WO2015046549A1 - 加飾シート及び加飾樹脂成形品 - Google Patents
加飾シート及び加飾樹脂成形品 Download PDFInfo
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- WO2015046549A1 WO2015046549A1 PCT/JP2014/075972 JP2014075972W WO2015046549A1 WO 2015046549 A1 WO2015046549 A1 WO 2015046549A1 JP 2014075972 W JP2014075972 W JP 2014075972W WO 2015046549 A1 WO2015046549 A1 WO 2015046549A1
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- Prior art keywords
- decorative sheet
- decorative
- meth
- acrylate
- raised portion
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- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
-
- 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 is a decorative sheet having a raised portion on the surface, the crack of the raised portion at the time of molding is effectively suppressed, and further, the design characteristics and scratch resistance due to the uneven shape of the raised portion after molding It is related with the decoration sheet
- the present invention also relates to a decorative resin molded product 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.
- Patent Document 1 discloses a decorative sheet having a concavo-convex shape by a method different from embossing, and has a thickness of 2 ⁇ m or more on one side of a base sheet and a test method defined in Japanese Industrial Standard (JIS) K5400.
- JIS Japanese Industrial Standard
- a concavo-convex insert sheet is disclosed in which at least fine concavo-convex layers having a pencil hardness of HB or higher are laminated.
- Patent Document 2 the arrangement and size of the raised portion that forms the uneven pattern on the surface of the decorative decorative film, the total area with respect to the entire surface of the base sheet is 45% or less, and one raised portion It has been proposed to improve the problem that cracks occur at the top of the ridge by defining the area of 2 mm 2 or less.
- the present invention is a decorative sheet having a raised portion on the surface, the crack of the raised portion during molding is effectively suppressed, and the uneven shape of the raised portion after molding.
- the main object is to provide a decorative sheet that is also excellent in design and scratch resistance.
- the present inventor has intensively studied to solve the above problems.
- the cured product of the ionizing radiation curable resin is heated at a temperature of 25 ° C. and relative
- Martens hardness at a humidity of 50% in the range of 10 to 120 N / mm 2
- cracks in the raised portion during molding are effectively suppressed, and further, the design properties due to the uneven shape of the raised portion after molding. It was found that scratch resistance was also achieved.
- 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 On the base sheet, it has a raised portion formed of a cured product of an ionizing radiation curable resin composition,
- the cured product of the ionizing radiation curable resin is a decorative sheet having a Martens hardness of 10 to 120 N / mm 2 at a temperature of 25 ° C. and a relative humidity of 50%.
- Item 2. Item 2. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin composition at the top includes a urethane (meth) acrylate oligomer.
- Item 3. Item 3.
- the decorative sheet according to item 1 or 2 wherein a thickness of the raised portion is 10 ⁇ m or more.
- Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the plurality of raised portions are independent of each other.
- Item 6. The decorative sheet according to any one of Items 1 to 5, wherein each of the plurality of raised portions has an area of 100 mm 2 or less when viewed from the lamination direction of the decorative sheet.
- Item 7. Item 7.
- Item 8. Item 8.
- Item 9. Item 9. The decorative sheet according to Item 7 or 8, wherein the content of the silicone component in the ionizing radiation curable resin composition of the surface protective layer is 5% by mass or less.
- Item 10. Item 10. The decorative sheet according to any one of Items 7 to 9, wherein the ionizing radiation curable resin composition of the surface protective layer contains polycarbonate (meth) acrylate.
- Item 11 Item 11.
- the decorative sheet according to Item 10 wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 5000 or more.
- Item 12. Item 12.
- Item 13 Item 12.
- the mass ratio of the polycarbonate (meth) acrylate and the urethane (meth) acrylate contained in the ionizing radiation curable resin composition of the surface protective layer is in the range of 50:50 to 99: 1.
- Item 14. Item 14.
- Item 16. Item 16.
- Item 17. A molded resin layer, a base sheet, and a raised portion formed of a cured product of an ionizing radiation curable resin composition on the base sheet are laminated in this order, The cured product of the ionizing radiation curable resin composition at the top is a decorated resin molded product having a Martens hardness in the range of 10 to 120 N / mm 2 at a temperature of 25 ° C. and a relative humidity of 50%.
- Item 18. Item 18.
- the decorative sheet of the present invention has a raised portion formed of a cured product of an ionizing radiation curable resin composition on a substrate sheet, and the cured product of the ionizing radiation curable resin has a temperature of 25.
- the Martens hardness at 10 ° C. and 50% relative humidity is in the range of 10 to 120 N / mm 2 .
- the Martens hardness at a temperature of 25 ° C. and a relative humidity of 50% of the cured product of the ionizing radiation curable resin composition forming the raised portion is in the range of 10 to 120 N / mm 2.
- molding is suppressed effectively, Furthermore, the design property by the uneven
- the decorative sheet according to the present invention is formed with a cured product of an ionizing radiation curable resin composition having a raised portion having a Martens hardness in the specific range. The crack of the said upper part at the time of shaping
- the decorative sheet of the present invention may not have a decorative layer or a concealing layer, and may be, for example, transparent.
- 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 a raised portion 2 is formed on a base sheet 1.
- a raised portion 2 is formed on a base sheet 1.
- an uneven shape is formed on the surface of the decorative sheet by the raised portion 2 on the base sheet 1.
- the support sheet 3 may be provided as necessary for the purpose of improving the moldability of the decorative sheet.
- the primer layer 6 is provided as necessary for the purpose of improving the adhesion between the surface protective layer 5 and the layer located below (on the opposite side of the raised portion 2). May be.
- a laminated structure of the decorative sheet of the present invention a laminated structure in which the base sheet / the upper part is laminated in this order; a laminated structure in which the adhesive layer / the decorative layer / the base sheet / the upper part are laminated in this order; a support sheet / Laminated structure in which decorative layer / base material sheet / upper portion is laminated in this order; laminated structure in which base material sheet / decorative layer / primer layer / surface protective layer / upper portion are laminated in this order; decorative layer / base material sheet / Surface protective layer / laminated structure in which the upper part is laminated in this order; adhesive layer / support sheet / decoration layer / base material sheet / laminated structure in which the laminated structure in which the upper part is laminated in this order is laminated Can be mentioned.
- FIG. 1 and 2 show schematic cross-sectional views of an example of a decorative sheet in which the base sheet / the upper portion are stacked in this order as an aspect of the laminated structure of the decorative sheet of the present invention.
- FIG. 3 is a schematic cross-sectional view of an example of a decorative sheet in which a support sheet / adhesive layer / decorative layer / base material sheet / upper portion is laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention Indicates.
- FIG. 4 is a schematic cross-sectional view of an example of a decorative sheet in which a base sheet / decoration layer / primer layer / surface protective layer / laminated layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. Indicates.
- the base material sheet 1 is a layer that functions as a base material of the decorative sheet.
- a raised portion 2 described later is formed on the surface of the base material sheet 1.
- the surface protective layer 5 is provided between the base sheet 1 and the raised portion 2, the raised portion 2 is formed on the surface of the surface protective layer 5.
- the base sheet 1 is made of resin. Although it does not restrict
- thermoplastic resin forming the base sheet 1 examples include acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins Polyester resins such as polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylate resin;
- PET polyethylene terephthalate
- ABS resin acrylonitrile-butadiene-styrene resin
- the base material sheet 1 is provided on the surface side of the decorative sheet (the upper part 2 side) and the upper part 2 is formed on the base material sheet 1, among these, the upper part 2 at the time of molding.
- Acrylic resin is preferable from the viewpoint of effectively suppressing cracking and further enhancing the design by the uneven shape of the raised portion 2 after molding.
- ABS resin is preferable among these resins from the viewpoint of moldability and the like.
- a thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- thermosetting resin for forming the base sheet 1 is not particularly limited, and examples thereof include acrylic polyols; polyester polyols; urethane polyols such as polyester urethane polyols and acrylic urethane polyols; polyethylene polyols, polypropylene polyols, polybutadiene polyols, polyisoprenes.
- Polyol resins such as polyols such as polyols; Among these, acrylic polyol is preferable among these from the viewpoint of improving the moldability of the decorative sheet.
- Specific examples of preferred acrylic polyols include those exemplified in the primer layer 6 described later.
