5]
The concealing layer 5 is provided with the
本発明の加飾シートは、表面保護層2の延伸部に微細な割れや白化を生じにくくすることなどを目的として、所望により、基材層1と表面保護層2との間、絵柄層3を設ける場合には絵柄層3と表面保護層2との間などに、プライマー層4を設けてもよい。プライマー層4は、表面保護層2の直下に設けることが好ましい。すなわち、表面保護層2とプライマー層4とが接するように設けられていることにより、表面保護層2に含まれるブロックイソシアネートが加飾樹脂成形品を成形する過程でプライマー層4を構成する下記のプライマー組成物と反応し、表面保護層2とプライマー層4とが強固に接着され、得られる加飾樹脂成形品の耐薬品性をより一層高めることが可能となる。 [Primer layer 4]
The decorative sheet of the present invention has a pattern layer 3 between the
接着層6は、加飾シートと成形樹脂との接着性や密着性を向上させることなどを目的として、基材層1の裏面に必要に応じて設けられる層である。接着層6を形成する樹脂としては、加飾シートと成形樹脂との接着性や密着性を向上させることができるものであれば、特に制限されず、例えば、熱可塑性樹脂または熱硬化性樹脂が用いられる。熱可塑性樹脂としては、例えば、アクリル樹脂、アクリル変性ポリオレフィン樹脂、塩素化ポリオレフィン樹脂、塩化ビニル-酢酸ビニル共重合体、熱可塑性ウレタン樹脂、熱可塑性ポリエステル樹脂、ポリアミド樹脂、ゴム系樹脂などが挙げられる。熱可塑性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。また、熱硬化性樹脂としては、例えば、ウレタン樹脂、エポキシ樹脂等挙げられる。熱硬化性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。 [Adhesive layer 6]
The adhesive layer 6 is a layer provided on the back surface of the
本発明の加飾樹脂成形品は、本発明の加飾シートに成形樹脂を一体化させることにより成形されてなるものである。即ち、本発明の加飾樹脂成形品は、少なくとも、成形樹脂層と、表面保護層とが積層されており、表面保護層が、ブロックイソシアネートを含む電離放射線硬化性樹脂組成物により形成されてなることを特徴とする。本発明の加飾樹脂成形品では、必要に応じて、加飾シートに上述の絵柄層3、プライマー層4、隠蔽層5などの少なくとも1層がさらに設けられていてもよい。 2. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention is formed by laminating at least a molded resin layer and a surface protective layer, and the surface protective layer is formed of an ionizing radiation curable resin composition containing a blocked isocyanate. It is characterized by that. In the decorative resin molded product of the present invention, if necessary, the decorative sheet may further be provided with at least one layer such as the above-described pattern layer 3, primer layer 4, and concealing layer 5.
本発明の加飾シートを真空成形型により予め立体形状に成形する真空成形工程、
真空成形された加飾シートの余分な部分をトリミングして成形シートを得るトリミング工程、及び
成形シートを射出成形型に挿入し、射出成形型を閉じ、流動状態の樹脂を射出成形型内に射出して樹脂と成形シートを一体化する一体化工程。 More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum forming die,
Trimming process to trim the excess part of the vacuum-decorated decorative sheet to obtain the molded sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the fluid resin into the injection mold Integration process to integrate the resin and the molded sheet.
本発明の加飾シートを、所定形状の成形面を有する可動金型の当該成形面に対し、加飾シートの基材層の表面が対面するように設置した後、当該加飾シートを加熱、軟化させると共に、可動金型側から真空吸引して、軟化した加飾シートを当該可動金型の成形面に沿って密着させることにより、加飾シートを予備成形する予備成形工程、
成形面に沿って密着された加飾シートを有する可動金型と固定金型とを型締めした後、両金型で形成されるキャビティ内に、流動状態の樹脂を射出、充填して固化させることにより樹脂成形体を形成し、樹脂成形体と加飾シートを積層一体化させる一体化工程、及び
可動金型を固定金型から離間させて、加飾シート全層が積層されてなる樹脂成形体を取り出す取出工程。 More specifically, the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated, A pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold,
After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.
