WO2022118967A1 - 積層フィルムおよび成形体、ならびにそれらの製造方法 - Google Patents
積層フィルムおよび成形体、ならびにそれらの製造方法 Download PDFInfo
- Publication number
- WO2022118967A1 WO2022118967A1 PCT/JP2021/044529 JP2021044529W WO2022118967A1 WO 2022118967 A1 WO2022118967 A1 WO 2022118967A1 JP 2021044529 W JP2021044529 W JP 2021044529W WO 2022118967 A1 WO2022118967 A1 WO 2022118967A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- laminated film
- uncured
- optical interference
- less
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 230000003287 optical effect Effects 0.000 claims abstract description 156
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000010410 layer Substances 0.000 claims description 420
- 239000000463 material Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 87
- 239000002245 particle Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 39
- 239000011254 layer-forming composition Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 30
- 238000005034 decoration Methods 0.000 claims description 27
- 238000010030 laminating Methods 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000002346 layers by function Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 23
- 238000001746 injection moulding Methods 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 128
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 292
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 235000019589 hardness Nutrition 0.000 description 55
- 239000000047 product Substances 0.000 description 52
- 230000001681 protective effect Effects 0.000 description 47
- 238000011156 evaluation Methods 0.000 description 40
- -1 polyethylene terephthalate Polymers 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 239000010419 fine particle Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 21
- 229910052809 inorganic oxide Inorganic materials 0.000 description 19
- 239000003999 initiator Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229920000058 polyacrylate Polymers 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 102100025639 Sortilin-related receptor Human genes 0.000 description 3
- 101710126735 Sortilin-related receptor Proteins 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000000427 thin-film deposition Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 210000003811 finger Anatomy 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- ZMZHRHTZJDBLEX-UHFFFAOYSA-N (2-phenylphenyl) prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1C1=CC=CC=C1 ZMZHRHTZJDBLEX-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 101000642347 Homo sapiens Splicing factor 45 Proteins 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 102100036374 Splicing factor 45 Human genes 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- LZWJWPDVARVFJI-UHFFFAOYSA-N antimony;nickel;oxotitanium Chemical compound [Ni].[Sb].[Ti]=O LZWJWPDVARVFJI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 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
- 150000001875 compounds Chemical class 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
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 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
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14688—Coating articles provided with a decoration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14688—Coating articles provided with a decoration
- B29C2045/14713—Coating articles provided with a decoration decorations in contact with injected material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14811—Multilayered articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/007—Hardness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0094—Geometrical properties
- B29K2995/0097—Thickness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Definitions
- the present invention relates to a laminated film and a molded product, and a method for producing them.
- displays include digital meters, instrument panels, navigation systems, console panels, center clusters, and heater control panels. It is used in various fields such as display panels for mobile phones.
- Such products are often covered with protective material.
- the protective material is usually obtained by molding a film having a hardcourt layer.
- the protective material of the display may be further provided with a low refractive index layer for the purpose of reducing the reflectance of the surface on the visual side.
- Patent Document 1 teaches a laminated film in which a hard coat layer and a low refractive index layer (optical interference layer) are sequentially laminated on a transparent support.
- the present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide an aftercure type laminated film and a molded product having a low reflectance, and a method for producing them.
- the present invention provides the following aspects.
- An uncured hardcourt layer formed on at least one surface of the transparent supporting substrate A laminated film comprising an uncured optical interference layer formed on the uncured hard coat layer.
- the uncured hard coat layer contains an active energy ray-curable hard coat layer forming composition.
- the uncured optical interference layer contains an active energy ray-curable optical interference layer forming composition.
- the thickness of the transparent supporting substrate is 50 ⁇ m or more and 600 ⁇ m or less.
- the stretch ratio of the laminated film at 160 ° C. is 50% or more.
- the minimum value RAH of the reflectance between the wavelengths of 380 nm and 780 nm measured from the uncured optical interference layer side of the laminated film heat-treated at a temperature of 90 ° C. for 30 minutes is 2% or less. There is a laminated film.
- the optical interference layer forming composition contains a first layer forming component and low refraction particles.
- the first layer-forming component contains a first reactive component having two or more polymerizable functional groups in one molecule.
- the first reactive component is selected from the group consisting of a first polymer having a weight average molecular weight of more than 10,000, a first oligomer having a weight average molecular weight of 10,000 or less, and a first monomer having a weight average molecular weight of 10,000 or less.
- the hardcourt layer-forming composition contains a second layer-forming component.
- the second layer-forming component contains a second reactive component having two or more polymerizable functional groups in one molecule.
- the second reactive component is described in any one of the above [1] to [3], which comprises at least one of a second oligomer having a weight average molecular weight of 10,000 or less and a second monomer having a weight average molecular weight of 10,000 or less. Laminated film.
- the total content of the second oligomer and the second monomer is 25 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the solid content of the hardcourt layer forming composition. 5] The laminated film according to.
- the hardness HAC measured by the nanoindentation method from the optical interference layer side of the laminated film irradiated with an active energy ray having an integrated light amount of 2000 mJ / cm 2 is 0.25 GPa or more and 0.7 GPa or less.
- the laminated film according to any one of [1] to [8].
- the hardcoat layer is arranged on one main surface of the transparent support substrate.
- a laminated film is obtained by laminating the surface of the uncured hard coat layer opposite to the transparent supporting substrate and the surface of the uncured optical interference layer opposite to the other supporting substrate. With a laminating process, The stretch ratio of the laminated film at 160 ° C. is 50% or more.
- the minimum value RAH of the reflectance between the wavelengths of 380 nm and 780 nm measured from the uncured optical interference layer side of the laminated film heated at a temperature of 90 ° C. for 30 minutes is 2% or less.
- the laminated film is provided with a curing step of irradiating the laminated film with active energy rays.
- the decoration step is a method for producing a molded product, which comprises a heating step of heating the laminated film at 80 ° C. or higher for 20 minutes or longer.
- the mold imparts a three-dimensional shape to the laminated film and gives the laminated film a three-dimensional shape.
- an aftercure type laminated film and a molded product having a low reflectance it is possible to provide an aftercure type laminated film and a molded product having a low reflectance, and a method for producing them.
- a laminated film called a precure type As a protective film for a display, a laminated film called a precure type is usually used. As shown in Patent Document 1, in the precure type laminated film, each layer is already cured at the time of preform. Therefore, in the injection molding into a three-dimensional shape and the preform performed before that, the laminated film cannot follow the mold of the deep three-dimensional shape, and the laminated film may be cracked or whitened.
- the laminated film may be cured after preform.
- Such a laminated film is called an aftercure type.
- the aftercure type laminated film includes an uncured hard coat layer and an uncured optical interference layer.
- phase mixture may occur at the interface between the uncured hard coat layer and the optical interference layer due to the heat treatment applied when forming the decorative layer on the laminated film.
- the reflectance increases.
- the laminated film according to the present embodiment can be decorated or molded into a complicated shape while maintaining a low reflectance.
- the laminated film is an aftercure type and has a draw ratio of 50% or more at 160 ° C. Therefore, the occurrence of cracks and whitening in the preform and injection molding processes is suppressed, and the appearance of the molded product is improved. Since cracks are unlikely to occur, the functions of the hard coat layer and the optical interference layer are more effectively exerted. In addition, since the stretch ratio of the laminated film at 160 ° C. is 50% or more and the thickness of the transparent supporting base material is 50 ⁇ m or more and 600 ⁇ m or less, the obtained molded product can be obtained even when molded into a complicated shape. Has sufficient rigidity.
- each layer can be formed by a layer forming composition having a high crosslink density. That is, the hardness of each layer after curing can be further increased.
- both the hard coat layer and the optical interference layer are uncured, so that the adhesion between the layers is high. Further, by heat treatment, the unevenness of the surface of each layer can be leveled. Thereby, a laminated film having high smoothness can be obtained.
- the laminated film according to the present embodiment is formed on a transparent support base material, an uncured hard coat layer formed on at least one surface of the transparent support base material, and an uncured hard coat layer. It has an uncured optical interference layer.
- the uncured hardcoat layer contains an active energy ray-curable hardcoat layer forming composition.
- the uncured optical interference layer contains an active energy ray-curable optical interference layer forming composition.
- Uncured means a state in which it is not completely cured.
- the hard coat layer and the light interference layer contained in the laminated film may be in a semi-cured state.
- the laminated film is an aftercure type.