- a thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- a resin sheet formed of the above resin can be used. It does not restrict
- the base sheet 1 is usually about 30 to 300 ⁇ m, preferably about 50 to 200 ⁇ m.
- the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.
- the surface protective layer 5 and the raised portion 2 are laminated on the base sheet 1, the thickness of the base sheet 1 can be the same as that of the support sheet 3 described later.
- the raised portion 2 is formed on the base material sheet 1, and the decorativeness formed by the raised portion 2 imparts design properties to the decorated sheet.
- the raised portion 2 can be formed on the surface of the base material sheet 1, and when the decorative sheet of the present invention has a surface protective layer 5 described later, it is formed on the surface of the surface protective layer 5. be able to.
- the individual raised portions 2 may be independent from each other as shown in FIG. 1, or may be connected to each other as shown in FIG. 2.
- the raised portion 2 is formed of a cured product of an ionizing radiation curable resin composition, and further, the Martens hardness of the cured product forming the raised portion 2 at a temperature of 25 ° C. and a relative humidity of 50% is 10 to 120 N / It is in the range of mm 2.
- the raised portion 2 is formed on a cured product of the ionizing radiation curable resin composition having the Martens hardness within the specific range. The crack of the said upper part 2 at the time of shaping
- the upper part 2 having the Martens hardness also has an appropriate elasticity, the shape of the upper part 2 is suitably maintained even when heating / pressurization is applied during molding, It is also excellent in design due to the uneven shape of the raised portion 2. Furthermore, since the upper portion 2 having the Martens hardness is formed of a cured product of the ionizing radiation curable resin composition, it has excellent scratch resistance.
- the Martens hardness of the cured product forming the raised portion 2 at a temperature of 25 ° C. and a relative humidity of 50% may be in the range of 10 to 120 N / mm 2 , but preferably in the range of 10 to 115 N / mm 2. Can be mentioned.
- the above-mentioned Martens hardness of the cured product forming the raised portion 2 is measured at a temperature of 25 ° C. and a relative humidity of 50% using a surface film property tester (PICODETOR HM-500, manufactured by Fisher Instruments Co., Ltd.).
- the specific measurement method is as follows. In this measuring method, a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used to push the diamond indenter into the raised portion 2 and from the indentation load F and the indentation depth h (indentation depth).
- the hardness is obtained by the following formula (1).
- the indentation conditions are as follows.
- the load from 0 to 2 mN is first applied for 2 seconds to the top 2 of the decorative sheet, and then at a load of 2 mN. Hold for 5 seconds, and finally unload from 2 to 0 mN in 2 seconds.
- the Martens hardness of the cured product of the ionizing radiation curable resin composition is the molecular weight of the ionizing radiation curable resin, the number of polymerizable functional groups contained in one molecule, and the ionizing radiation curable contained in the ionizing radiation curable resin composition.
- the ionizing radiation curable resin composition is composed of a resin composition containing an ionizing radiation curable resin.
- a resin composition containing an ionizing radiation curable resin containing an ionizing radiation curable resin.
- the ionizing radiation curable resin used for forming the upper portion 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group is present in the molecule. What mixed the prepolymer, oligomer, and / or monomer which it has suitably is mentioned.
- 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 and stable curing characteristics can be obtained.
- 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.
- the urethane (meth) acrylate oligomer is effective from the viewpoint of effectively suppressing cracks in the raised portion during molding and further enhancing the design and scratch resistance of the raised and recessed portions after shaping. Is preferred.
- 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.
- these ionizing radiations Among the curable resins, it is preferable to use at least one of urethane (meth) acrylate and polyester (meth) acrylate, and it is more preferable to use urethane (meth) acrylate.
- the urethane (meth) acrylate used suitably as ionizing radiation curable resin in formation of the upper part 2 is explained in full detail.
- 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 raised portion 2 may further contain other (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, but examples include a weight average molecular weight of 1,000 or more, preferably 2,000 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.
- the content of urethane (meth) acrylate in the ionizing radiation curable resin composition used for forming the upper portion 2 is particularly limited as long as the effect of the present invention is achieved. However, from the viewpoint of further improving the moldability of the decorative sheet, it is preferably about 5 to 50% by mass, more preferably about 20 to 50% by mass.
- various additives can be blended in the upper portion 2 according to desired physical properties to be provided in the upper portion 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 raised portion 2 after curing is not particularly limited, but is preferably 10 ⁇ m or more, more preferably about 10 to 100 ⁇ m, and still more preferably about 20 to 40 ⁇ m.
- the thickness in such a range is satisfied, the crack of the upper portion 2 at the time of molding the decorative sheet is further effectively suppressed, and further, the design property and the scratch resistance due to the uneven shape of the upper portion after molding are further improved. This can be further improved.
- Formation of the upper portion 2 is performed, for example, by preparing the above ionizing radiation curable resin composition, applying it, and curing by crosslinking.
- the viscosity of the ionizing radiation curable resin composition is not applied on the base material sheet 1 (on the surface of the base material sheet 1 or on the surface of the surface protective layer 5) which forms the raised portion 2 by a coating method described later. Any viscosity that can form a cured resin layer may be used.
- the prepared coating solution is formed on the base sheet 1 (on the surface of the base sheet 1 or on the surface of the surface protective layer 5) so as to have the above thickness, gravure coating, bar coating, It is applied by a known method such as roll coating, reverse roll coating, comma coating, or a molding plate cylinder method described in JP-A No. 2002-240078 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, thereby forming the raised portion 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 acceleration voltage is selected so that the transmission depth of the electron beam and the thickness of the raised portion 2 are substantially equal.
- 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 ionizing radiation curable resin composition forming the surface protective layer 5 is used.
- an ionizing radiation curable resin composition for forming the raised portion 2 is laminated on the ionizing radiation curable resin composition, and then both the surface protective layer 5 and the raised portion 2 are formed.
- FIG. 1 When the ionizing radiation is irradiated twice in forming the surface protective layer 5 and the raised portion 2, the type of ionizing radiation used in each step may be the same or different. More specifically, a case where both the surface protective layer 5 and the raised portion 2 are cured by irradiation with an electron beam, a case where the surface protective layer 5 is cured by an electron beam, and the raised portion 2 is cured by irradiation with ultraviolet rays are exemplified.
- the ionizing radiation is irradiated twice in forming the surface protective layer 5 and the raised portion 2
- the type of ionizing radiation used in each step may be the same or different. More specifically, a case where both the surface protective layer 5 and the raised portion 2 are cured by irradiation with an electron beam, a case where the surface protective layer 5 is cured by
- the area of the raised portion 2 is not particularly limited and is appropriately set according to a desired design to be applied to the decorative sheet. For example, it is 100 mm 2 or less, preferably 50 mm 2 or less, more preferably 20 mm 2. More preferably, it is 10 mm 2 or less, more preferably 5 mm 2 or less.
- the cured product of the electron radiation curable resin composition forming the raised portion 2 has a Martens hardness in the specific range. Even when the area is 2 mm 2 or more, cracking of the raised portion 2 at the time of molding of the decorative sheet is effectively suppressed, and furthermore, the design and unevenness due to the uneven shape of the raised portion after molding are excellent. Yes.
- the decorative sheet is excellent in moldability and scratch resistance.
- the lower limit of the area is not particularly limited, but is preferably 0.01 mm 2 or more from the viewpoint of being visually recognized as an uneven pattern.
- the areas of the plurality of raised portions 2 may be the same as or different from each other.
- the area of the raised portion 2 or the like refers to an area when viewed from the lamination direction of the decorative sheet, and more specifically, a value measured by a measurement method described later.
- each raised portion 2 may be independent as shown in FIGS. 7A and 7C, for example, and the horizontal of the decorative sheet as shown in FIGS. 2, 7 ⁇ / b> B and 7 ⁇ / b> D, for example.
- the raised portions 2 may be connected to each other.
- FIG. 7D a rectangular pattern of one minimum unit is formed by four linear raised portions 2.
- the raised portion 2 is the entire surface on the side where the raised portion 2 of the decorative sheet is formed (the surface of the base sheet 1 on which the raised portion 2 is formed or the surface of the surface protective layer 5). It may be formed.
- the total area of the raised portion 2 relative to the entire area of the decorative sheet (for example, the entire surface on the side where the raised portion 2 of the decorative sheet is formed (the surface of the base sheet 1 on which the raised portion 2 is formed, the surface protective layer)
- the ratio of the total area of the raised portion 2 to the area of the surface 5) is not particularly limited, but is usually 90% or less, preferably 60% or less, more preferably 55% or less.