(加飾シートの作製)
基材としてのABS樹脂フィルム(厚さ:400μm)上に、塩化ビニル-酢酸ビニル-アクリル系共重合体樹脂を含むインキを用いて、グラビア印刷により絵柄層(厚み5μm)を形成した。次に絵柄層の上に、プライマー組成物(アクリルポリオール樹脂(重量平均分子量8000)89.9質量部、ポリウレタン樹脂(重量平均分子量6000)10.1質量部、ヘキサメチレンジイソシアネート7質量部)を用いてグラビア印刷によりプライマー層(厚み3μm)を設けた。次に、表1及び表2に記載の電子線硬化性樹脂を、樹脂組成物の硬化後の厚みが10μmとなるようにバーコートにより塗工し、未硬化の電子線硬化性樹脂からなる表面保護層を形成した。次に、未硬化の表面保護層に対して、加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、電子線硬化性樹脂を硬化させ、基材層/絵柄層/プライマー層/表面保護層がこの順に積層された加飾シートを得た。次に、得られた加飾シートの成形性、耐薬品性、及び耐熱密着性を以下のようにして評価した。結果を表1及び表2に示す。なお、実施例19では、プライマー層の架橋剤(硬化剤)として用いたヘキサメチレンジイソシアネートの量を3質量部とした。 <Examples 1 to 12, 19 and Comparative Examples 1 and 2>
(Preparation of decorative sheet)
On an ABS resin film (thickness: 400 μm) as a substrate, a pattern layer (thickness: 5 μm) was formed by gravure printing using an ink containing vinyl chloride-vinyl acetate-acrylic copolymer resin. Next, a primer composition (acrylic polyol resin (weight average molecular weight 8000) 89.9 parts by mass, polyurethane resin (weight average molecular weight 6000) 10.1 parts by mass, hexamethylene diisocyanate 7 parts by mass) is used on the pattern layer. A primer layer (thickness 3 μm) was provided by gravure printing. Next, the electron beam curable resin described in Table 1 and Table 2 is applied by bar coating so that the cured thickness of the resin composition is 10 μm, and the surface is made of an uncured electron beam curable resin. A protective layer was formed. Next, the uncured surface protective layer is 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, and the base layer / pattern layer / primer layer / A decorative sheet in which the surface protective layers were laminated in this order was obtained. Next, the moldability, chemical resistance, and heat-resistant adhesion of the obtained decorative sheet were evaluated as follows. The results are shown in Tables 1 and 2. In Example 19, the amount of hexamethylene diisocyanate used as a crosslinking agent (curing agent) for the primer layer was 3 parts by mass.
プライマー組成物にヘキサメチレンジイソシアネートを配合しなかったこと以外は、実施例1~12及び比較例1~2と同様にして、加飾シートを得た。また、得られた加飾シートの成形性及び耐薬品性を以下のようにして評価した。結果を表1及び表2に示す。 <Examples 13 to 18>
A decorative sheet was obtained in the same manner as in Examples 1 to 12 and Comparative Examples 1 and 2, except that hexamethylene diisocyanate was not added to the primer composition. Moreover, the moldability and chemical resistance of the obtained decorative sheet were evaluated as follows. The results are shown in Tables 1 and 2.
真空成形にて、加飾シートを180℃に加熱し、延伸倍率が100~250%となる部分を有する型、延伸倍率が100~300%となる部分を有する型、及び延伸倍率が100~350%となる部分を有する型を用いて成形を行った。成形後の加飾シートの表面状態を目視で観察し、成形性を以下の基準で評価した。
◎◎◎:伸度350%の部分で塗膜の割れがなく、成形性が特に高い
◎◎:伸度300%の部分で塗膜の割れがなく、成形性が極めて高い
◎:伸度250%の部分で塗膜の割れがなく、成形性が非常に高い
○:伸度200%の部分で塗膜の割れがなく、成形性が高い
△:伸度150%の部分で塗膜の割れがなく、成形性は実用上問題がない
××:伸度150%未満の部分で塗膜の割れがあり、成形性は実用上問題がある (Formability evaluation)
In vacuum forming, the decorative sheet is heated to 180 ° C., a mold having a part with a stretching ratio of 100 to 250%, a mold having a part with a stretching ratio of 100 to 300%, and a stretching ratio of 100 to 350 Molding was performed using a mold having a portion that is%. The surface state of the decorative sheet after molding was visually observed, and the moldability was evaluated according to the following criteria.
