WO2015147006A1 - Feuille décorative et article décoratif en résine moulée - Google Patents

Feuille décorative et article décoratif en résine moulée Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
decorative sheet
resin
layer
meth
surface protective
Prior art date
Application number
PCT/JP2015/058970
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English (en)
Japanese (ja)
Inventor
咲恵 片岡
齋藤　信雄
愛 阿波
秀明 小池
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014196998A external-priority patent/JP2015193210A/ja
Priority claimed from JP2014196999A external-priority patent/JP6806425B2/ja
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to CN201580015872.8A priority Critical patent/CN106103086A/zh
Priority to KR1020167028298A priority patent/KR20160138111A/ko
Priority to EP15770105.3A priority patent/EP3124233A4/fr
Priority to US15/128,180 priority patent/US10286634B2/en
Publication of WO2015147006A1 publication Critical patent/WO2015147006A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille décorative présentant une excellente aptitude au moulage, et un article décoratif en résine moulée qui fait appel à ladite feuille décorative et présente une excellente résistance chimique. Dans la feuille décorative, au moins une couche de substrat et une couche de protection de surface formée d'une composition de résine durcissable par rayonnement ionisant sont empilées. La couche de protection de surface renferme un isocyanate bloqué.
PCT/JP2015/058970 2014-03-24 2015-03-24 Feuille décorative et article décoratif en résine moulée WO2015147006A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201580015872.8A CN106103086A (zh) 2014-03-24 2015-03-24 装饰片和装饰树脂成型品
KR1020167028298A KR20160138111A (ko) 2014-03-24 2015-03-24 장식 시트 및 장식 수지 성형품
EP15770105.3A EP3124233A4 (fr) 2014-03-24 2015-03-24 Feuille décorative et article décoratif en résine moulée
US15/128,180 US10286634B2 (en) 2014-03-24 2015-03-24 Decorative sheet and decorative resin-molded article

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2014-060828 2014-03-24
JP2014-060827 2014-03-24
JP2014060828 2014-03-24
JP2014060827 2014-03-24
JP2014196998A JP2015193210A (ja) 2013-09-27 2014-09-26 加飾シート及び加飾樹脂成形品
JP2014-196999 2014-09-26
JP2014-196998 2014-09-26
JP2014196999A JP6806425B2 (ja) 2013-09-27 2014-09-26 加飾シート及び加飾樹脂成形品

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03157414A (ja) * 1989-07-25 1991-07-05 Sekisui Chem Co Ltd 熱硬化性被覆用シートと被覆物の製造方法
JP2000102949A (ja) * 1998-09-30 2000-04-11 Dainippon Printing Co Ltd 被覆成形品の製造方法
JP2007062254A (ja) * 2005-09-01 2007-03-15 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法
JP2009184284A (ja) * 2008-02-08 2009-08-20 Toray Ind Inc 積層フィルム
JP2013082216A (ja) * 2011-09-26 2013-05-09 Dainippon Printing Co Ltd 加飾シート及びその製造方法、並びに加飾成形品
JP2013082217A (ja) * 2011-09-26 2013-05-09 Dainippon Printing Co Ltd 加飾シート及びその製造方法、並びに加飾成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03157414A (ja) * 1989-07-25 1991-07-05 Sekisui Chem Co Ltd 熱硬化性被覆用シートと被覆物の製造方法
JP2000102949A (ja) * 1998-09-30 2000-04-11 Dainippon Printing Co Ltd 被覆成形品の製造方法
JP2007062254A (ja) * 2005-09-01 2007-03-15 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法
JP2009184284A (ja) * 2008-02-08 2009-08-20 Toray Ind Inc 積層フィルム
JP2013082216A (ja) * 2011-09-26 2013-05-09 Dainippon Printing Co Ltd 加飾シート及びその製造方法、並びに加飾成形品
JP2013082217A (ja) * 2011-09-26 2013-05-09 Dainippon Printing Co Ltd 加飾シート及びその製造方法、並びに加飾成形品

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3124233A4 *

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