- the decorative sheet of the present invention since the cured product of the electron radiation curable resin composition forming the raised portion 2 has the Martens hardness in the specific range, the entire surface of the decorative sheet. Even in the case where the ratio of the total area of the raised portion 2 to the area is within such a ratio range, cracking of the raised portion 2 at the time of molding the decorative sheet is effectively suppressed, and further, Excellent in design and scratch resistance due to the uneven shape.
- one area of the raised portion 2 (area when the decorative sheet is viewed from the stacking direction), the ratio of the total area of the raised portion 2 to the total area of the decorative sheet, the distance between the raised portions 2 Specifically, the thickness of the raised portion 2 is a value measured as follows.
- the raised portion 2 is, for example, a cross-sectional shape as shown in FIG. 6A formed by applying an ionizing radiation curable resin composition on the surface of the base sheet 1 or the surface protective layer 5 and dripping the composition. Moreover, it becomes a cross-sectional shape like FIG. 6B formed intentionally.
- one area of the raised portion 2 is the area of the portion where the raised portion 2 and the base sheet 1 or the surface protective layer 5 are in contact (the portion surrounded by W). Area), and the total area is the sum.
- the ratio of the total area of the raised portion 2 to the area of the entire surface of the decorative sheet can be obtained by dividing the total area by the area of the entire surface of the decorative sheet.
- the distance between the adjacent raised portions 2 is the distance between the end portions (L portion) when the outer edge of the portion where the raised portion 2 and the base sheet 1 or the surface protective layer 5 are in contact with each other.
- the thickness of the raised portion 2 is the height of the highest portion of the raised portion 2 (H portion), that is, the raised portion 2 and the base sheet 1 in contact with the raised portion 2. Or the height difference from the surface protective layer 5.
- the shape of the raised portion 2 is not particularly limited, and is circular, elliptical, triangular, quadrangular (for example, FIG. 7A), FIG. 7B, etc., 5 to 10 square, star shape, linear (for example, FIG. 7C, FIG. 7D). Etc.), and a shape such as an arc shape, a geometric pattern, and a character shape is preferable.
- the shape of each raised part 2 may mutually be the same, and may differ.
- the design expressed by each raised portion 2 may be a regular pattern shape in which the raised portions 2 are regularly arranged, or may be an irregular pattern.
- An irregular pattern is preferable because it has excellent tactile sensation, matte feeling, glossiness, and design, and if it has a regular pattern shape that is regularly arranged, stress during decorative molding concentrates on a specific part. It is preferable in that it is difficult and cracks on the surface uneven pattern are less likely to occur.
- the pattern formed by the upper part 2 is not particularly limited.
- a geometric pattern such as a circle, an ellipse, a polygon, a line drawing, a polka dot, a stripe, a lattice, a character, a wood pattern, a bamboo pattern, a stone A pattern, a tiled pattern, a brick laminated pattern, a cloth pattern, a leather pattern, etc. are preferably mentioned, and these may be used alone or in combination of two or more.
- the support sheet 3 is a layer provided as necessary for the purpose of enhancing the moldability, and has a complicated shape that requires a high degree of elongation of the decorative sheet. It is preferably provided when used for decorating a molded product.
- seat 3 does not need to be provided.
- the support sheet 3 is formed of a resin sheet (resin film) that serves as a support member.
- the resin component used for the support sheet 3 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the injection resin layer, and the like, and preferably a thermoplastic resin.
- the thermoplastic resin 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.
- a resin component which forms the support body sheet 3 only 1 type may be used and 2 or more types may be mixed and used. Further, the support sheet 3 may be formed of a single layer sheet of these resins, or may be formed of a multilayer sheet of the same kind or different kind of resin.
- the support sheet 3 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 with an adjacent layer.
- the oxidation method performed as the surface treatment of the support sheet 3 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method.
- corrugated method performed as surface treatment of the support body sheet 3 the sandblasting method, the solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the support sheet 3, and preferably a corona discharge treatment method from the viewpoints of effects and operability.
- the support sheet 3 may be colored with a coloring agent, painted for adjusting the color, or formed with a pattern for imparting design.
- the thickness of the support sheet 3 is not particularly limited and is appropriately set depending on 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 support sheet 3 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 5 is a layer provided as necessary between the base sheet 1 and the raised portion 2 for the purpose of enhancing the scratch resistance and chemical resistance of the decorative resin molded product.
- the raised portion 2 is formed on the surface protective layer 5.
- the resin for forming the surface protective layer 5 is not particularly limited as long as it can enhance the scratch resistance and chemical resistance of the decorative resin molded product and can form the raised portion 2.
- a thermoplastic resin, a heat Examples thereof include curable resins and ionizing radiation curable resins, and ionizing radiation curable resins are preferred from the viewpoint of scratch resistance and chemical resistance. It does not restrict
- the surface protective layer 5 is formed of an ionizing radiation curable resin, it is possible to leave it as an uncured layer in the state of the decorative sheet, and to cure after laminating with the molded resin layer.
- the surface protective layer 5 since the raised portion 2 is formed of a cured product of the ionizing radiation curable resin composition, the surface protective layer 5 is also formed as a cured product of the ionizing radiation curable resin composition in a decorative sheet state. Is preferable for the convenience of producing a decorative sheet and a decorative resin molded product.
- the surface protective layer 5 can be blended with various additives exemplified in the above-described raised portion 2 according to desired physical properties to be provided in the surface protective layer 5.
- the ionizing radiation curable resin composition is crosslinked on a base sheet formed of an acrylic resin or the like like the decorative sheet disclosed in Patent Document 2 described above.
- the substrate sheet may be deteriorated by irradiating not only the uncured ridge but also the substrate sheet with ionizing radiation.
- the folding workability of the decorative sheet is deteriorated.
- the trimming sheet is cracked when trimming to remove an excess portion after preforming is performed. There may be a problem with the formability of the sheet.
- the surface protective layer 5 formed of the cured product of the ionizing radiation curable resin composition is provided on the base sheet 1, and the embossed portion 2 is formed on the surface of the surface protective layer 5.
- the surface protective layer 5 is not easily deteriorated by ionizing radiation irradiated when forming the raised portion, the surface protective layer 5 is not easily cracked during molding, and is excellent in moldability. Furthermore, by forming both the surface protective layer 5 and the raised portion 2 with a cured product of the ionizing radiation curable resin composition, a decorative sheet having excellent scratch resistance can be obtained.
- the ionizing radiation curable resin contained in the composition is preferably polycarbonate (meta). It is preferable to use acrylate. 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 is not particularly limited as long as it has a carbonate bond in the polymer main chain and has a (meth) acrylate in the terminal or side chain, as already described in the explanation of the top 2. .
- 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.
- the polycarbonate polyol used for the production of the polycarbonate (meth) acrylate has a carbonate bond in the polymer main chain and has 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. It is a polymer having.
- a typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction of a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as 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.
- R1 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 the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.
- the content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition used for forming the surface protective layer 5 is particularly limited as long as the effects of the present invention are exhibited. Although it does not restrict
- urethane (meth) acrylate used for forming the surface protective layer 5
- those described in the upper part 2 can be used.
- the molecular weight of the urethane (meth) acrylate used for forming the surface protective layer 5 is not particularly limited.
- the weight average molecular weight is 5,000 or more, preferably 10,000 or more, and the upper limit does not make the viscosity too high. From the viewpoint of control, the weight average molecular weight is 100,000 or less, preferably 50,000 or less.
- 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 content of the silicone component in the ionizing radiation curable resin composition for forming the surface protective layer 5 from the viewpoint of enhancing the adhesion between the surface protective layer 5 and the above-described raised portion 2. Is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and most preferably substantially free of a silicone component.
- the silicone component in the ionizing radiation curable resin composition refers to a component having a structure in the molecule formed by alternately bonding silicon having organic groups and oxygen, specifically, a polysiloxane skeleton.
- Reactive silicone in which a reactive organic group such as amino group, vinyl group, epoxy group, carboxyl group, acrylic group, methacryl group is introduced into the side chain or terminal of the silicone oil as the main component, or in the side chain or terminal
- a reactive organic group such as amino group, vinyl group, epoxy group, carboxyl group, acrylic group, methacryl group
- Non-reactive silicones introduced with non-reactive organic groups such as alkyl groups, ether groups, higher fatty acids, silicone-modified resins with modified side chains or terminals such as organic resins, ionizing radiation curable resins, etc. Can be mentioned.