◎◎◎: No cracking of coating film at 350% elongation and particularly high moldability ◎◎: No cracking of coating film at 300% elongation and extremely high formability ◎: 250 elongation %: No cracking of the coating film and very high moldability ○: No cracking of the coating film at 200% elongation, high moldability Δ: Cracking of the coating film at 150% elongation No, there is no practical problem with formability XX: There is a crack in the coating film at a portion where the elongation is less than 150%, and the moldability is practically problematic
加飾シートを180℃に加熱し、ABS樹脂を成形樹脂として用いた射出成形によって得られた加飾樹脂成形品について、以下の試験を行った。なお、射出成形時の成形樹脂の温度は、240℃とした。 (Chemical resistance evaluation)
The decorative sheet was heated to 180 ° C., and the following test was performed on the decorative resin molded product obtained by injection molding using ABS resin as a molding resin. The temperature of the molding resin at the time of injection molding was 240 ° C.
市販の日焼け止め化粧料を加飾シート表面に滴下し、上からガーゼを重ね、80℃のオーブン内に1時間放置した。加飾シートを取り出し、洗浄液で表面を洗い流した後、滴下部分の状態を目視で観察して、日焼け止め化粧料について耐薬品性を以下の基準で評価した。日焼け止め化粧料は、市販のSPF50のものであり、成分として、1-(4-メトキシフェニル)-3-(4-tert-ブチルフェニル)-1,3-プロパンジオン 3%、サリチル酸3,3,5-トリメチルシクロヘキシル 10%、サリチル酸2-エチルヘキシル 5%、2-シアノ-3,3-ジフェニルアクリル酸2-エチルヘキシル 10%を含有している。
◎:ガーゼ跡が残らず、耐薬品性が非常に高い
○:ガーゼ跡は残るものの軽微であり、耐薬品性が高い
△:ガーゼ跡が滴下面全体には残らず、耐薬品性は実用上問題ない
××:ガーゼ跡が滴下面全体に残り、耐薬品性は実用上問題ある Sunscreen cosmetics Commercially available sunscreen cosmetics were dropped on the surface of the decorative sheet, gauze was stacked from above, and left in an oven at 80 ° C. for 1 hour. After the decorative sheet was taken out and the surface was washed away with a cleaning solution, the state of the dripping portion was visually observed, and the chemical resistance of the sunscreen cosmetic was evaluated according to the following criteria. Sunscreen cosmetics are those of commercially available SPF 50. As ingredients, 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) -1,3-propanedione 3%, salicylic acid 3,3 , 5-trimethylcyclohexyl 10%, 2-ethylhexyl salicylate 5% and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate 10%.
◎: No gauze traces left and chemical resistance is very high ○: Gauze traces remain but slight and high in chemical resistance △: No gauze traces remain on the entire dripping surface, and chemical resistance is practical No problem XX: Gauze marks remain on the entire dripping surface, and there is a practical problem with chemical resistance
市販の虫除け剤を加飾シート表面に滴下し、ガーゼを重ね、80℃のオーブン内に1時間放置した。加飾シートを取り出し、洗浄液で表面を洗い流した後、滴下部分の状態を目視で観察して、虫除け剤について耐薬品性を以下の基準で評価した。虫除け剤は、市販のものであり、成分として、ディート(N,N-ジエチル-m-トルアミド)25%、その他75%を含む。
◎:ガーゼ跡が残らず、耐薬品性が非常に高い
○:ガーゼ跡は残るものの軽微であり、耐薬品性が高い
△:ガーゼ跡が滴下面全体には残らず、耐薬品性は実用上問題ない
××:ガーゼ跡が滴下面全体に残り、耐薬品性は実用上問題ある Insect repellent A commercially available insect repellent was dropped on the surface of the decorative sheet, gauze was piled up, and left in an oven at 80 ° C. for 1 hour. After the decorative sheet was taken out and the surface was washed away with a cleaning solution, the state of the dripping portion was visually observed, and the chemical resistance of the insect repellent was evaluated according to the following criteria. Insect repellents are commercially available and contain 25% diet (N, N-diethyl-m-toluamide) and 75% other ingredients.
◎: No gauze traces left and chemical resistance is very high ○: Gauze traces remain but slight and high in chemical resistance △: No gauze traces remain on the entire dripping surface, and chemical resistance is practical No problem XX: Gauze marks remain on the entire dripping surface, and there is a practical problem with chemical resistance
エタノール(純度99.5%)を含むガーゼを用いて加飾シートに対して500gの荷重をかけながら、加飾シート表面をラビングした。
◎:100回以上のラビングでも、表面保護層の剥がれがなく、耐薬品性が非常に高い
○:50回以上のラビングで保護層の剥がれがなく、耐薬品性が高い
△:30回以上のラビングで保護層の剥がれがなく、耐薬品性は実用上問題ない
××:30回未満のラビングで保護層の剥がれがあり、耐薬品性は実用上問題ある The surface of the decorative sheet was rubbed while applying a load of 500 g to the decorative sheet using gauze containing ethanol ethanol (purity 99.5%).