- Curing is synonymous with "curing and drying” defined in JIS K5500 (paint term). That is, for curing, a) the center of the test piece is strongly pinched between the thumb and the index finger, and the coated surface does not have dents due to fingerprints, the movement of the coating film is not felt, and the coated surface is rapidly pressed with the fingertips. It means that after repeated rubbing, it becomes a state without scratches (dry hard).
- the laminated film irradiated with the active energy rays having an integrated light amount of 200 mJ / cm 2 is completely cured.
- Semi-curing is synonymous with "semi-curing drying" defined in JIS K 5500 (paint term). That is, semi-curing refers to a state in which the center of the painted surface is lightly rubbed with a fingertip and no scratch marks are left on the painted surface (dry to touch). It can be said that the laminated film irradiated with the active energy rays having an integrated light amount of 1 mJ / cm 2 or more and less than 200 mJ / cm 2 is semi-cured.
- a state in which the hard coat layer and the optical interference layer are not exposed to the active energy rays or exposed to the active energy rays of less than 1 mJ / cm 2 can be said to be uncured.
- the wavelength between 380 nm and 780 nm measured from the uncured optical interference layer side of the laminated film subjected to the heat treatment for 30 minutes at a temperature of 90 ° C. (hereinafter, may be referred to as a specific heat treatment).
- the minimum value RAH of the reflectance is 2.0% or less.
- the fact that the minimum reflectance RAH is within this range means that the generation of multiphase between the uncured hard coat layer and the uncured optical interference layer is suppressed, and it is clear between the two layers. Indicates that an interface is formed.
- the minimum value RAH of the reflectance is preferably 1.8% or less, more preferably 1.6% or less.
- the minimum value of the reflectance of the laminated film according to the present embodiment may be 2.0% or less even after heat treatment at 90 ° C. or higher and 120 ° C. or lower and 30 minutes or longer and 90 minutes or shorter.
- the laminated film according to this embodiment has excellent antireflection performance.
- the molded product obtained by curing this also has excellent antireflection performance.
- the antireflection effect reduces the reflection of external light on the molded product.
- the molded product has good display characteristics and good visibility.
- the minimum value RAH of the reflectance is obtained by measuring all the reflected light including the specular reflected light in the wavelength region of 380 nm or more and 780 nm or less.
- the minimum value RAH of the reflectance is the smallest value among the reflectances at each wavelength measured by the so-called SCI (Specular Component Include) method. Since this method is not easily affected by the surface condition of the object to be measured, the reflectance of the uncured layer can be measured.
- the minimum value RAH of the reflectance of the laminated film can be measured by the following method.
- a black paint for example, product name: CZ-805 BLACK (manufactured by Nikko Bics)
- CZ-805 BLACK manufactured by Nikko Bics
- the coating is applied so as to be 6 ⁇ m or less, and then heat-treated at a temperature of 90 ° C. for 30 minutes to prepare an evaluation sample M.
- the reflectance by the SCI method in the wavelength region of 380 nm or more and 780 nm or less is measured for each wavelength of 10 nm. Measure.
- the reflectance is measured at any 5 points or more (preferably 10 points) of the evaluation sample M.
- the minimum value of reflectance is determined for each measurement point.
- the minimum value RAH of the reflectance of the laminated film according to the present embodiment does not exceed 2% at all measurement points.
- the minimum value RAH of the reflectance may be measured by using the evaluation sample N in which the evaluation sample M is irradiated with an active energy ray having an integrated light amount of 200 mJ / cm 2 or more. This is because the reflectance hardly changes before and after curing.
- the minimum reflectance RAH and the minimum reflectance RBH measured from the uncured optical interference layer side of the laminated film before the specific heat treatment are 100 ⁇
- / R BH is more preferably 10% or less, and particularly preferably 5% or less.
- the reflectance is maintained low even if the specific heat treatment is applied. Further, the curing of the hard coat layer forming composition and the light interference layer forming composition hardly progresses by the specific heat treatment. Therefore, the laminated film can be subjected to a specific heat treatment and other heat treatments without affecting the adhesion and the stretch ratio in addition to the reflectance before the film is completely cured. By heat treatment, the smoothness of each layer can be improved. Therefore, the smoothness of the obtained molded product is also improved.
- the temperature of the other heat treatment may be 90 ° C. or higher and 220 ° C. or lower, 100 ° C. or higher and 220 ° C. or lower, and 110 ° C. or higher and 220 ° C. or lower.
- the time of the other heat treatment may be 10 seconds or more and 10 minutes or less.
- the laminated film is formed into a desired three-dimensional shape by thermoforming.
- Other heat treatments may be carried out using this heat applied in the preform step.
- thermoforming at about 150 ° C. or higher and 190 ° C. or lower for 10 seconds or longer and 5 minutes or shorter, each uncured layer can be sufficiently leveled while being preformed.
- the stretch ratio E 160 of the laminated film at 160 ° C. is 50% or more.
- the laminated film is sufficiently stretched at a molding temperature of 150 ° C. or higher and 190 ° C. or lower. Therefore, the laminated film can be formed into a complicated three-dimensional shape without causing cracks.
- damage to the laminated film is easily suppressed. Therefore, it is possible to obtain a molded product having the functions of a hard coat layer and an optical interference layer and having a complicated three-dimensional shape.
- the laminated film is molded into a three-dimensional shape by, for example, a preform and an insert molding method, depending on the required physical properties, shape, and the like.
- the functions of the hard coat layer and the optical interference layer are, for example, excellent hard coat performance and antireflection performance.
- Hardcourt performance includes, for example, high hardness, wear resistance and chemical resistance.
- the stretch ratio E 160 of the laminated film is preferably 60% or more, more preferably 70% or more.
- the stretch ratio E 160 of the laminated film may be less than 400%, may be less than 350%, and may be less than 300%.
- the stretch ratio of the molded product obtained by curing the laminated film at 160 ° C. is less than 15% and may be 5% or less.
- the stretch ratio E 160 can be measured, for example, as follows. A tensile tester having a chuck-to-chuck distance of 150 mm and an evaluation sample cut into a length of 200 mm and a width of 10 mm are prepared. The evaluation sample is stretched by 10% in the long side direction under the conditions of a tensile force of 5.0 kgf and a tensile speed of 300 mm / min in an atmosphere of 160 ° C. Visually check the presence or absence of cracks in the stretched evaluation sample.
- the thickness of the transparent supporting substrate is 50 ⁇ m or more and 600 ⁇ m or less.
- the laminated film can maintain its rigidity even when the laminated film is stretched.
- warpage of the laminated film and the molded product is easily suppressed.
- the transparent support base material and the laminated film can be wound into a roll, roll-to-roll processing can be performed.
- the thickness of the transparent supporting base material is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more.
- the thickness of the transparent supporting substrate is preferably 500 ⁇ m or less, more preferably 480 ⁇ m or less, further preferably 450 ⁇ m or less, and particularly preferably 400 ⁇ m or less.
- the thickness of the uncured hardcoat layer is not particularly limited.
- the thickness of the uncured hardcoat layer is 2 ⁇ m or more and 30 ⁇ m or less.
- the uncured hard coat layer is a hard coat layer that has been dried and has not been cured (hereinafter, simply referred to as an uncured hard coat layer). Since the uncured hard coat layer has such a thickness, warpage after curing is likely to be suppressed. Further, a hard coat layer having excellent hard coat performance can be obtained.
- the thickness of the uncured hard coat layer is more preferably 3 ⁇ m or more.
- the thickness of the uncured hardcoat layer is more preferably 25 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the thickness of the uncured optical interference layer is not particularly limited.
- the thickness of the uncured light interference layer is, for example, 15 nm or more and 200 nm or less.
- the thickness of the uncured optical interference layer is preferably 60 nm or more, more preferably 65 nm or more.
- the thickness of the uncured optical interference layer is preferably 180 nm or less. When the thickness of the uncured optical interference layer is in this range, good antireflection property can be imparted to the molded product.
- the hardness HBC by the nanoindentation method measured from the optical interference layer side of the laminated film is preferably 0.1 GPa or more in that damage in the subsequent process is easily suppressed.
- the hardness HBC is 0.1 GPa or more, defects such as dents and damages during slit formation and cutting, dents due to foreign substances mixed when a plurality of laminated films are laminated, squeegee marks or suction marks are suppressed. , Yield is likely to improve.
- the hardness HBC is preferably 0.5 GPa or less because the adhesion between the uncured hard coat layer and the uncured optical interference layer can be easily improved.
- the hardness HBC is 0.5 GPa or less, when the uncured optical interference layer is laminated on the uncured hard coat layer, the two tend to adhere to each other easily. Further, when the uncured hard coat layer and the uncured optical interference layer are laminated by laminating, air entry into the layers (air biting) is suppressed.