- the thickness of the surface protective layer 5 is not particularly limited, but is preferably 1000 ⁇ m or less, more preferably about 1 to 50 ⁇ m, still more preferably about 1 to 30 ⁇ m, and still 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, when the surface protective layer 5 is formed of an ionizing radiation curable resin composition, it can be uniformly irradiated with ionizing radiation, so that it can be uniformly cured, which is economically advantageous. become.
- the above-mentioned resin for forming the surface protective layer 5 is formed on the layer positioned below the surface protective layer 5 so as to have the thickness, gravure coat, bar coat, roll coat, reverse roll coat. It can be formed by applying a known method such as comma coating, preferably gravure coating.
- an uncured resin layer can be hardened similarly to the above-described raised portion 2.
- the primer layer 6 is a layer provided as necessary for the purpose of improving the adhesion between the surface protective layer 5 and the layer located therebelow.
- Primer compositions constituting the primer layer 6 include urethane resin, (meth) acrylic resin, (meth) acrylic-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 these resins can be used alone or in combination of two or more. Among these, urethane resins, (meth) acrylic resins, and (meth) acrylic-urethane copolymer resins are preferable.
- polyurethane resin polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used.
- polyol polyhydric alcohol
- isocyanate as a crosslinking agent
- the polyol one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used.
- 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.
- 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.
- acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking material. It is preferable to use in combination with hexamethylene diisocyanate.
- (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 layer 6 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 6 is not particularly limited, but preferably 0.1 ⁇ m or more. When it is 0.1 ⁇ m or more, the surface protective layer 5 has an effect of preventing cracking, breaking, whitening, and the like. On the other hand, if the thickness of the primer layer 6 is 10 ⁇ m or less, it is preferable that when the primer layer 6 is applied, the coating film is stable in drying and curing, so that the three-dimensional formability does not vary.
- the decoration layer 4 is a layer provided as necessary for the purpose of imparting decoration to the resin molded product.
- the decorative layer 4 can be provided on the raised portion 2 side of the base sheet 1, and the base sheet 1 is transparent (including translucent). Can be provided on the opposite side of the raised portion 2.
- the decorative layer 4 may form a pattern, may be solid, or a combination thereof.
- the decoration layer 4 is formed, for example, by printing various patterns using ink and a printing machine.
- the pattern formed by the decorative layer 4 is not particularly limited, and for example, a wood pattern, a marble pattern (for example, a travertine marble pattern) or the like, a stone pattern that simulates the surface of a rock, or a cloth that simulates a cloth or cloth 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 a 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 decoration layer 4 is not particularly limited, but may be about 1 to 30 ⁇ m, preferably about 1 to 20 ⁇ m, for example.
- the decoration layer 4 may be a metal thin film layer.
- the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these.
- the method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above-described metal.
- the concealing layer may be provided with a concealing layer (not shown) as needed for the purpose of suppressing color change and variation of the decorative sheet.
- the concealing layer is usually provided in order to prevent the sheet provided on the back side of the decorative layer 4 or the molded resin layer 8 from adversely affecting the color tone or pattern of the decorative resin molded product, it is generally an opaque color. Formed as a layer.
- the hiding layer is formed 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 concealing layer is appropriately selected from those used for the picture layer 4 described above.
- the concealing layer is usually set to a thickness of about 1 to 20 ⁇ m and is desirably formed as a so-called solid printing layer.
- the adhesive layer 7 can be provided on the back surface of the decorative sheet (on the opposite side to the raised portion 2) as necessary for the purpose of improving the adhesion between the decorative sheet and the molded resin layer 8 and the like.
- the resin that forms the adhesive layer 7 is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molded resin layer 8.
- a thermoplastic resin or a thermosetting resin can be used. Resin is used.
- thermoplastic resin examples 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. .
- a thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- thermosetting resin examples include a urethane resin and an epoxy resin.
- a thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.
- the adhesive layer 7 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decoration method by sticking on a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided. When used in the vacuum pressure 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 the molded resin layer 8 with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention includes at least a molded resin layer, a base sheet, and a raised portion formed of a cured product of an ionizing radiation curable resin composition formed on the base sheet. And a cured product of the ionizing radiation curable resin having a Martens hardness in the range of 10 to 120 N / mm 2 at a temperature of 25 ° C. and a relative humidity of 50%. .
- FIG. 8 shows a molded resin layer / support sheet obtained by laminating the decorative sheet of the mode shown in FIG. 3 on the molded resin layer 8 as one mode of the laminated structure of the decorated resin molded product of the present invention.
- 1 shows a schematic cross-sectional view of an example of a decorative sheet in which / adhesive layer / decorative layer / base sheet / upper portion is laminated in this order.
- 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.
- an insert molding method and an injection molding simultaneous decorating method are preferable.
- the decorative resin molded product of the present invention is a decorative molding method in which the decorative sheet of the present invention is adhered onto a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be produced.
- the raised portion 2 is formed on a cured product of the ionizing radiation curable resin composition having the Martens hardness in the specific range, so that the raised portion 2 has appropriate flexibility and elasticity. Even if it is manufactured by the above-described decorative molding methods involving heating and pressurization, cracks and deformation of the raised portion 2 are effectively suppressed.
- the raised portion 2 of the decorative sheet of the present invention is pressed against the injection mold and receives a large pressure. Even in such a case, the decorative decoration of the present invention is used. The raised portion 2 in the resin molded product is maintained in a good shape before molding.
- 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, but can usually be 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.
- the decorative sheet of the present invention is such that the surface of the decorative sheet on the base sheet 1 side (opposite to the raised portion 2) faces the molding surface of the movable mold having a molding surface of a predetermined shape.
- the decorative sheet is heated and softened, and vacuumed from the movable mold side, and the softened decorative sheet is brought into close contact with the molding surface of the movable mold, thereby decorating the decorative sheet.
- a preforming step to preform 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. Usually, it can 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 sheet is the first.
- 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. Finally, 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 this step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but can usually be about 60 to 200 ° C.
- cured material of the ionizing radiation curable resin composition was provided on the base material sheet 1, and the embossed part 2 was formed on the said surface protection layer 5
- the surface protective layer 5 is not easily deteriorated by ionizing radiation irradiated when forming the raised portion, the surface protective layer 5 is hardly cracked at the time of molding, and is excellent in moldability.
- a conventional decorative sheet having a raised portion is liable to be cracked when bent, and problems are likely to occur when performing trimming as described in the explanation of the insert molding method and the vacuum pressure bonding method.
- a decorative sheet in which a surface protective layer 5 formed of a cured product of the curable resin composition is provided and a raised portion 2 is formed on the surface protective layer 5 is used in a molding method in which trimming is performed during molding. Useful in some cases.
- 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 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 cracks at the top of the decorative sheet after the molding of the decorative sheet are effectively suppressed, and further, the design and the scratch resistance due to the uneven shape of the top after the molding.
- 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; home appliances such as television receivers and air conditioners Product casing; can be used as a container.
- Examples 1A to 4A and Comparative Examples 1A to 2A >> (Preparation of decorative sheet)
- Example 1A> A decorative layer (thickness: polybutylmethacrylate / vinyl chloride-vinyl acetate copolymer) on the back surface of a base sheet made of a non-colored transparent acrylic resin sheet having a thickness of 75 ⁇ m mainly composed of polymethyl methacrylate. 1 ⁇ m), and an adhesive layer (thickness 10 ⁇ m) composed of polymethyl methacrylate and a two-component curable urethane resin adhesive was sequentially laminated. Next, a support sheet (thickness 400 ⁇ m) made of ABS resin was laminated on the adhesive layer by dry lamination.
- Example 2A A decorative sheet for three-dimensional molding was obtained in the same manner as in Example 1A, except that the following ionizing radiation curable resin composition was used.
- ionizing radiation curable resin composition Urethane acrylate oligomer (weight average molecular weight of about 8000) 30% by mass, trifunctional acrylate monomer 50% by mass, photosensitive compound 5% by mass, photopolymerization initiator: 5% by mass, a mixture of filler and pigment in total 10% by mass
- Example 3A A decorative sheet for three-dimensional molding was obtained in the same manner as in Example 1A, except that the following ionizing radiation curable resin composition was used.