A: Even when rubbing 100 times or more, the surface protective layer is not peeled off, and the chemical resistance is very high. ○: The rubbing of 50 times or more does not peel off the protective layer, and the chemical resistance is high. Protective layer is not peeled off by rubbing and chemical resistance is not a problem for practical use XX: The protective layer is peeled off by rubbing less than 30 times, and chemical resistance is practically problematic
実施例4、11、17、19、比較例1、2で得られた加飾シートを、それぞれ、180℃に加熱し、延伸倍率が100~300%となる部分を有する型を用いて真空成形を行った。次に、ABS樹脂を成形樹脂として用いた射出成形によって、加飾樹脂成形品を得た。なお、射出成形時の成形樹脂の温度は、240℃とした。得られた加飾樹脂成形品を、110℃、相対湿度15%の環境下で1週間静置した後、表面保護層の剥がれについて評価した。評価基準は、以下の通りである。結果を表2に示す。
◎:表面保護層の剥がれは全く見られず、耐熱密着性は非常に良好である。
〇:表面保護層の剥がれが若干見られたが、軽微であり、耐熱密着性は良好である。
△:表面保護層の剥がれが若干見られたが、実用上問題ない。
××:表面保護層が剥がれ、実用上問題がある。 (Heat resistant adhesion evaluation)
The decorative sheets obtained in Examples 4, 11, 17, 19 and Comparative Examples 1 and 2 were each heated to 180 ° C., and vacuum forming was performed using a mold having a part with a draw ratio of 100 to 300%. Went. Next, a decorative resin molded product was obtained by injection molding using ABS resin as a molding resin. The temperature of the molding resin at the time of injection molding was 240 ° C. The obtained decorative resin molded product was allowed to stand for 1 week in an environment of 110 ° C. and a relative humidity of 15%, and then evaluated for peeling of the surface protective layer. The evaluation criteria are as follows. The results are shown in Table 2.
A: The surface protective layer is not peeled off at all, and the heat resistant adhesion is very good.
◯: Some peeling of the surface protective layer was observed, but it was slight and good in heat-resistant adhesion.
Δ: Some peeling of the surface protective layer was observed, but there was no practical problem.
XX: The surface protective layer is peeled off and there is a problem in practical use.
電離放射線硬化性樹脂
(EB1)
2官能ポリカーボネートアクリレート(重量平均分子量:1万) 64.7質量部
2官能ポリカーボネートアクリレート(重量平均分子量:2万) 32.3質量部
4官能シリコーン変性ウレタンアクリレート(重量平均分子量:6千) 3質量部
(EB2)
2官能ポリカーボネートアクリレート(重量平均分子量:8千) 48.5質量部
2官能ポリカーボネートアクリレート(重量平均分子量:2万) 48.5質量部
4官能シリコーン変性ウレタンアクリレート(重量平均分子量:6千) 3質量部
ブロックイソシアネート
A:ヘキサメチレンジイソシアネートのブロック体(反応開始温度90℃)
B:ヘキサメチレンジイソシアネートのブロック体(反応開始温度110℃) In Table 1 and Table 2, the ionizing radiation curable resin and the blocked isocyanate are as follows. Dibutyltin dilaurate was used as the catalyst.
Ionizing radiation curable resin (EB1)
Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 64.7 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 32.3 parts by mass tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) 3 masses Department (EB2)
Bifunctional polycarbonate acrylate (weight average molecular weight: 8,000) 48.5 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 48.5 parts by mass Tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) 3 masses Part
Block isocyanate A: Block of hexamethylene diisocyanate (reaction initiation temperature 90 ° C.)
B: Block of hexamethylene diisocyanate (reaction start temperature 110 ° C.)