- the hardness HBC is preferably 0.1 GPa or more and 0.5 GPa or less.
- the hardness HBC is more preferably 0.15 GPa or more.
- the hardness HBC is more preferably 0.4 GPa or less.
- the hardness HAC by the nanoindentation method measured from the optical interference layer side of the laminated film (that is, the cured laminated film (molded body)) irradiated with the active energy ray of the integrated light amount of 2000 mJ / cm 2 is 0. 25 GPa or more is preferable.
- the hardness HAC is preferably 0.7 GPa or less. Specifically, the hardness HAC is preferably 0.25 GPa or more and 0.7 GPa or less.
- the hardness of the laminated film cured after the specific heat treatment also satisfies the above range.
- the hardness HAC is particularly preferably 0.3 GPa or more.
- the hardness HAC may be 0.6 GPa or less.
- the hardness HAC of the molded product is larger than the hardness HBC of the laminated film.
- the hardness H BC satisfies 0.1 GPa or more and 0.5 GPa or less.
- Hardnesses HBC and HAC are calculated from the optical interference layer side of the laminated film or molded product based on the values measured by the nanoindentation method. However, the hardness HBC and HAC are measured under conditions where the surface condition of the optical interference layer and the hardness of the transparent supporting substrate are not easily affected. That is, the hardness HBC and HAC are measured by pushing the indenter from the optical interference layer side to the hard coat layer. It can be said that the hardness HBC and HAC reflect the hardness of the uncured or cured hardcoat layer. For example, hardness HBC and HAC are measured within 1000 nm from the surface of the optical interference layer.
- the hardness by the nanoindentation method is determined by, for example, a continuous stiffness measurement method using a nanoindentation device.
- a minute load (alternating current (AC) load) is applied to the sample in addition to a quasi-static test load (direct current (DC) load).
- AC alternating current
- DC direct current
- the stiffness with respect to the depth is calculated from the vibration component of the resulting displacement and the phase difference between the displacement and the load. This makes it possible to obtain a continuous profile of hardness with respect to the depth.
- NANOMECHANICS, INC. IMicro Nanoindenter made by the company can be used as a nanoindentation device.
- the continuous rigidity measuring method includes, for example, Advanced Dynamic E and H. NMT methods can be used.
- IMicro dedicated software may be used to calculate the load and stiffness.
- the sample is loaded by an indenter until a maximum load of 50 mN is reached.
- the indenter for example, a verkovic type diamond indenter is used.
- the Poisson's ratio and the load of the object to be measured may be appropriately set to appropriate values.
- the hardness HBC After measuring the hardness HBC by the nanoindentation method, if there is no imprint on the surface of the optical interference layer that matches the shape of the indenter used, it can be judged that the measured hardness HBC is not accurate. .. The above events are believed to occur because the uncured hardcourt layer is excessively soft. That is, this measured hardness is strongly influenced by the transparent supporting substrate, not the uncured hardcourt layer. Therefore, in the above case, the hardness HBC may be considered to be less than 0.1 GPa .
- the cured laminated film has excellent wear resistance.
- the surface of the optical interference layer of the laminated film irradiated with the active energy ray of the integrated light amount of 2000 mJ / cm 2 is rubbed 3,000 times while applying a vertical load of 19.6 N per 4 cm 2 , scratches are visible on the optical interference layer. It is preferable not to do so. In this case, the deterioration of visibility due to the change in the appearance of the molded product is likely to be suppressed.
- the laminated film cured after being subjected to the specific heat treatment also has wear resistance satisfying the above.
- the scratches are not visible means that the scratches cannot be observed visually.
- a “scratch” is, for example, a rough surface. As long as no scratches are visually observed, very slight scratches may be observed when the sample after the wear test is observed using a microscope having a magnification of 100 times.
- the wear test is performed under the above conditions using a known method.
- a friction element to which a cotton cloth is fixed is usually used for the wear test.
- This friction element applies a vertical load (specifically, 19.6 N per 4 cm 2 ) to the sample.
- the laminated film may be subjected to a specific heat treatment before irradiation with active energy rays.
- the laminated film may be heat-treated in an atmosphere of 150 to 190 ° C. for 30 to 60 seconds in addition to or in place of the specific heat treatment. By these heat treatments, the surface of the laminated film is flattened by leveling, and the wear resistance is easily improved.
- the electrostatic friction coefficient ⁇ AC of the optical interference layer of the laminated film irradiated with the active energy ray having an integrated light amount of 2000 mJ / cm 2 is preferably 0.3 or less, more preferably 0.25 or less, and particularly preferably 0.20 or less.
- the coefficient of static friction is measured according to JIS K 7125. The coefficient of static friction of the laminated film cured after the specific heat treatment also satisfies the above range.
- the optical interference layer is laminated with the uncured hard coat layer in an uncured state. Further, the laminated film is subjected to various processing in an uncured state. Therefore, in addition to antireflection performance, the optical interference layer has high hardness, low tack and is not easily contaminated, damage during processing and appearance change are suppressed, and it is different from other layers. It is required that curl due to the difference in heat shrinkage is suppressed. In particular, the light interference layer has excellent antireflection performance, low tack and is not easily contaminated, and damage during processing (for example, dents such as suction marks in the decoration process, squeegee marks), etc. are suppressed. Is required.
- the physical characteristics of the uncured light interference layer can be adjusted by the thickness thereof, the composition of the light interference layer forming composition, and the like.
- the hard coat layer is also laminated with the uncured optical interference layer in an uncured state. Further, as described above, the laminated film is subjected to various processing in an uncured state. Therefore, the uncured hardcourt layer has high hardness, low tack and is not easily contaminated, and is damaged during processing and changes in appearance (for example, foaming in the preform process), as in the case of the optical interference layer. , Cracks) and curl due to the difference in heat shrinkage from other layers are required.
- the physical characteristics of the uncured hardcoat layer can be adjusted by the thickness thereof, the composition of the hardcoat layer forming composition, and the like.
- the transparent supporting base material is not particularly limited as long as it is transparent. "Transparent” specifically means that the total light transmittance is 80% or more.
- the total light transmittance of the transparent supporting substrate is 80% or more, preferably 90% or more.
- the total light transmittance can be measured by a method according to JIS K 7631-1.
- As the transparent supporting base material those known in the art are used without particular limitation.
- the transparent supporting substrate may be colorless or colored.
- the transparent support base material is appropriately selected according to the application.
- the transparent supporting base material include a polycarbonate (PC) film, a polyester film such as polyethylene terephthalate and polyethylene naphthalate; a cellulose film such as diacetyl cellulose and triacetyl cellulose; an acrylic film such as polymethyl methacrylate (PMMA); and polystyrene.
- a styrene film such as an acrylonitrile / styrene copolymer; an olefin film such as polyvinyl chloride, polyethylene, polypropylene, a polyolefin having a cyclic or norbornene structure, an olefin film such as an ethylene / propylene copolymer; an amide film such as nylon and an aromatic polyamide. ..
- the transparent supporting base material is a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinylbutyral, polyallylate, polyoxymethylene, and epoxy resin. It may be a film containing a mixture of these polymers.
- the transparent support base material may be a laminate of a plurality of films.
- the transparent support base material may be, for example, a laminate of a film made of an acrylic resin and a film made of a polycarbonate resin.
- the transparent supporting substrate may be optically anisotropic or isotropic.
- the magnitude of birefringence of the optically anisotropic transparent supporting substrate is not particularly limited.
- the phase difference of the transparent supporting substrate having anisotropy may be 1/4 ( ⁇ / 4) of the wavelength and may be 1/2 ( ⁇ / 2) of the wavelength.
- the uncured optical interference layer contains an active energy ray-curable optical interference layer forming composition (hereinafter, may be referred to as composition R).
- composition R is cured by the active energy rays.
- Active energy rays are ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- the composition R is particularly preferably ultraviolet curable.
- the optical interference layer functions as a layer having a low refractive index.
- the refractive index of the cured optical interference layer may be, for example, 1.20 or more and 1.55 or less, 1.25 or more and 1.50 or less, and 1.30 or more and 1.45 or less. As a result, good antireflection property is exhibited.
- the optical interference layer forming composition contains, for example, a first layer forming component and low refraction particles.
- Low-refractive particles are particles having a low refractive index and lower the refractive index of the optical interference layer.
- the low refraction particles include hollow silica fine particles and hollow resin particles.
- the low refractive index particles can reduce the refractive index while maintaining the strength of the optical interference layer.
- the low refraction particles are a structure filled with gas and / or a porous structure containing gas.