- ionizing radiation curable resin composition Urethane acrylate oligomer (weight average molecular weight of about 5000) 20% by mass, bifunctional acrylate monomer 60% by mass, photosensitive compound 5% by mass, photopolymerization initiator: 5% by mass, a mixture of filler and pigment in total 10% by mass
- Example 4A A decorative sheet for three-dimensional molding was obtained in the same manner as in Example 1A, except that the following ionizing radiation curable resin composition was used.
- ionizing radiation curable resin composition Urethane acrylate oligomer (weight average molecular weight of about 8000) 20% by mass, bifunctional acrylate monomer 60% by mass, photosensitive compound 5% by mass, photopolymerization initiator: 5% by mass, a mixture of filler and pigment in total 10% by mass
- Example 1A A decorative sheet for three-dimensional molding was obtained in the same manner as in Example 1A, except that the following ionizing radiation curable resin composition was used.
- ionizing radiation curable resin composition Polyester acrylate oligomer (weight average molecular weight of about 2000) 10% by mass, bifunctional acrylate monomer 68% by mass, thermoplastic resin 10% by mass, photosensitive compound 5% by mass, photopolymerization initiator 5% by mass, total of filler and pigment 2% by weight of mixture
- Example 2A A decorative sheet for three-dimensional molding was obtained in the same manner as in Example 1A, except that the following ionizing radiation curable resin composition was used.
- ionizing radiation curable resin composition Urethane acrylate oligomer (weight average molecular weight of about 5000) 40% by mass, bifunctional acrylate monomer 40% by mass, photosensitive compound 5% by mass, photopolymerization initiator 5% by mass, filler and pigment in total 10% by mass
- Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows.
- a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used.
- a diamond indenter was pushed into the upper portion, and the hardness was determined from the indentation load F and the indentation depth h (indentation depth) by the following equation (2).
- the indentation conditions are as follows.
- the load from 0 to 2 mN is first applied for 2 seconds to the top 2 of the decorative sheet, and then the load is 2 mN. This was held for 5 seconds, and finally unloading from 2 to 0 mN was performed in 2 seconds.
- the arithmetic average roughness Ra of the surface of the decorative resin molded product obtained from the decorative sheets of Examples 1A to 4A and Comparative Examples 1A to 2A was measured as follows. Using a surface roughness measuring instrument (product surface “Handy Surf E-35A” manufactured by Tokyo Seimitsu Co., Ltd.), in accordance with JIS B 0601: 2001, the roughness curve of length L is folded from the center line, and each roughness is measured. The value obtained by dividing the total area obtained by the length curve and the center line by the length L was expressed in micrometers ( ⁇ m), and the results are shown in Table 1.
- the Martens hardness of the cured product of the ionizing radiation curable resin composition forming the raised portion is in the range of 10 to 120 N / mm 2.
- cracks in the upper portion due to heat and pressure during molding were effectively suppressed.
- these decorative sheets were excellent in unevenness after molding, had a large arithmetic average roughness Ra, and were also excellent in scratch resistance.
- Reference Examples 1 to 10 and Comparative Reference Example 1 >> (Preparation of a decorative sheet before forming the top) A decorative layer (thickness 5 ⁇ m) was formed by gravure printing on an ABS resin film (thickness: 400 ⁇ m) as a base material using an ink containing vinyl chloride-vinyl acetate-acrylic copolymer resin. Next, a primer layer (thickness 3 ⁇ m) was provided on the decorative layer by gravure printing using the primer composition.
- the primer composition is a composition containing 89.9 parts by mass of acrylic polyol resin (weight average molecular weight 8000), 10.1 parts by mass of polyurethane resin (weight average molecular weight 6000), and 7 parts by mass of hexamethylene diisocyanate.
- an electron beam curable resin having the composition shown in Table 2 is applied by bar coating so that the cured thickness of the resin composition is 10 ⁇ m or 5 ⁇ 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 a base sheet / decoration layer / primer layer /
- the decorative sheet before the formation of the raised portion in which the surface protective layers were laminated in this order was obtained.
- the following test 1 was performed on the decorative sheet before forming the top.
- a laminated film of an acrylic resin substrate (thickness 75 ⁇ m) and an ABS resin film (thickness 400 ⁇ m) was used for Test 1 as it was. The results are shown in Table 3.
- the uncured raised portion is irradiated with an ultraviolet ray having an accumulated light amount of 600 mJ / cm 2 to cure the ultraviolet curable resin, and the base sheet / decoration layer / primer layer / surface protective layer / raised portion becomes A decorative sheet laminated in this order was obtained.
- the ratio of the total area of the raised portion to the area of the entire surface protective layer was 35%.
- the following test 2 was performed about this decorating sheet. The results are shown in Table 4. In Comparative Reference Example 2, a raised portion was formed on the acrylic resin substrate.
- the electron beam curable resins in Table 2 are as follows.
- ⁇ Test 1 Test for a decorative sheet before forming a raised portion> Scratch resistance (claw scratch) The surface of the decorative sheet was scratched 10 times with a nail, the surface was visually observed and evaluated according to the following criteria. The results are shown in Table 3. ⁇ : Trace disappears after scratch and scratch resistance is high ⁇ : Trace remains slightly after scratch and scratch resistance is slightly low, but there is no problem in practical use ⁇ : Trace remains after scratch, scratch resistance is low, practical use There is an upper problem
- Scratch resistance (steel wool) The surface of the decorative sheet was rubbed 10 times with a load of 1.5 kgf using steel wool (# 0000), and the surface was visually observed and evaluated according to the following criteria. The results are shown in Table 3. ⁇ : Scratches disappear after rubbing and scratch resistance is high ⁇ : Scratches remain a little after rubbing and scratch resistance is slightly low, but there is no problem in practical use ⁇ : Scratches remain after rubbing, and scratch resistance is high Low, practical problem
- the decorative sheet was heated in an oven set at 160 ° C. for 60 seconds and pulled at 1000 mm / sec using a Tensilon universal testing machine, and evaluated according to the following criteria: did.
- the results are shown in Table 3.
- ⁇ Not stretched 100%, poor tensile properties at high temperature, causing problems in practical use
- ⁇ Test 2 Test for a decorative sheet having a raised portion> Evaluation of adhesion
- the surface of the decorative sheet on which the upper part of the evaluation is formed is cut into 11 vertical and 11 horizontal cuts at a length of 5 cm and an interval of 2 mm with a cutter. A grid-like cut was formed. From the top of this notch, Nichiban's cellophane tape (registered trademark, No. 405-1P) was pressure-bonded and then peeled off rapidly to evaluate the adhesion of the upper portion.
- the evaluation criteria are as follows. The results are shown in Table 4. ⁇ : no peeling was observed ⁇ : peeling was observed
- Scratch resistance (steel wool) The surface of the decorative sheet on which the upper portion was formed was rubbed 10 times with a load of 1.5 kgf using steel wool (# 0000), and the surface was visually observed and evaluated according to the following criteria. The results are shown in Table 4. ⁇ : Scratches disappear after rubbing and scratch resistance is high ⁇ : Scratches remain a little after rubbing and scratch resistance is slightly low, but there is no problem in practical use ⁇ : Scratches remain after rubbing, and scratch resistance is high Low, practical problem
- the decorative sheet was heated for 120 seconds in an oven set at 170 ° C. and 1000 mm / sec using a Tensilon universal testing machine.
- the surface of the decorative sheet when it was pulled and stretched by 50% was visually observed and evaluated according to the following criteria. The results are shown in Table 4.
- ⁇ There is no crack in the portion located between the upper parts of the surface protective layer, and the tensile properties at high temperature are very good.
- ⁇ The part located between the upper parts of the surface protective layer is cracked in about 30%. Although there are good tensile properties at high temperatures.
- the ultraviolet curable resin in Table 4 is as follows.