(加飾シートの作製)
基材としてのABS樹脂フィルム(厚さ:400μm)上に、アクリル樹脂をバインダーとするインキを用いて、グラビア印刷により木目柄の絵柄層(厚み5μm)を形成した。次に絵柄層の全面に、表3及び表4に記載の組成を有するプライマー組成物を用いてグラビア印刷によりプライマー層(厚み2μm)を設けた。次に、表3及び表4に記載の樹脂(電子線硬化性樹脂、熱硬化性樹脂、または熱可塑性樹脂)を、樹脂組成物の硬化後の厚みが10μmとなるようにバーコートにより塗工した。次に、樹脂組成物を硬化させて、表面保護層を形成した。次に、電子線硬化性樹脂を用いた場合については、未硬化の表面保護層に対して、加速電圧165kV、照射線量50kGy(5Mrad)の電子線を照射して、電子線硬化性樹脂を硬化させた。また、熱硬化性樹脂を用いた場合については、硬化が完了するまで40℃で養生した。熱可塑性樹脂を用いた場合については、塗工後特に何もしなかった。以上のようにして、基材層/絵柄層/プライマー層/表面保護層がこの順に積層された加飾シートを得た。次に、得られた加飾シートの成形性、密着性、耐薬品性、及び耐熱密着性を以下のようにして評価した。結果を表3及び表4に示す。 <Reference Examples 1 to 5, Examples 20 to 22 and Comparative Examples 3 to 7>
(Preparation of decorative sheet)
On an ABS resin film (thickness: 400 μm) as a substrate, a woodgrain pattern layer (thickness: 5 μm) was formed by gravure printing using an ink having an acrylic resin as a binder. Next, a primer layer (
真空成形にて、加飾シートを180℃に加熱し、延伸倍率が100~250%となる部分を有する型、延伸倍率が100~300%となる部分を有する型、及び延伸倍率が100~350%となる部分を有する型を用いて成形を行った。成形後の加飾シートの表面状態を目視で観察し、成形性を以下の基準で評価した。
◎◎◎:伸度350%の部分で塗膜の割れがなく、成形性が特に高い
◎◎:伸度300%の部分で塗膜の割れがなく、成形性が極めて高い
◎:伸度250%の部分で塗膜の割れがなく、成形性が非常に高い
○:伸度200%の部分で塗膜の割れがなく、成形性が高い
△:伸度150%の部分で塗膜の割れがなく、成形性は実用上問題がない
××:伸度150%未満の部分で塗膜の割れがあり、成形性は実用上問題がある (Formability evaluation)
In vacuum forming, the decorative sheet is heated to 180 ° C., a mold having a part with a stretching ratio of 100 to 250%, a mold having a part with a stretching ratio of 100 to 300%, and a stretching ratio of 100 to 350 Molding was performed using a mold having a portion that is%. The surface state of the decorative sheet after molding was visually observed, and the moldability was evaluated according to the following criteria.
◎◎◎: No cracking of coating film at 350% elongation and particularly high moldability ◎◎: No cracking of coating film at 300% elongation and extremely high formability ◎: 250 elongation %: No cracking of the coating film and very high moldability ○: No cracking of the coating film at 200% elongation, high moldability Δ: Cracking of the coating film at 150% elongation No, there is no practical problem with formability XX: There is a crack in the coating film at a portion where the elongation is less than 150%, and the moldability is practically problematic
上記の成形性評価を行った後の各加飾シートの表面に対して、カッターで長さ5mm、間隔2mmで縦11本、横11本の切れ込みを入れ、縦10マス×横10マスの合計100マスの碁盤目状の切れ込みを形成した。この切れ込みの上から、ニチバン社製のセロテープ(登録商標)(No.405-1P)を圧着した後、急激に剥離することにより、表面保護層の密着性を評価した。評価基準は以下の通りである。
◎:剥離が全く見られない
○:剥離が目視では見られない
×:剥離が見られる (Evaluation of adhesion)
With respect to the surface of each decorative sheet after performing the above-described moldability evaluation, a length of 5 mm and an interval of 2 mm are cut by a cutter with 11 vertical and 11 horizontal cuts, and a total of 10 vertical by 10 horizontal A 100 square grid cut was formed. From the top of this notch, cello tape (registered trademark) (No. 405-1P) manufactured by Nichiban was pressed and then peeled off rapidly to evaluate the adhesion of the surface protective layer. The evaluation criteria are as follows.