- the refractive index decreases in inverse proportion to the occupancy of the gas. Therefore, the low-refractive index particles have a low refractive index as compared with the refractive index of the particles having no hollow.
- silica fine particles having a nanoporous structure formed inside and / or at least a part of the surface may be used.
- the nanoporous structure is formed according to the morphology, structure, aggregated state, and dispersed state inside the coating film of the silica fine particles.
- the volume average particle size (primary particle size) of the low refraction particles is preferably 50 nm or more and 200 nm or less.
- the film thickness of the optical interference layer is designed in consideration of the volume average particle diameter (primary particle diameter) of the low refraction particles and the like. Specifically, the optical interference layer is designed to be thicker than the volume average particle diameter of the low refraction particles. As a result, the low-refractive particles are less likely to be exposed from the surface of the optical interference layer, and when the surface of the optical interference layer is rubbed, the low-refractive particles are suppressed from falling off from the optical interference layer, and the wear resistance is easily improved. Become.
- the content of the low refraction particles is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more with respect to 100 parts by mass of the solid content of the composition R.
- the content of the low refraction particles is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R.
- the first layer-forming component contains a first reactive component having two or more polymerizable functional groups in one molecule.
- the first reactive component comprises at least one selected from the group consisting of a first monomer, a first oligomer and a first polymer.
- the weight average molecular weight of the first monomer and the first oligomer is 10,000 or less, and may be 9000 or less.
- the weight average molecular weight of the first polymer is more than 10,000 and may be 20,000 or more.
- the weight average molecular weight of the first polymer may be 100,000 or less.
- the weight average molecular weight (Mw) can be calculated from the chromatogram measured by the gel permeation chromatograph based on the molecular weight of standard polystyrene.
- the first reactive component preferably contains a (meth) acrylate compound.
- the (meth) acrylate compound include acrylic (meth) acrylate compounds such as acrylic (meth) acrylate monomer, acrylic (meth) acrylate oligomer and acrylic (meth) acrylate polymer; urethane (meth) acrylate monomer and urethane (meth).
- Urethane (meth) acrylate compounds such as acrylate oligomers and urethane (meth) acrylate polymers; examples include silicon (meth) acrylate compounds such as silicon (meth) acrylate monomers, silicon (meth) acrylate oligomers and silicon (meth) acrylate polymers. These may be used alone or in combination of two or more.
- “(Meta) acrylate” represents acrylate and / or methacrylate.
- the acrylic equivalents of the first monomer and the first oligomer are not particularly limited. In terms of reactivity, the acrylic equivalents of the first monomer and the first oligomer were 100 g / eq. The above is preferable, and 110 g / eq. The above is more preferable, and 115 g / eq. The above is particularly preferable.
- the acrylic equivalents of the first monomer and the first oligomer are 200 g / eq. It may be 180 g / eq. It may be 160 g / eq. It may be:
- Examples of the (meth) acrylate monomer as a raw material for the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- 2-ethylhexyl acrylate acrylic acid, methacrylic acid, isostearyl (meth) acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl Succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) Examples thereof include acrylate, dipentaerythritol hexaacrylate (DPHA), pentaerythritol (tri / tetra) acrylate (PETA), N-methylol (meth) acrylamide, and N-hydroxy (meth) acrylamide.
- DPHA dipentaery
- acrylic (meth) acrylate oligomer or polymer examples include at least one polymer of the above (meth) acrylate monomer.
- Urethane (meth) acrylate monomers or oligomers can also be prepared by reacting, for example, a polycarbonate diol with a (meth) acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule, and a polyisocyanate. can.
- Examples of the urethane (meth) acrylate polymer include at least one polymer of the above-mentioned urethane (meth) acrylate monomer and oligomer.
- the silicon (meth) acrylate compound is a (meth) acrylate compound having a siloxane bond.
- the silicon (meth) acrylate compound makes it possible to reduce the surface tension of the uncured optical interference layer, improve the leveling property, and reduce the tack.
- the first reactive component (typically, a (meth) acrylate compound) may contain a fluorine atom.
- the first layer-forming component may contain a non-reactive component having less than 2 polymerizable functional groups contained in one molecule.
- the mixed phase mainly occurs when the monomer and / or oligomer having a small molecular weight contained in the hard coat layer diffuses by heat and reaches the optical interference layer. Then, the low refraction particles can suppress the thermal diffusion of the monomer and / or the oligomer from the hard coat layer to the optical interference layer.
- the first polymer has a small effect of suppressing the thermal diffusion of the monomer and / or the oligomer from the hard coat layer to the light interference layer.
- the content of the first polymer is different.
- 100 x Z / (X + Z) ⁇ 40 (%) It is preferable to include the first polymer so as to satisfy the above relationship. It is more preferable to satisfy the relationship of 100 ⁇ Z / (X + Z) ⁇ 35 (%), and it is particularly preferable to satisfy the relationship of 100 ⁇ Z / (X + Z) ⁇ 30 (%).
- the low refractive particles are contained in an amount of 30% by mass or more (X ⁇ 30) with respect to the total of the first oligomer, the first monomer, the first polymer and the low refractive particles, the content X of the low refractive particles and the first
- the first monomer and / or the first oligomer has a slightly smaller effect of suppressing multiphase flow than the low refraction particles, it is important in that it improves various physical properties of the cured laminated film (molded body).
- the composition R may contain inorganic oxide fine particles.
- the inorganic oxide fine particles suppress the volume shrinkage of the uncured optical interference layer and facilitate the increase in rigidity. Therefore, changes in appearance during the manufacturing process of the uncured optical interference layer are likely to be suppressed. Further, the appearance change and the generation of curl of the cured optical interference layer are suppressed. In addition, the tackiness of the cured optical interference layer is reduced and the wear resistance is likely to be increased.
- the content of the inorganic oxide fine particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more with respect to 100 parts by mass of the solid content of the composition R.
- the content of the inorganic oxide fine particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R.
- the solid content of the composition R is all the components of the composition R excluding the solvent. The same applies to the solid content of the hard coat layer forming composition.
- the inorganic oxide fine particles are not particularly limited.
- examples of the inorganic oxide fine particles include silica (SiO 2 ) particles (excluding hollow ones), alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, and zinc oxide particles. ..
- the surface of the inorganic oxide fine particles may be modified with a functional group containing an unsaturated double bond.
- a (meth) acryloyl group is desirable.
- silica particles and alumina particles are preferable from the viewpoint of cost and coating stability, and silica particles and alumina particles whose surface is modified with a functional group are particularly preferable.
- the form of the inorganic oxide fine particles may be a sol.
- the average particle size of the inorganic oxide fine particles is not particularly limited. From the viewpoint of transparency and paint stability, the average particle size of the inorganic oxide fine particles is preferably 5 nm or more and 100 nm or less.
- the average particle size of the inorganic oxide fine particles is a value measured by using image processing software from an image of a cross section obtained by an electron microscope. The average particle size of other particles can also be determined by the same method.
- the composition R preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy ray-curable resin component.
- photopolymerization initiator examples include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, and an oxime ester-based polymerization initiator.
- alkylphenone-based photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-.
- acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide.
- titanosen-based photopolymerization initiator for example, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium is used. Can be mentioned.
- Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2). -Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy) Ethoxy) ethyl ester can be mentioned.
- These photopolymerization initiators may be used alone or in combination of two or more.
- the content of the photopolymerization initiator is preferably 0.01 part by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more with respect to 100 parts by mass of the solid content of the composition R.
- the content of the photopolymerization initiator is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R.
- the composition R may contain a solvent.
- the solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of the transparent supporting base material, the coating method, and the like.
- the solvent examples include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether.
- aromatic solvents such as toluene and xylene
- ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone
- diethyl ether isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether.
- Ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone.
- Amid-based solvents such as; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; halogen-based solvents such as dichloromethane and chloroform.
- cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve
- alcohol-based solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol
- halogen-based solvents such as dichloromethane and chloroform.
- the composition R can contain various additives, if necessary.
- Additives include, for example, antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, surface modifiers, surface modifiers, leveling agents and light stabilizers (eg, hindered amine light stabilizers (eg, hindered amine light stabilizers). HALS))).
- the content of each additive is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more with respect to 100 parts by mass of the solid content of the composition R.
- the content of each additive is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the solid content of the composition R.
- the uncured hard coat layer contains an active energy ray-curable hard coat layer forming composition (hereinafter, may be referred to as composition HC).
- composition HC is cured by active energy rays. By adjusting the integrated light amount of the active energy rays, the hardness and / or the stretch ratio of the hard coat layer can be controlled.