- Resin G 10% by mass of polyester-based acrylate oligomer (weight average molecular weight of about 2000), 68% by mass of bifunctional acrylate monomer, 10% by mass of thermoplastic resin (weight average molecular weight: 5000), 5% by mass of photosensitive compound, photopolymerization 5% by mass of initiator, 2% by mass in total of filler and pigment
- Resin H 20% by mass of urethane acrylate oligomer (weight average molecular weight of about 2000), 60% by mass of bifunctional acrylate monomer, 5% by mass of photosensitive compound
- Photopolymerization initiator a mixture of 5% by mass and a total of 10% by mass of filler and pigment
- the decorative sheets of Reference Examples 11 and 12 and Examples 1B and 2B using a polyfunctional polycarbonate (meth) acrylate having a large weight average molecular weight of 20,000 for the surface protective layer are excellent from the viewpoint of scratch resistance. It was.
- Comparative Reference Example 2 in which a raised portion was formed on a laminated film of an acrylic resin base material and an ABS resin film, since the acrylic resin deteriorated due to ultraviolet irradiation, the bending test results were both poor and the moldability was inferior. It became clear.
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
項1. 基材シートの上に、電離放射線硬化性樹脂組成物の硬化物により形成された盛上部を有し、
前記電離放射線硬化性樹脂の硬化物は、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にある、加飾シート。
項2. 前記盛上部の電離放射線硬化性樹脂組成物が、ウレタン(メタ)アクリレートオリゴマーを含む、項1に記載の加飾シート。
項3.前記盛上部の厚みが、10μm以上である、項1または2に記載の加飾シート。
項4. 前記盛上部の総面積は、加飾シートの全面の面積に対して、90%以下である、項1~3のいずれかに記載の加飾シート。
項5. 複数の前記盛上部が互いに独立している、項1~4のいずれかに記載の加飾シート。
項6. 複数の前記盛上部は、それぞれ、加飾シートの積層方向から見た場合の面積が100mm2以下である、項1~5のいずれかに記載の加飾シート。
項7. 前記基材シートと前記盛上部との間に表面保護層を有し、前記盛上部が前記表面保護層の表面上に形成されている、項1~6のいずれかに記載の加飾シート。
項8. 前記表面保護層が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、項7に記載の加飾シート。
項9. 前記表面保護層の前記電離放射線硬化性樹脂組成物におけるシリコーン成分の含有量が、5質量%以下である、項7または8に記載の加飾シート。
項10. 前記表面保護層の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7~9のいずれかに記載の加飾シート。
項11. 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、5000以上である、項10に記載の加飾シート。
項12. 前記表面保護層の前記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10または11に記載の加飾シート。
項13. 前記表面保護層の前記電離放射線硬化性樹脂組成物に含まれる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)アクリレートの質量比が、50:50~99:1の範囲にある、項12に記載の加飾シート。
項14. 前記表面保護層の厚みが、1~50μmである、項7~13のいずれかに記載の加飾シート。
項15. さらに装飾層を備える、項1~14のいずれかに記載の加飾シート。
項16. 前記基材シートの前記盛上部とは反対側に支持体シートを有する、項1~15のいずれかに記載の加飾シート。
項17. 成形樹脂層と、基材シートと、前記基材シートの上に電離放射線硬化性樹脂組成物の硬化物により形成された盛上部とがこの順に積層されており、
前記盛上部の電離放射線硬化性樹脂組成物の硬化物は、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にある、加飾樹脂成形品。
項18. 前記基材シートと前記盛上部との間に表面保護層を有し、前記盛上部が前記表面保護層の表面上に形成されている、項17に記載の加飾樹脂成形品。
本発明の加飾シートは、基材シートの上に、電離放射線硬化性樹脂組成物の硬化物により形成された盛上部を有し、電離放射線硬化性樹脂の硬化物は、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にあることを特徴とする。本発明の加飾シートにおいては、盛上部を形成する電離放射線硬化性樹脂組成物の硬化物の温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にあることにより、成形時における当該盛上部の割れが効果的に抑制されており、さらに、成形後における盛上部の凹凸形状による意匠性、耐傷付き性にも優れている。より具体的には、本発明の加飾シートは、盛上部が上記特定範囲のマルテンス硬度を有する電離放射線硬化性樹脂組成物の硬化物に形成されているため、盛上部が適度な柔軟性を有しており、成形時における当該盛上部の割れが効果的に抑制されている。さらに、当該マルテンス硬度を有する盛上部は、適度な弾性も有しているため、成形時に加熱・加圧が加えられた際にも、盛上部の形状が好適に保持され、成形後における盛上部の凹凸形状による意匠性にも優れている。さらに、当該マルテンス硬度を有する盛上部は、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いるため、耐傷付き性にも優れている。なお、後述の通り、本発明の加飾シートは、装飾層や隠蔽層などを有していなくてもよく、例えば透明であってもよい。以下、本発明の加飾シートについて詳述する。
本発明の加飾シートは、基材シート1の上に盛上部2が形成された積層構造を有する。本発明の加飾シートにおいては、例えば図1~図3に示されるように、基材シート1の上の盛上部2によって、加飾シートの表面に凹凸形状が形成されている。
[基材シート1]
基材シート1は、加飾シートの基材としての機能を果たす層であり、加飾シートの表面側に設けられる場合は、基材シート1の表面上に後述の盛上部2が形成される。なお、後述の通り、基材シート1と盛上部2との間に表面保護層5を有する場合、盛上部2は、表面保護層5の表面上に形成される。
本発明の加飾シートにおいて、盛上部2は、基材シート1の上に形成されており、盛上部2により形成された凹凸形状によって、加飾シートに意匠性を付与している。盛上部2は、上記の基材シート1の表面上に形成することができ、本発明の加飾シートが後述の表面保護層5を有する場合には、表面保護層5の表面上に形成することができる。
盛上部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、安定な硬化特性が得られる。
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。盛上部2の形成に使用される電離放射線硬化性樹脂組成物に、ウレタン(メタ)アクリレートに加えて、他の(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。
支持体シート3は、本発明の加飾シートにおいて、成形性を高めることなどを目的として、必要に応じて設けられる層であり、加飾シートに高度な伸びが要求される、複雑な形状の成形品の加飾に用いる場合には設けられていることが好ましい。なお、上記の基材シート1が成形性に優れる樹脂により形成されている場合、支持体シート3は設けなくてもよい。
表面保護層5は、加飾樹脂成形品の耐傷性や耐薬品性を高めることなどを目的として、基材シート1と盛上部2との間に、必用に応じて設けられる層である。本発明の加飾シートが表面保護層5を有する場合、上記の盛上部2は表面保護層5の上に形成される。
ポリカーボネート(メタ)アクリレートとしては、盛上部2の説明で既に述べたように、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、特に制限されない。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。
表面保護層5の形成に用いるウレタン(メタ)アクリレートは、盛上部2で説明したものが使用できる。表面保護層5の形成に用いるウレタン(メタ)アクリレートの分子量については、特に制限されないが、例えば、重量平均分子量が5千以上、好ましくは1万以上が挙げられ、上限は粘度が高くなり過ぎないように制御するという観点から、例えば、重量平均分子量が10万以下、好ましくは5万以下が挙げられる。