◎: No peeling at all ○: No peeling is observed visually ×: Peeling is seen
エタノール水溶液
上記の成形性評価を行った後の各加飾シートの表面に、ガーゼ(縦20mm×横20mm×厚み約1mm)を3枚重ねにして置き、エタノール(純度99.5%)をガーゼ全面が浸されるまでエタノール水溶液を滴下し(滴下量は3~5ml)、上から時計皿で被覆した。これを室温(25℃)で1時間放置した後、時計皿及びガーゼを取り除いて、加飾シートのガーゼをのせていた部分(試験表面)の状態を目視で観察した。評価基準は以下の通りである。
◎:試験表面に塗膜の割れや白化、膨潤、艶低下、剥離等の異常が見られず、外観は良好だった
○:試験表面の一部に軽微な塗膜の割れや白化、膨潤、艶低下、剥離等が確認されたが、外観は実用上問題なかった
△:試験表面の全体に軽微な塗膜の割れや白化、膨潤、艶低下、剥離等が確認され、外観が悪く実用上問題があった
×:試験表面の全面に塗膜の割れや白化、膨潤、艶低下、剥離等の異常が確認され、外観が悪く実用上問題があった (Chemical resistance evaluation)
Ethanol aqueous solution Three gauze layers (20 mm long x 20 mm wide x about 1 mm thick) are placed on the surface of each decorative sheet after the above-described evaluation of moldability, and ethanol (purity 99.5%) is placed on the gauze. An ethanol aqueous solution was dropped until the entire surface was immersed (the amount dropped was 3 to 5 ml), and covered with a watch glass from above. After leaving this at room temperature (25 ° C.) for 1 hour, the watch glass and gauze were removed, and the state of the decorative sheet on which the gauze was placed (test surface) was visually observed. The evaluation criteria are as follows.
A: No abnormalities such as cracking, whitening, swelling, loss of gloss, peeling, etc. were observed on the test surface, and the appearance was good. Deterioration of gloss, peeling, etc. were confirmed, but the appearance was not a problem for practical use. Δ: Slight cracking, whitening, swelling, loss of gloss, peeling, etc. were observed on the entire test surface, and the appearance was poor and practical. There was a problem x: Abnormalities such as cracking, whitening, swelling, gloss loss, peeling, etc. were confirmed on the entire test surface, and the appearance was poor and there were practical problems
上記の成形性評価を行った後の各加飾シートの表面に対して、縦50mm×横50mmの部分に市販の日焼け止め化粧料0.5gを均一に塗布した。これを80℃のオーブン内に1時間放置した。加飾シートを取り出し、洗浄液で表面を洗い流した後、日焼け止め化粧料を塗布した部分(試験表面)の状態を目視で観察して、日焼け止め化粧料について耐薬品性を以下の基準で評価した。日焼け止め化粧料は、市販のSPF50のものであり、成分として、1-(4-メトキシフェニル)-3-(4-tert-ブチルフェニル)-1,3-プロパンジオン 3%、サリチル酸3,3,5-トリメチルシクロヘキシル 10%、サリチル酸2-エチルヘキシル 5%、2-シアノ-3,3-ジフェニルアクリル酸2-エチルヘキシル 10%を含有している。
◎:試験表面に塗膜の割れや白化、膨潤、艶低下、剥離等の異常が見られず、外観は良好だった
○:試験表面の一部に軽微な塗膜の割れや白化、膨潤、艶低下、剥離等が確認されたが、外観は実用上問題なかった
△:試験表面の全体に軽微な塗膜の割れや白化、膨潤、艶低下、剥離等が確認され、外観が悪く実用上問題があった
×:試験表面の全面に塗膜の割れや白化、膨潤、艶低下、剥離等の異常が確認され、外観が悪く実用上問題があった Sunscreen Cosmetics 0.5 g of commercially available sunscreen cosmetics were uniformly applied to the surface of each decorative sheet after the above-described evaluation of moldability was performed on a portion of 50 mm length × 50 mm width. This was left in an oven at 80 ° C. for 1 hour. After taking out the decorative sheet and rinsing the surface with a cleaning solution, the state of the part where the sunscreen cosmetic was applied (test surface) was visually observed, and the chemical resistance of the sunscreen cosmetic was evaluated according to the following criteria. . Sunscreen cosmetics are those of commercially available SPF 50. As ingredients, 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) -1,3-propanedione 3%, salicylic acid 3,3 , 5-trimethylcyclohexyl 10%, 2-ethylhexyl salicylate 5% and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate 10%.