- the composition HC is preferably cured by the same type of active energy rays as the composition R.
- Hardcourt layer forming composition contains a second layer-forming component.
- the second layer-forming component contains a second reactive component having two or more polymerizable functional groups in one molecule.
- the second reactive component preferably contains at least one of the second monomer and the second oligomer.
- the weight average molecular weight of the second monomer and the second oligomer is 10,000 or less, and may be 9000 or less.
- the total content of the second oligomer and the second monomer is preferably 25 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC.
- the hardness HBC is easily controlled to 0.5 GPa or less. Therefore, the uncured hard coat layer and the uncured optical interference layer are likely to adhere to each other. Further, when laminating the uncured hard coat layer and the uncured optical interference layer, it becomes easy to suppress air from entering between the layers (air biting).
- the total content of the second oligomer and the second monomer is more preferably 28 parts by mass or more and particularly preferably 30 parts by mass or more with respect to 100 parts by mass of the solid content of the composition HC.
- the hardness HBC is easily controlled to 0.1 GPa or more. Therefore, defects such as dents and damages during slit formation and cutting, dents due to foreign matter mixed when a plurality of laminated films are laminated, squeegee marks or suction marks are suppressed, and the yield is easily improved.
- the total content of the second oligomer and the second monomer is more preferably 62 parts by mass or less, particularly preferably 60 parts by mass or less, based on 100 parts by mass of the solid content of the composition HC.
- the second reactive component preferably contains a second polymer having a weight average molecular weight of more than 10,000 together with the second monomer and / or the second oligomer in that the tackiness of the uncured hard coat layer can be suppressed.
- the weight average molecular weight of the second polymer is more than 10,000 and may be 20,000 or more.
- the weight average molecular weight of the second polymer may be 100,000 or less.
- Preferred second reactive components include (meth) acrylate compounds similar to those exemplified as the first reactive component. From the viewpoint of adhesion to the transparent supporting substrate and the light interference layer and transparency, the second reactive component preferably contains a (meth) acrylate compound.
- the composition HC may contain inorganic oxide fine particles.
- the inorganic oxide fine particles include those exemplified with respect to the composition R.
- the content of the inorganic oxide fine particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC.
- the content of the inorganic oxide fine particles is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more with respect to 100 parts by mass of the solid content of the composition HC.
- the composition HC preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy ray-curable resin component.
- the photopolymerization initiator include those exemplified with respect to the composition R as well.
- the content of the photopolymerization initiator is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC.
- the composition HC may contain a solvent.
- the solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of the transparent supporting base material, the coating method, and the like. Examples of the solvent include those exemplified for the composition R as well. Of these, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferable.
- the composition HC can contain various additives, if necessary.
- the additive include those exemplified with respect to the composition R as well.
- the resin components of the composition HC and the composition R may be the same or different. Above all, it is preferable that the resin components of both are the same or the same kind. This is because the adhesion between the uncured hard coat layer and the uncured optical interference layer is improved, and peeling between the layers is less likely to occur.
- the laminated film may further have at least one uncured functional layer between the uncured hardcoat layer and the uncured optical interference layer.
- the functional layer reinforces the optical function of the laminated film or imparts a new optical function.
- the functional layer may be another optical interference layer having optical characteristics different from those of the above optical interference layer.
- the functional layer may be a combination of two or more other optical interference layers having characteristics different from those of the above-mentioned optical interference layer.
- the preferred functional layer is, for example, at least one of an optical interference layer having a high refractive index and an optical interference layer having a medium refractive index.
- the refractive index of the high refractive index layer may be more than 1.55 and 2.00 or less.
- the refractive index of the medium refractive index layer is not particularly limited, and may be between the optical interference layer (low refractive index layer) and the high refractive index layer.
- the refractive index of the medium refractive index layer may be, for example, 1.55 or more and 1.75 or less.
- the thickness of other optical interference layers is not particularly limited.
- the thickness of each other optical interference layer may be 10 nm or more and 300 nm or less.
- the thickness of the optical interference layer per layer is preferably 15 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more.
- the thickness of the optical interference layer per layer is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.
- the functional layer forming composition forming the functional layer may contain the same components as those contained in the above composition HC or composition R.
- the functional layer forming composition forming another light interference layer may contain the same components as those contained in the composition R.
- the functional layer forming composition forming another light interference layer may contain highly refracted particles.
- the components contained in the plurality of functional layers may be the same or different.
- the high refractive index layer and the medium refractive index layer may contain a resin component other than the active energy ray-curable type.
- resin components include thermoplastic resins such as alkyd resins, polyester resins, and acrylic resins; and thermosetting properties such as epoxy resins, phenolic resins, melamine resins, urethane resins, and silicon resins.
- Resin; Polyisocyanate can be mentioned.
- the laminated film may have a protective film on the surface of the uncured optical interference layer opposite to the uncured hard coat layer. As a result, damage is easily suppressed when the laminated film is wound into a roll or unwound from the roll.
- the protective film protects the optical interference layer and the laminated film, and also functions as a release paper for forming the composition R into a film.
- the protective film may have an adhesive layer on the coated surface.
- a protective film known in the art is used without particular limitation.
- the protective film may be colorless or colored.
- the protective film may be transparent.
- the thickness of the protective film is not particularly limited.
- the thickness of the protective film may be 20 ⁇ m or more and 100 ⁇ m or less. As a result, the protective effect of the uncured optical interference layer tends to be enhanced.
- the thickness of the protective film is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, further preferably 33 ⁇ m or more, and particularly preferably 35 ⁇ m or more.
- the thickness of the protective film is preferably 85 ⁇ m or less, more preferably 80 ⁇ m or less, and particularly preferably 65 ⁇ m or less.
- the thickness of the protective film is a value that does not include the thickness of the adhesive layer.
- the protective film is made of resin, for example.
- the resin film include a polyolefin film such as a polyethylene film and a polypropylene film (including a non-stretched polypropylene film (CPP film) and a biaxially stretched polypropylene film (OPP film)), and a modification obtained by modifying these polyolefins to add further functions.
- Polyethylene film, polyethylene terephthalate, polyester film such as polycarbonate and polylactic acid, polystyrene film, polystyrene resin film such as AS resin film and ABS resin film, nylon film, polyamide film, polyvinyl chloride film and polyvinylidene chloride film, polymethyl Penten film can be mentioned.
- Additives such as an antistatic agent and an ultraviolet ray inhibitor may be added to the resin film, if necessary.
- the surface of the resin film may be subjected to corona treatment or low temperature plasma treatment.
- At least one selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film is preferable.
- At least one selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film having a thickness of 30 ⁇ m or more and 100 ⁇ m or less is preferable.
- FIG. 1 is a cross-sectional view schematically showing a laminated film according to this embodiment.
- the laminated film 10 includes a transparent support base material 11, an uncured hard coat layer 12 arranged on one of the main surfaces thereof, and an uncured optical interference layer 13 formed on the uncured hard coat layer 12. , Equipped with.
- the molded body according to the present embodiment is obtained by curing the above-mentioned laminated film.
- the molded product is a completely cured product of the laminated film.
- the molded body has a transparent support base material, a cured hard coat layer, and a cured optical interference layer.
- the molded product may further have at least one cured functional layer between the cured hardcourt layer and the cured optical interference layer.
- the molded product may or may not have a protective film.
- the protective film is used according to the purpose of use.
- the molded body is obtained by irradiating the laminated film with, for example, an active energy ray having an integrated light amount of 200 mJ / cm 2 or more to cure the uncured hard coat layer and the uncured optical interference layer.
- the molded body is particularly suitable as a protective material for various sensors arranged in and around the display.
- the display include a liquid crystal display, an organic EL display, and a plasma display.
- the molded body is particularly suitable as a protective material for an in-vehicle touch panel display and its surroundings.
- the molded body is arranged so that the light interference layer is outside the hard coat layer.
- the molded body may further include a decorative layer.
- a decorative layer According to the laminated film according to the present embodiment, low reflectance can be maintained even when heat treatment is applied when forming the decorative layer.
- the decorative layer is provided, for example, on the bezel portion surrounding the display.
- the molded body is, for example, a transparent support base material, a hard coat layer and a light interference layer arranged on one main surface of the transparent support base material, and a decorative layer arranged on the other main surface of the transparent support base material. And.
- the decorative layer may be provided on a portion of the other main surface of the transparent supporting substrate.
- the decorative layer is a layer that gives a decoration such as a pattern, characters, or metallic luster to a molded body. The decorative layer enhances the design of the molded product.