プライマー層6は、表面保護層5とその下に位置する層との密着性を高めることなどを目的として、必要に応じて設けられる層である。
装飾層4は、樹脂成形品に装飾性を与えることを目的として、必用に応じて設けられる層である。本発明の加飾シートが表面保護層5を有する場合、装飾層4は基材シート1の盛上部2側に設けることができ、基材シート1が透明(半透明を含む)である場合には、盛上部2とは反対側に設けることができる。装飾層4は、絵柄を形成していてもよく、ベタであってもよく、これらの組合せであってもよい。
隠蔽層は、加飾シート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、必要に応じて、隠蔽層を設けてもよい(図示していない)。
接着層7は、加飾シートと成形樹脂層8との密着性を高めることなどを目的として、必要に応じて、加飾シートの裏面(盛上部2と反対側)に設けることができる。接着層7を形成する樹脂としては、加飾シートと成形樹脂層8との密着性や接着性を向上させることができるものであれば、特に制限されず、例えば、熱可塑性樹脂または熱硬化性樹脂が用いられる。熱可塑性樹脂としては、例えば、アクリル樹脂、アクリル変性ポリオレフィン樹脂、塩素化ポリオレフィン樹脂、塩化ビニル-酢酸ビニル共重合体、熱可塑性ウレタン樹脂、熱可塑性ポリエステル樹脂、ポリアミド樹脂、ゴム系樹脂などが挙げられる。熱可塑性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。また、熱硬化性樹脂としては、例えば、ウレタン樹脂、エポキシ樹脂等挙げられる。熱硬化性樹脂は、1種類単独で使用してもよいし、2種類以上を組み合わせて使用してもよい。
本発明の加飾樹脂成形品は、本発明の加飾シートに成形樹脂層8を一体化させることにより成形されてなるものである。即ち、本発明の加飾樹脂成形品は、少なくとも、成形樹脂層と、基材シートと、基材シートの上に形成された、電離放射線硬化性樹脂組成物の硬化物により形成された盛上部とがこの順に積層された積層体からなり、電離放射線硬化性樹脂の硬化物が、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にあ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支持体シート3、装飾層4、表面保護層5、プライマー層6、隠蔽層、接着層7などの少なくとも1層がさらに設けられていてもよい。図8に、本発明の加飾樹脂成形品の積層構造の一態様として、図3に示される態様の加飾シートを成形樹脂層8上に積層して得られる、成形樹脂層/支持体シート/接着層/装飾層/基材シート/盛上部がこの順に積層された加飾シートの一例の略図的断面図を示す。
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。
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、加飾シートの基材シート1側(盛上部2とは反対側)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。
(加飾シートの作製)
<実施例1A>
ポリメタクリル酸メチルを主成分とする厚さ75μmの無着色透明なアクリル樹脂シートからなる基材シートの裏面に、ポリブチルメタクリレート/塩化ビニル-酢酸ビニル共重合体をバインダーとした装飾層(厚さ1μm)、ポリメチルメタクリレート及び2液硬化型ウレタン樹脂系接着剤からなる接着層(厚さ10μm)を順次積層した。次に、接着層の上から、ABS樹脂からなる支持体シート(厚さ400μm)をドライラミネーションにより積層した。次に、下記の電離放射線硬化性樹脂組成物を用いて、基材シートの表面に、円形状の盛上部を多数配列した平面視パターン状(1つの盛上部の面積約0.3mm2、基材シート表面における盛上部の面積の割合約45%)に印刷した。次に、盛上部の上から、紫外線を160W/cmの条件で照射して印刷版の版形状を保ったまま硬化させた。以上の手順により、基材シート上に厚さ30μmの盛上部が多数形成された三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ウレタンアクリレートオリゴマー(重量平均分子量約2000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物
下記の電離放射線硬化性樹脂組成物を用いたこと以外は、実施例1Aと同様にして、三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ウレタンアクリレートオリゴマー(重量平均分子量約8000)30質量%、3官能性アクリレートモノマー50質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物
下記の電離放射線硬化性樹脂組成物を用いたこと以外は、実施例1Aと同様にして、三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ウレタンアクリレートオリゴマー(重量平均分子量約5000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物
下記の電離放射線硬化性樹脂組成物を用いたこと以外は、実施例1Aと同様にして、三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ウレタンアクリレートオリゴマー(重量平均分子量約8000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物
下記の電離放射線硬化性樹脂組成物を用いたこと以外は、実施例1Aと同様にして、三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ポリエステルアクリレートオリゴマー(重量平均分子量約2000)10質量%、2官能性アクリレートモノマー68質量%、熱可塑性樹脂10質量%、感光性化合物5質量%、光重合開始剤5質量%、フィラーおよび顔料の合計2質量%の混合物
下記の電離放射線硬化性樹脂組成物を用いたこと以外は、実施例1Aと同様にして、三次元成形用加飾シートを得た。
(電離放射線硬化性樹脂組成物)
ウレタンアクリレートオリゴマー(重量平均分子量約5000)40質量%、2官能性アクリレートモノマー40質量%、感光性化合物5質量%、光重合開始剤5質量%、フィラーおよび顔料の合計10質量%の混合物
マルテンス硬度は、表面皮膜物性試験機(PICODENTOR HM-500、株式会社フィッシャー・インストルメンツ製)を用いて測定される値であり、具体的な測定方法は以下の通りである。この測定方法では、温度25℃及び相対湿度50%の環境下、図5Aに示されるような対面角136°のダイヤモンド圧子(ビッカース圧子)を用いて、各実施例及び比較例の加飾シートにおける盛上部にダイヤモンド圧子を押し込み、押し込み荷重Fと押し込み深さh(圧痕深さ)から下記の式(2)により硬さを求めた。押し込み条件は、加飾シートの盛上部2に対して、室温(実験室環境温度)において、図5Bに示される通り、先ず0~2mNまでの負荷を2秒間で加え、次に2mNの負荷で5秒間保持し、最後に2~0mNまでの除荷を2秒間で行った。
実施例1A~4A及び比較例1A~2Aで得られた加飾シートを固定枠に固定し、加飾シートの温度が約160℃になるまで約300℃のヒーターで加熱した。加熱され軟化した加飾シートを、上述のように、真空成形工程、トリミング工程及び温度約240℃でABS樹脂を成形用樹脂とする射出成形工程を経て加飾樹脂成形品を得た。
実施例1A~4A及び比較例1A~2Aの加飾シートから得られた上記加飾樹脂成形品の盛上部の割れを目視で観察し、300%の伸長部でも割れがないものを◎、250%の伸長部まで割れがないものを○、200%の伸長部まで割れがないものを△、150%の伸長部まで割れがないものを×とした。結果を表1に示す。
実施例1A~4A及び比較例1A~2Aの加飾シートから得られた上記加飾樹脂成形品の表面を手で触り、凹凸感を評価した。評価基準としては、凹凸感がはっきりと感じられたものを◎、凹凸感が感じられたものを○、凹凸感が僅かに感じられたものを△、凹凸感が全く感じられなかったものを×とした。結果を表1に示す。
実施例1A~4A及び比較例1A~2Aの加飾シートから得られた上記加飾樹脂成形品の表面の算術平均粗さRaを以下のようにして測定した。株式会社東京精密製の表面粗さ測定器(商品面「ハンディーサーフE-35A」を使用し、JIS B 0601:2001に準拠し、長さLの粗さ曲線を中心線から折り返し、それぞれの粗さ曲線と中心線によって得られた全面積を長さLで割った値をマイクロメータ(μm)で表した。結果を表1に示す。
実施例1A~4A及び比較例1A~2Aの加飾シートから得られた上記加飾樹脂成形品の表面を、スチールウール(#0000)を用いて荷重1.5kgfで10往復擦り、目視で盛上部の表面を観察して、以下の基準に従って評価した。結果を表1に示す。
◎:擦った後に盛上部の傷跡がすぐに消え、耐傷付き性が高い
○:擦った後に盛上部の傷跡が消え、耐傷付き性が高い
△:擦った後に盛上部に傷跡が少し残り、耐傷付き性が少し低いが、実用上問題がない
×:擦った後に盛上部に傷跡が残り、耐傷付き性が低く、実用上問題がある
(盛上部を形成する前の加飾シートの作製)
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装飾層(厚み5μm)を形成した。次に装飾層の上に、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3μm)を設けた。なお、プライマー組成物は、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質量部を含む組成物である。次に、表2の組成を有する電子線硬化性樹脂を、樹脂組成物の硬化後の厚みが10μmまたは5μm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、基材シート/装飾層/プライマー層/表面保護層がこの順に積層された、盛上部を形成する前の加飾シートを得た。盛上部を形成する前の加飾シートについて、以下の試験1を行なった。なお、比較参考例1については、アクリル樹脂基材(厚み75μm)とABS樹脂フィルム(厚み400μm)の積層フィルムをそのまま試験1に供した。結果を表3に示す。