A: No abnormalities such as cracking, whitening, swelling, loss of gloss, peeling, etc. were observed on the test surface, and the appearance was good. Deterioration of gloss, peeling, etc. were confirmed, but the appearance was not a problem for practical use. Δ: Slight cracking, whitening, swelling, loss of gloss, peeling, etc. were observed on the entire test surface, and the appearance was poor and practical. There was a problem x: Abnormalities such as cracking, whitening, swelling, gloss loss, peeling, etc. were confirmed on the entire test surface, and the appearance was poor and there were practical problems
実施例20~22、比較例5で得られた加飾シートを、それぞれ、180℃に加熱し、延伸倍率が100~300%となる部分を有する型を用いて真空成形を行った。次に、ABS樹脂を成形樹脂として用いた射出成形によって、加飾樹脂成形品を得た。なお、射出成形時の成形樹脂の温度は、240℃とした。得られた加飾樹脂成形品を、110℃、相対湿度15%の環境下で1週間静置した後、表面保護層の剥がれについて評価した。評価基準は、以下の通りである。結果を表4に示す。
◎:表面保護層の剥がれは全く見られず、耐熱密着性は非常に良好である。
〇:表面保護層の剥がれが若干見られたが、軽微であり、耐熱密着性は良好である。
△:表面保護層の剥がれが若干見られたが、実用上問題ない。
××:表面保護層が剥がれ、実用上問題がある。 (Heat resistant adhesion evaluation)
The decorative sheets obtained in Examples 20 to 22 and Comparative Example 5 were each heated to 180 ° C., and vacuum-molded using molds having portions with a draw ratio of 100 to 300%. Next, a decorative resin molded product was obtained by injection molding using ABS resin as a molding resin. The temperature of the molding resin at the time of injection molding was 240 ° C. The obtained decorative resin molded product was allowed to stand for 1 week in an environment of 110 ° C. and a relative humidity of 15%, and then evaluated for peeling of the surface protective layer. The evaluation criteria are as follows. The results are shown in Table 4.
A: The surface protective layer is not peeled off at all, and the heat resistant adhesion is very good.
◯: Some peeling of the surface protective layer was observed, but it was slight and good in heat-resistant adhesion.
Δ: Some peeling of the surface protective layer was observed, but there was no practical problem.
XX: The surface protective layer is peeled off and there is a problem in practical use.
樹脂
A:熱硬化性樹脂
アクリルポリオール(水酸基価:55、重量平均分子量:8千)
B:電子線硬化性樹脂
2官能ポリカーボネートアクリレート(重量平均分子量:1万) 65質量部
2官能ポリカーボネートアクリレート(重量平均分子量:2万) 32質量部
4官能シリコーン変性ウレタンアクリレート(重量平均分子量:6千)3質量部
C:熱可塑性樹脂
アクリル樹脂(PMMA、重量平均分子量1万)
硬化剤
a:ヘキサメチレンジイソシアネートトリマーのブロック体(反応開始温度110℃)
b:ヘキサメチレンジイソシアネート(HMDI) In Tables 3 and 4, the resins and curing agents used for the surface protective layer are as follows. Dibutyltin dilaurate was used as the catalyst.
Resin A: Thermosetting resin Acrylic polyol (Hydroxyl value: 55, Weight average molecular weight: 8,000)
B: Electron curable resin Bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) 65 parts by mass Bifunctional polycarbonate acrylate (weight average molecular weight: 20,000) 32 parts by mass Tetrafunctional silicone-modified urethane acrylate (weight average molecular weight: 6,000) ) 3 parts by mass C: thermoplastic resin acrylic resin (PMMA, weight average molecular weight 10,000)
Curing agent a: Block of hexamethylene diisocyanate trimer (reaction start temperature 110 ° C.)
b: Hexamethylene diisocyanate (HMDI)
2…表面保護層
3…絵柄層
4…プライマー層 DESCRIPTION OF
Claims (18)
- 少なくとも、基材層と、電離放射線硬化性樹脂組成物により形成された表面保護層とが積層されており、
前記表面保護層が、ブロックイソシアネートを含む、加飾シート。 At least, a base material layer and a surface protective layer formed of an ionizing radiation curable resin composition are laminated,
The decorative sheet, wherein the surface protective layer contains a blocked isocyanate. - 前記表面保護層が、前記ブロックイソシアネートの解離反応を促進する触媒をさらに含む、請求項1に記載の加飾シート。 The decorative sheet according to claim 1, wherein the surface protective layer further comprises a catalyst that promotes a dissociation reaction of the blocked isocyanate.
- 前記電離放射線硬化性樹脂組成物が、ポリカーボネート(メタ)アクリレートを含む、請求項1または2に記載の加飾シート。 The decorative sheet according to claim 1 or 2, wherein the ionizing radiation curable resin composition contains polycarbonate (meth) acrylate.
- 前記ポリカーボネート(メタ)アクリレートの重量平均分子量が、5千以上である、請求項3に記載の加飾シート。 The decorative sheet according to claim 3, wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 5,000 or more.