- the decorative layer examples include at least one of a printing layer and a thin-film deposition layer.
- the print layer and the vapor deposition layer are each one or more layers, and may include a plurality of layers.
- the thickness of the decorative layer is not particularly limited, and is appropriately set according to the design and the like.
- the print layer is formed of, for example, a colored ink containing a binder resin and a colorant.
- the binder resin is not particularly limited.
- the binder resin include polyvinyl chloride resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and celluloses. Examples thereof include ester-based resins, alkyd resins, and chlorinated polyolefin-based resins.
- the colorant is not particularly limited, and examples thereof include known pigments or dyes.
- the yellow pigment include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as titanium nickel antimony oxide.
- the red pigment include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as valve stems.
- the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue.
- the black pigment include organic pigments such as aniline black.
- the white pigment include inorganic pigments such as titanium dioxide.
- the vapor deposition layer is formed of, for example, at least one metal selected from the group of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof. Will be done.
- the molded body may further include a molding resin layer.
- the molded resin layer supports the hard coat layer and the optical interference layer together with the transparent supporting base material.
- the molded body is, for example, a transparent support base material, a hard coat layer and a light interference layer arranged on one main surface of the transparent support base material, and a molding resin layer arranged on the other main surface of the transparent support base material.
- the shape of the molded resin layer is not limited. Therefore, the degree of freedom in designing the molded body is increased.
- the molded body includes a transparent support base material, a hard coat layer and a light interference layer arranged on one main surface of the transparent support base material, and a decorative layer arranged on the other main surface of the transparent support base material. It may be provided with a molding resin layer. In this case, the decorative layer is arranged so as to be sandwiched between the transparent support base material and the molding resin layer.
- the resin forming the molding resin layer is not particularly limited.
- the molded resin layer contains, for example, a thermosetting resin and / or a thermoplastic resin.
- the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester, and thermosetting polyimide.
- the thermoplastic resin include so-called engineering plastics. Examples of engineering plastics include polyamide, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polysulfone, polyether sulfone, polyphenylene sulfide, and liquid crystal polymers.
- FIG. 2 is a cross-sectional view schematically showing a molded body according to the present embodiment.
- the molded body 20 is decorated with a transparent support base material 11, a cured hard coat layer 22 arranged on one of the main surfaces thereof, and a cured optical interference layer 23 formed on the hard coat layer 22.
- a layer 24 and a molding resin layer 25 are provided.
- the decorative layer 24 is arranged so as to cover a part of the other main surface of the transparent support base material 11.
- the molding resin layer 25 is arranged so as to cover the entire other main surface of the transparent support base material 11 and the entire decorative layer 24.
- the active energy ray-curable hard coat layer forming composition is applied on one surface of a transparent supporting substrate having a thickness of 50 ⁇ m or more and 600 ⁇ m or less, and has not been formed.
- FIG. 3 is a flowchart showing a method for manufacturing a laminated film according to the present embodiment.
- Step of forming an uncured hard coat layer (S11)
- the method for forming the uncured hardcoat layer is not particularly limited.
- the uncured hardcourt layer is formed, for example, by applying the composition HC on one surface of the transparent supporting substrate.
- the composition HC can be prepared by a method usually used by those skilled in the art. For example, it can be prepared by mixing each of the above components using a commonly used mixing device such as a paint shaker or a mixer.
- the method for applying the composition HC is not particularly limited, and is carried out by a method usually used by those skilled in the art.
- the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a bar coating method (for example, a wire bar coating method), a die coating method, an inkjet method and a gravure coating method.
- the coating amount of the composition HC is not particularly limited.
- the composition HC is applied, for example, after drying so that the thickness of the uncured hardcoat layer is 2 ⁇ m or more and 30 ⁇ m or less.
- a drying step may be performed.
- the drying conditions are not particularly limited, and are appropriately set so that at least a part of the solvent contained in the composition HC is removed.
- Examples of the drying method include air drying (natural drying), heat drying, and vacuum drying. Of these, heat drying is preferable.
- the uncured hardcourt layer can be leveled as it dries. Drying is performed between the formation of the uncured hardcoat layer on the transparent supporting substrate and the time when the uncured hardcoat layer is subjected to the laminating step. For example, the uncured hardcourt layer is dried before the transparent support substrate with the uncured hardcourt layer is carried into the laminating machine.
- the transparent supporting substrate may be wound into a roll. This enables roll-to-roll processing up to the laminating process. Further, the transparent supporting base material may be wound up after the protective film is attached to the surface of the uncured hard coat layer. The protective film and the uncured hardcoat layer may be bonded via an adhesive layer.
- Step of forming an uncured optical interference layer (S12)
- the method for forming the uncured optical interference layer is not particularly limited.
- the uncured light interference layer is formed by, for example, applying the composition R on one surface of another supporting base material (typically, the above-mentioned protective film).
- the method of applying the composition R is the same as that of the composition HC, and is carried out by a method usually used by those skilled in the art.
- the coating amount of the composition R is not particularly limited.
- the composition R is applied, for example, after drying so that the thickness of the uncured light interference layer is 15 nm or more and 200 nm or less.
- a drying step may be performed.
- the drying conditions are not particularly limited, and are appropriately set so that at least a part of the solvent contained in the composition R is removed.
- Examples of the drying method include the same method as for drying the hard coat layer. Of these, heat drying is preferable. By heating, the uncured optical interference layer can be leveled as it dries.
- Drying is performed between the formation of the uncured optical interference layer on the other supporting substrate and the time when the uncured optical interference layer is subjected to the laminating step.
- the uncured optical interference layer is dried before the other supporting substrate with the uncured optical interference layer is carried into the laminating machine.
- the other supporting substrate may be wound into a roll. This enables roll-to-roll processing up to the laminating process. Further, after the protective film is attached to the surface of the uncured optical interference layer, another supporting base material may be wound up. The protective film and the uncured optical interference layer may be bonded to each other via an adhesive layer.
- the transparent supporting base material having an uncured hard coat layer is carried into the laminating machine, and the other supporting base material that has been wound up is carried into the laminating machine.
- the supporting base material is carried into the laminating machine while being unwound.
- the bonding is performed while applying pressure.
- the pressure may be, for example, 0.1 N / cm or more and 50 N / cm or less.
- the pressure is preferably 0.5 N / cm or more.
- the pressure is preferably 30 N / cm or less.
- each layer at the time of bonding is not particularly limited. Since each layer is uncured, it can be bonded at a low temperature. On the other hand, since the laminated film according to the present embodiment tends to suppress the generation of multiphase, each layer may be heated at the time of bonding. The temperature of each layer at the time of bonding may be 0 ° C. or higher and 100 ° C. or lower.
- a laminated film having an uncured functional layer between an uncured hard coat layer and an uncured optical interference layer is produced, for example, by the following steps. First, another uncured functional layer is formed on a new supporting substrate. Next, the surface of the uncured hardcoat layer opposite to the transparent supporting substrate and the surface of the uncured functional layer opposite to the new supporting substrate are bonded together. After peeling off the new supporting base material, the uncured optical interference layer supported by the other supporting base material is attached to the exposed uncured functional layer. If necessary, the step of bonding the uncured functional layer to the uncured hard coat layer or the uncured functional layer laminated on the uncured functional layer is repeated before the optical interference layer is bonded.
- a laminated film containing a transparent supporting base material, an uncured hard coat layer, at least one uncured functional layer, an optical interference layer, and another supporting base material can be obtained in this order.
- the other supporting substrate may or may not be peeled off.
- the laminated film may be wound into a roll. In this case, it is preferable that the other supporting base material is not peeled off.
- FIG. 4 is a schematic diagram illustrating a laminating process in the method for producing a laminated film according to the present embodiment.
- An uncured hardcoat layer 12 is formed on one surface of the transparent support base material 11. This laminate is obtained in the step of forming an uncured hardcoat layer.
- This laminated body is conveyed in a flat state from the left direction to the right direction in FIG.
- the uncured optical interference layer 13 is laminated on one surface of the other supporting base material 14. This laminate is obtained in the step of forming the uncured optical interference layer. This laminated body is conveyed in a flat state from the left direction to the right direction in FIG.
- each layer and each base material may be appropriately set.
- the molded product according to the present embodiment is, for example, a decorative step of forming a decorative layer on the other main surface of the transparent support base material of the above-mentioned laminated film, and a laminated film after the decorative step. It is manufactured by a method comprising a curing step of irradiating an active energy ray having an integrated light amount of 200 mJ / cm 2 or more.