(盛上部を有する加飾シートの作製)
次に、参考例1~10で得られた盛上部を有する前の加飾シートの表面保護層上に、表4に記載の紫外線硬化型樹脂GまたはHからなる直径2mmのドット(面積約3mm2)を塗布厚30μmとなるようにスクリーン印刷により印刷し、複数の未硬化の盛上部を形成した。次に、未硬化の盛上部に対して、積算光量600mJ/cm2の紫外線を照射し、紫外線硬化型樹脂を硬化させて、基材シート/装飾層/プライマー層/表面保護層/盛上部がこの順に積層された、加飾シートを得た。得られた加飾シートにおいて、表面保護層全面の面積に対する盛上部の合計面積の割合は、35%であった。この加飾シートについて、以下の試験2を行なった。結果を表4に示す。なお、比較参考例2については、アクリル樹脂基材上に盛上部を形成した。
A: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)
B: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)
C:4官能ウレタンアクリレート(重量平均分子量:5百)
D:2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:1千)
E:4官能ウレタンアクリレート(重量平均分子量:8千)
F:3官能アクリレートモノマー(重量平均分子量:約3百)
耐傷付き性(爪スクラッチ)
加飾シートの表面を爪で10往復スクラッチし、目視で表面を観察して、以下の基準に従って評価した。結果を表3に示す。
○:スクラッチ後に跡が消え、耐傷付き性が高い
△:スクラッチ後に跡が少し残り、耐傷付き性が少し低いが、実用上問題がない
×:スクラッチ後に跡が残り、耐傷付き性が低く、実用上問題がある
加飾シートの表面を、スチールウール(#0000)を用いて荷重1.5kgfで10往復擦り、目視で表面を観察して、以下の基準に従って評価した。結果を表3に示す。
○:擦った後に傷跡が消え、耐傷付き性が高い
△:擦った後に傷跡が少し残り、耐傷付き性が少し低いが、実用上問題がない
×:擦った後に傷跡が残り、耐傷付き性が低く、実用上問題がある
成形性を確認するため、160℃に設定したオーブンにて、加飾シートを60秒間加熱し、テンシロン万能試験機を用いて1000mm/secで引っ張って、以下の基準に従って評価した。結果を表3に示す。
◎:150%以上伸び、高温下での引張特性が非常に良好である
○:120%以上伸び、高温下での引張特性が良好である
△:100%以上伸び、高温下での引張特性は悪くなく、実用上問題がない
×:100%伸びず、高温下での引張特性が悪く、実用上問題がある
成形性を確認するため、加飾シートを常温下において、手で折り曲げて、以下の基準に従い評価した。結果を表3に示す。
○:180°に折り曲げた場合にも、折り曲げた部分に亀裂が生じない
△:90°に折り曲げた場合、折り曲げた部分に亀裂が生じず、実用上問題がない
×:90°に折り曲げた場合、折り曲げた部分に亀裂が生じ、実用上問題がある
密着性の評価
盛上部を形成した加飾シートの表面に対して、カッターで長さ5cm、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、盛上部の密着性を評価した。評価基準は以下の通りである。結果を表4に示す。
○:剥離が見られなかった
×:剥離が見られた
盛上部を形成した加飾シートの表面を爪で10往復スクラッチし、目視で表面を観察して、以下の基準に従って評価した。結果を表4に示す。
○:スクラッチ後に跡が消え、耐傷付き性が高い
△:スクラッチ後に跡が少し残り、耐傷付き性が少し低いが、実用上問題がない
×:スクラッチ後に跡が残り、耐傷付き性が低く、実用上問題がある
盛上部を形成した加飾シートの表面を、スチールウール(#0000)を用いて荷重1.5kgfで10往復擦り、目視で表面を観察して、以下の基準に従って評価した。結果を表4に示す。
○:擦った後に傷跡が消え、耐傷付き性が高い
△:擦った後に傷跡が少し残り、耐傷付き性が少し低いが、実用上問題がない
×:擦った後に傷跡が残り、耐傷付き性が低く、実用上問題がある
盛上部を形成した加飾シートの成形性を確認するため、170℃に設定したオーブンにて、加飾シートを120秒間加熱し、テンシロン万能試験機を用いて1000mm/secで引っ張って、50%伸ばしたときの加飾シートの表面を目視で観察し、以下の基準に従って評価した。結果を表4に示す。
◎:表面保護層の盛上部間に位置する部分に亀裂がなく、高温下での引張特性は非常に良好である
○:表面保護層の盛上部間に位置する部分に3割程度に亀裂があるが、高温下での引張特性は良好である
△:表面保護層の盛上部間に位置する部分に4割程度に亀裂があるが、高温下での引張特性は悪くなく、実用上問題がない
×:表面保護層の盛上部間に位置する部分に5割以上に亀裂があり、高温下での引張特性が悪く、実用上問題がある
盛上部を形成した加飾シートの成形性を確認するため、加飾シートを常温下において、手で折り曲げて、以下の基準に従い評価した。結果を表4に示す。
○:180°に折り曲げた場合にも、折り曲げた部分に亀裂が生じない
△:90°に折り曲げた場合、折り曲げた部分に亀裂が生じず、実用上問題がない
×:90°に折り曲げた場合、折り曲げた部分に亀裂が生じ、実用上問題がある
樹脂G:ポリエステル系アクリレートオリゴマー(重量平均分子量約2000)10質量%、2官能性アクリレートモノマー68質量%、熱可塑性樹脂(重量平均分子量:5000)10質量%、感光性化合物5質量%、光重合開始剤5質量%、フィラーおよび顔料の合計2質量%の混合物
樹脂H:ウレタン系アクリレートオリゴマー(重量平均分子量約2000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物
上記樹脂G:マルテンス硬度140N/mm2
上記樹脂H:マルテンス硬度112N/mm2
樹脂I:ウレタンアクリレートオリゴマー(重量平均分子量約8000)30質量%、3官能性アクリレートモノマー50質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物、マルテンス硬度12N/mm2
樹脂J:ウレタンアクリレートオリゴマー(重量平均分子量約5000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物、マルテンス硬度82N/mm2
樹脂K:ウレタンアクリレートオリゴマー(重量平均分子量約8000)20質量%、2官能性アクリレートモノマー60質量%、感光性化合物5質量%、光重合開始剤:5質量%、フィラーおよび顔料の合計10質量%の混合物、マルテンス硬度70N/mm2
1…基材シート
2…盛上部
3…支持体シート
4…装飾層
5…表面保護層
6…プライマー層
7…接着層
8…成形樹脂層
Claims (18)
- 基材シートの上に、電離放射線硬化性樹脂組成物の硬化物により形成された盛上部を有し、
前記電離放射線硬化性樹脂の硬化物は、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にある、加飾シート。 - 前記盛上部の電離放射線硬化性樹脂組成物が、ウレタン(メタ)アクリレートオリゴマーを含む、請求項1に記載の加飾シート。
- 前記盛上部の厚みが、10μm以上である、請求項1または2に記載の加飾シート。
- 前記盛上部の総面積は、加飾シートの全面の面積に対して、90%以下である、請求項1~3のいずれかに記載の加飾シート。
- 複数の前記盛上部が互いに独立している、請求項1~4のいずれかに記載の加飾シート。
- 複数の前記盛上部は、それぞれ、加飾シートの積層方向から見た場合の面積が100mm2以下である、請求項1~5のいずれかに記載の加飾シート。
- 前記基材シートと前記盛上部との間に表面保護層を有し、前記盛上部が前記表面保護層の表面上に形成されている、請求項1~6のいずれかに記載の加飾シート。
- 前記表面保護層が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、請求項7に記載の加飾シート。
- 前記表面保護層の前記電離放射線硬化性樹脂組成物におけるシリコーン成分の含有量が、5質量%以下である、請求項7または8に記載の加飾シート。
- 前記表面保護層の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7~9のいずれかに記載の加飾シート。
- 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、5000以上である、請求項10に記載の加飾シート。
- 前記表面保護層の前記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10または11に記載の加飾シート。
- 前記表面保護層の前記電離放射線硬化性樹脂組成物に含まれる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)アクリレートの質量比が、50:50~99:1の範囲にある、請求項12に記載の加飾シート。
- 前記表面保護層の厚みが、1~50μmである、請求項7~13のいずれかに記載の加飾シート。
- さらに装飾層を備える、請求項1~14のいずれかに記載の加飾シート。
- 前記基材シートの前記盛上部とは反対側に支持体シートを有する、請求項1~15のいずれかに記載の加飾シート。
- 成形樹脂層と、基材シートと、前記基材シートの上に電離放射線硬化性樹脂組成物の硬化物により形成された盛上部とがこの順に積層されており、
前記盛上部の電離放射線硬化性樹脂組成物の硬化物は、温度25℃及び相対湿度50%下におけるマルテンス硬度が10~120N/mm2の範囲にある、加飾樹脂成形品。 - 前記基材シートと前記盛上部との間に表面保護層を有し、前記盛上部が前記表面保護層の表面上に形成されている、請求項17に記載の加飾樹脂成形品。
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JP2019177662A (ja) * | 2018-03-30 | 2019-10-17 | 大日本印刷株式会社 | 加飾シートおよび加飾樹脂成形品 |
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