- 前記表面保護層の電離放射線硬化性樹脂組成物が、ウレタン(メタ)アクリレートをさらに含む、請求項3または4に記載の加飾シート。 The decorative sheet according to claim 3 or 4, wherein the ionizing radiation curable resin composition of the surface protective layer further comprises urethane (meth) acrylate.
- 前記ポリカーボネート(メタ)アクリレートと、前記ウレタン(メタ)アクリレートとの質量比が、50:50~99:1の範囲にある、請求項5に記載の加飾シート。 The decorative sheet according to claim 5, wherein a mass ratio of the polycarbonate (meth) acrylate and the urethane (meth) acrylate is in the range of 50:50 to 99: 1.
- 前記表面保護層の厚みが、1~30μmである、請求項1~6のいずれかに記載の加飾シート。 The decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer has a thickness of 1 to 30 µm.
- 前記基材層と前記表面保護層との間に、プライマー層をさらに有する、請求項1~7のいずれかに記載の加飾シート。 The decorative sheet according to any one of claims 1 to 7, further comprising a primer layer between the base material layer and the surface protective layer.
- 前記プライマー層が、ポリオール樹脂を含む樹脂組成物により形成されている、請求項8に記載の加飾シート。 The decorative sheet according to claim 8, wherein the primer layer is formed of a resin composition containing a polyol resin.
- 前記ポリオール樹脂が、アクリルポリオール、ポリエステルポリオール、及びポリカーボネートジオールからなる群から選択された少なくとも1種である、請求項9に記載の加飾シート。 The decorative sheet according to claim 9, wherein the polyol resin is at least one selected from the group consisting of acrylic polyol, polyester polyol, and polycarbonate diol.
- 前記ポリオール樹脂のガラス転移点(Tg)が55℃以上であり、重量平均分子量が2千以上である、請求項9または10に記載の加飾シート。 The decorative sheet according to claim 9 or 10, wherein the polyol resin has a glass transition point (Tg) of 55 ° C or higher and a weight average molecular weight of 2,000 or higher.
- 前記基材層と前記表面保護層との間に、絵柄層をさらに有する、請求項1~11のいずれかに記載の加飾シート。 The decorative sheet according to any one of claims 1 to 11, further comprising a pattern layer between the base material layer and the surface protective layer.
- 前記基材層と前記プライマー層との間に、絵柄層をさらに有する、請求項8~11のいずれかに記載の加飾シート。 The decorative sheet according to any one of claims 8 to 11, further comprising a pattern layer between the base material layer and the primer layer.
- 少なくとも、成形樹脂層と、基材層と、表面保護層とが積層されており、
前記表面保護層が、ブロックイソシアネートを含む電離放射線硬化性樹脂組成物の硬化物により形成されてなる、加飾樹脂成形品。 At least a molded resin layer, a base material layer, and a surface protective layer are laminated,
A decorative resin molded product, wherein the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a blocked isocyanate. - 前記基材層と前記表面保護層との間に、プライマー層をさらに有する、請求項14に記載の加飾樹脂成形品。 The decorative resin molded product according to claim 14, further comprising a primer layer between the base material layer and the surface protective layer.
- 請求項1~13のいずれかに記載の加飾シートを射出成形型に挿入し、前記射出成形型を閉じ、流動状態の樹脂を前記射出成形型内に射出して前記樹脂と前記加飾シートとを一体化する一体化工程、
を備える、加飾樹脂成形品の製造方法。 The decorative sheet according to any one of claims 1 to 13 is inserted into an injection mold, the injection mold is closed, and a resin in a fluid state is injected into the injection mold so that the resin and the decorative sheet are injected. Integration process to integrate
A method for producing a decorated resin molded product. - 前記加飾シートを真空成形型により予め立体形状に成形する真空成形工程を前記一体化工程の前に備える、請求項16に記載の加飾樹脂成形品の製造方法。 The method for producing a decorated resin molded product according to claim 16, comprising a vacuum forming step of forming the decorative sheet into a three-dimensional shape in advance by a vacuum forming die before the integration step.
- 前記真空成形工程において前記加飾シートを加熱する工程を含む、請求項17に記載の加飾樹脂成形品の製造方法。 The manufacturing method of the decorative resin molded product of Claim 17 including the process of heating the said decorating sheet in the said vacuum forming process.
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EP15770105.3A EP3124233A4 (en) | 2014-03-24 | 2015-03-24 | Decorative sheet and decorative resin-molded article |
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