- the decorating step includes a heating step of heating the laminated film at 80 ° C. or higher for 20 minutes or longer.
- an injection molding process or a preform process and an injection molding process are performed as necessary.
- the laminated film is thermoformed into a shape along a desired three-dimensional shape.
- the curing process may be performed multiple times. For example, after the preform step, a semi-curing step of irradiating an active energy ray so as to cure a part of the laminated film may be performed. In this case, after the injection molding step, the main curing step of irradiating the active energy rays so as to cure the rest of the laminated film is performed.
- the molded body is manufactured by a method including, for example, a decoration step (S21), a preform step (S22), a curing step (S23), and an injection molding step (S24) in this order.
- FIG. 5 is a flowchart showing a method for manufacturing a molded product according to the present embodiment.
- the molded product also has, for example, a decoration step (S21), a preform step (S22), a semi-curing step (S23-1), an injection molding step (S24), and a main curing step (S23-2) in this order.
- a decoration step S21
- a preform step S22
- a semi-curing step S23-1
- an injection molding step S24
- a main curing step S23-2
- FIG. 6 is a flowchart showing a method of manufacturing another molded product according to the present embodiment.
- the laminated film When the laminated film is wound into a roll, the laminated film is unwound from the roll to form a slit or cut into a desired shape and size before the decoration step. May be good. Hereinafter, each step will be described.
- a decorative layer (typically a printed layer and a vapor-deposited layer) is formed on the other main surface of the transparent supporting base material of the laminated film.
- the method of forming the print layer is not particularly limited. Examples of the method for forming the print layer include an offset printing method, a gravure printing method, a screen printing method, a roll coating method, and a spray coating method.
- the method for forming the thin-film deposition layer is also not particularly limited. Examples of the method for forming the thin-film deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.
- the decoration step includes a heating step of heating the laminated film at 80 ° C. or higher for 20 minutes or longer.
- the heating step is performed, for example, for drying the decorative layer.
- the obtained molded product has a low reflectance even when undergoing such a heating step.
- the decoration process may be performed multiple times while changing the color, for example.
- heating at a temperature higher than 80 ° C. for 5 minutes or less, or heating at a temperature lower than 80 ° C. for 20 minutes or longer may be further performed. Such heating does not significantly contribute to the generation of multiphase.
- Preform process S22
- the laminated film is preformed into a shape that conforms to a desired three-dimensional shape.
- Injection molding typically, insert mold lamination (IML) molding
- IML insert mold lamination
- the laminated film is inserted into a mold, and the molding resin is injected toward the laminated film.
- a trimming step may be performed to remove unnecessary portions of the laminated film.
- the preform method is not particularly limited.
- the preform is performed by, for example, a vacuum forming method, a compressed air forming method, or a vacuum forming method.
- the mold and the laminated film are installed in the same processing chamber.
- the laminated film is installed so that the transparent support base material faces the mold.
- the laminated film is heated to put the treatment chamber in vacuum and / or pressure. As a result, the laminated film is deformed along the mold.
- the laminated film is then cooled and removed from the mold.
- the laminated film may be heated at 90 ° C. or higher and 190 ° C. or lower for 20 seconds or more and 5 minutes or less.
- Semi-curing step (S23-1) Irradiate the active energy rays so that a part of the laminated film is cured. As a result, a semi-cured laminated film can be obtained.
- the semi-curing step suppresses the sticking of the laminated film to the mold in the injection molding process, and the laminated film is adjusted to the draw ratio required for the injection molding process to suppress the generation of cracks in the injection molding process. can do.
- the integrated light amount of the active energy ray is, for example, 1 mJ / cm 2 or more and less than 200 mJ / cm 2 .
- a trimming step of removing unnecessary portions of the laminated film may be performed.
- the type of active energy ray is not particularly limited.
- the active energy ray is appropriately selected according to the type of the resin component contained in the layer forming composition.
- the active energy ray is not particularly limited, and may be ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays. Of these, ultraviolet rays having a wavelength of 380 nm or less are preferable. Ultraviolet rays are irradiated using, for example, a high-pressure mercury lamp or an ultra-high pressure mercury lamp.
- injection molding for example, the optical interference layer is opposed to the mold, and the molding resin is injected toward the transparent support base material. As a result, the laminated film is shaped into the shape of a mold, and a molding resin layer is formed on the other main surface of the transparent support base material.
- Curing step (S23), main curing step (S23-2) The laminated film is irradiated with active energy rays to completely cure the laminated film. As a result, a molded product is obtained.
- the integrated light amount of the active energy rays in this curing step is 200 mJ / cm 2 or more.
- the integrated light amount of the active energy ray may be 5000 mJ / cm 2 or less, and may be 3000 mJ / cm 2 or less.
- the active energy rays may be the same as or different from the semi-curing step.
- the above aspect is an example, and a known treatment, processing step, or the like may be introduced if desired.
- Acrylic polymers A, B and C were prepared as follows. [Preparation of acrylic polymer A] A mixture consisting of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate and 1.5 parts of t-butylperoxy-2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene was put into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel, and heated to 110 ° C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant velocity over 2 hours under a nitrogen atmosphere. After completion of the dropping, the reaction was carried out for 1 hour under the temperature condition of 110 ° C.
- reaction vessel having the same shape as above, 226.5 parts of precursor A1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, 56 parts of toluene were charged, and air was blown into the reaction vessel to stir. While heating to 90 ° C. Under the temperature condition of 90 ° C., a mixed solution of 3.0 parts of toluene and 0.81 part of tetrabutylammonium bromide was further added to this reaction vessel, and the mixture was reacted for 1 hour. Subsequently, the mixture was heated to 105 ° C., and the reaction was carried out under the temperature condition of 105 ° C. until the acid value of the solid content in the reaction solution became 8 or less.
- KOH potassium hydroxide
- reaction vessel having the same shape as above, 306.5 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, 56 parts of toluene were charged, and air was blown into the reaction vessel to stir. While heating to 90 ° C. Under the temperature condition of 90 ° C., a mixed solution of 3.0 parts of toluene and 0.81 part of tetrabutylammonium bromide was further added to this reaction vessel, and the mixture was reacted for 1 hour. Subsequently, the mixture was heated to 105 ° C., and the reaction was carried out under the temperature condition of 105 ° C. until the acid value of the solid content in the reaction solution became 8 or less.
- reaction vessel having the same shape as above, 295.8 parts of precursor C1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, 56 parts of toluene were charged, and air was blown into the reaction vessel to stir. While heating to 90 ° C. Under the temperature condition of 90 ° C., a mixed solution of 3.0 parts of toluene and 0.81 part of tetrabutylammonium bromide was further added to this reaction vessel, and the mixture was reacted for 1 hour. Subsequently, the mixture was heated to 105 ° C., and the reaction was carried out under the temperature condition of 105 ° C. until the acid value of the solid content in the reaction solution became 8 or less.
- KRM-8452 Dycel Ornex, Mw3,884, acrylic equivalent 120g / eq CN-9893: Arkema H-7M40: Negami Kogyo, Mw 10,000-15,000, UN-904M: Made by Negami Kogyo Co., Ltd., Mw4, 900
- Aronix M-402 Toagosei
- DPHA Aronix M-305 PETA manufactured by Toagosei Co., Ltd.
- OSCAL 1842 JGC Catalysts and Chemicals Co., Ltd., reactive silica organosol, particle diameter 10 nm
- NANON5 ZR-010 Solar Turbines, Zirconium Oxide, Volume Average Particle Size 20nm
- Omnirad 127 IGM RESINS, ⁇ -hydroxyacetophenone Omnirad 184: IGM RESINS, ⁇ -hydroxyalkylphenone
- TB1-TB5 (Transparent support base material) TB1-TB5: Product name AW-10U, manufactured by Wavelock Advanced Technology, a two-layer (PMMA / PC) film consisting of PMMA and PC, thickness 300 ⁇ m (TB1), 200 ⁇ m (TB2), 500 ⁇ m (TB3), 30 ⁇ m. (TB4), 100 ⁇ m (TB5)
- Trefan # 40-2500 manufactured by Toray Industries, Inc., biaxially stretched polypropylene film (OPP), thickness 40 ⁇ m
- composition LR1 Preparation of composition LR1
- Acrylic polymer B (first polymer) 3.1 parts, Aronix M-402 (first monomer) 27.7 parts, Optool DAC-HP (surface conditioner) 11.6 parts, Megafuck RS-57 (surface modification) Agent) 8.0 parts and Omnirad 127 (photopolymerization initiator) 3.5 parts were mixed. Further, 46.1 parts of thruri rear 4320 (low refraction particles) were blended. This mixture was diluted with propylene glycol monomethyl ether to prepare a milky white composition LR1 having a solid content concentration of 3%. The refractive index of the layer formed by the composition LR1 was 1.20 or more and 1.55 or less.
- composition LR2-LR15 A milky white composition LR2-LR11, LR13-LR15 and a transparent composition LR12 having a solid content concentration of 3% were prepared in the same manner as in the composition LR1 except that the formulations shown in Table 1A were used.
- the refractive index of the layers formed by the compositions LR2 to LR15 was 1.20 or more and 1.55 or less.
- composition HR1 A milky white functional layer-forming composition HR1 having a solid content concentration of 3% was prepared in the same manner as in the composition LR1 except that the formulations shown in Table 1B were used.
- the refractive index of the layer formed by the composition HR1 was more than 1.55 and 2.00 or less.
- composition HC1 Acrylic polymer A (second polymer) 32.0 parts by mass, KRM-8452 (second oligomer, polyfunctional urethane acrylate oligomer) 36.3 parts by mass, Aronix M-402 (second monomer) 21.3 parts, OSCAL 1842 4.1 parts by mass of (inorganic oxide fine particles) and 6.3 parts by mass of Monomer 184 (starting photopolymerization) were mixed. This mixture was diluted with methyl isobutyl ketone to prepare a transparent composition HC1 with a solid content concentration of 35%.
- composition HC2-HC5 A transparent composition HC2-HC5 having a solid content concentration of 35% was prepared in the same manner as the composition HC1 except that the formulations shown in Table 1C were used.
- Example 1 (1) Production of Laminated Film (1-1) Formation of Uncured Light Interference Layer
- the composition LR1 was applied to an OPP film (protective film) with a gravure coater so that the thickness after drying was 120 nm. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to form an uncured optical interference layer.
- the protective film on which the uncured optical interference layer was formed was wound into a roll.
- the optical interference layer formed by the composition LR1-LR15 may be referred to as "LR layer”.
- composition HC1 was applied to the surface of PMMA of the transparent support base material TB1 by a gravure coater so that the thickness after drying was 12 ⁇ m. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to form an uncured hardcoat layer.
- the hard coat layer formed by the composition HC1-HC5 may be referred to as "HC layer”.
- (B) Reflectance A black paint (product name: CZ-805 BLACK (manufactured by Nikko Bics Co., Ltd.) was applied to the surface of the transparent support base material of the laminated film opposite to the uncured HC layer using a bar coater. Then, the laminated film coated with the black paint was left to stand for 5 hours in a room temperature environment and dried to prepare an uncured evaluation sample. ..
- the reflectance by the SCI method was measured at any 10 points from the optical interference layer side of the evaluation sample.
- SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. The measurement was performed every 10 nm in the wavelength region of 380 nm or more and 780 nm or less.
- the minimum value of the reflectance was determined for each measurement point, and the maximum value among the minimum values of the 10 points was defined as the minimum value RBH of the reflectance.
- the evaluation sample was subjected to a specific heat treatment, and the minimum value RAH of the reflectance was obtained in the same manner as described above.
- Hardness of coating film Hardness HBC and hardness HAC were measured from the uncured LR layer side of the laminated film and the LR layer side of the molded product, respectively.
- the hardness is determined by NANOMECHANICS, INC. It was measured by a continuous rigidity measurement method (method used: Advanced Dynamic Eand H. NMT) using an iMicro Nanoindenter manufactured by M...
- a quasi-static test load and a minute AC load were applied to the surface of the evaluation sample.
- the load was applied until the maximum load of 50 mN was reached.
- a Berkovich-type diamond indenter tip radius of curvature of 20 nm was used. From the vibration component of the generated displacement and the phase difference between the displacement and the load, the continuous stiffness with respect to the depth was calculated, and the profile of the hardness with respect to the depth was obtained. The hardness of this profile at a depth of 1000 nm was calculated.
- the iMicro dedicated software was used to calculate the load and stiffness.
- the Poisson's ratio of the coating layer was set to 0.35.
- the load was controlled so that the strain rate ( ⁇ P / ⁇ t) / P was 0.2.
- (H) Warp of molded product An evaluation sample having a size of 200 mm ⁇ 200 mm was cut out from the laminated film and irradiated with an active energy ray having an integrated light amount of 2000 mJ / cm 2 . Next, the evaluation sample was placed on a horizontal plane, and the amount of lift (warp amount) from the horizontal plane at the four corners was measured using a ruler and averaged.
- the evaluation criteria are as follows. Best: Average warp amount is 10 mm or less Good: Average warp amount is 10 or more and less than 15 mm Possible: Average warp amount is 15 mm or more and less than 20 mm Bad: Average warp amount is 20 mm or more
- Pencil hardness The pencil hardness of the LR layer of the molded product was evaluated. The measurement was performed according to JIS K5600-5-4 (1999), scratch hardness (pencil method).
- (L) Abrasion resistance The surface of the LR layer of the molded product was rubbed 3,000 times with a friction element to which a cotton cloth was fixed while applying a vertical load of 19.6 N per 4 cm 2 of the surface of the laminated film. The surface of the LR layer of the molded product was visually observed.
- the evaluation criteria are as follows. Best: No scratches visible after 3,000 rubs Good: No visible scratches after 1,000 rubs, but scratches visible after 3,000 rubs Possible: 1,000 After rubbing once, 5 or less scratches were visible. Defective: After 1,000 frictions, many scratches were visible.
- Examples 2-10, 12-22, Comparative Example 3-10 Using the compositions prepared in the formulations shown in Tables 1A and 1C in the same manner as in Example 1, laminated films and molded bodies having the configurations shown in Tables 2A to 2C were prepared. The obtained laminated film and the molded product were evaluated in the same manner as in Example 1. The results are shown in Tables 2A to 2C.
- Example 11 An uncured hard coat layer and an uncured optical interference layer were formed in the same manner as in (1-1) and (1-2) of Example 1, respectively. Separately, in the same manner as in the step of forming the uncured optical interference layer (1-1), a protective film on which the uncured functional layer (HR layer) having the composition shown in Table 1B was formed was obtained. The protective film on which the uncured HR layer was formed was wound into a roll. While unwinding this protective film, the surface of the uncured HR layer supported by the protective film and the surface of the uncured HC layer supported by the transparent supporting substrate were bonded together.
- HR layer uncured functional layer having the composition shown in Table 1B
- the protective film was peeled off to expose the uncured HR layer.
- the uncured LR layer prepared in (1-1) was attached to this HR layer while being unwound.
- a laminated film and a molded product having an uncured HC layer, an HR layer, and an LR layer in this order were produced.
- the obtained laminated film and the molded product were evaluated in the same manner as in Example 1. The results are shown in Table 2A and Table 2B.
- Example 1 An uncured HC layer was formed on the transparent support base material TB1 in the same manner as in Example 1 except that the composition HC4 was used. Next, the HC layer was irradiated with an active energy ray having an integrated light intensity of 2000 mJ / cm 2 , and the HC layer was cured. The composition LR11 was applied to the cured HC layer. Subsequently, the composition LR11 was dried to form an LR layer having a dry thickness of 120 nm. Finally, an active energy ray having an integrated light intensity of 2000 mJ / cm 2 was irradiated to obtain a precure type laminated film. Using this laminated film, a molded product was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2C.
- Comparative Example 2 A precure type laminated film was obtained in the same manner as in Comparative Example 1 except that the composition LR1 was used instead of the composition LR11 and the composition HC5 was used instead of the composition HC4. Using this laminated film, a molded product was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2C.
- the laminated film according to this embodiment has a low reflectance even after being heat-treated. Further, although the laminated film has a high draw ratio (50% or more, specifically 70% or more), the molded product obtained from this has excellent hard coat performance (for example, high hardness, wear resistance, etc.). Has chemical resistance, etc.) and excellent antireflection properties. Further, the laminated film according to the present embodiment is excellent in followability to a deep three-dimensional mold in the preform process.
- the laminated films of Comparative Examples 1 and 2 are precure type.
- each layer is composed of a composition that enables three-dimensional molding to a certain extent after curing. Therefore, the crosslink density of the composition after curing is low, and the wear resistance and chemical resistance are inferior.
- each layer is composed of a composition having a high crosslink density of the cured composition and excellent wear resistance and chemical resistance. Therefore, the laminated film of Comparative Example 2 has poor three-dimensional moldability after curing, and cannot follow a shallow three-dimensional shape mold in the preform process.
- the laminated film of Comparative Example 3 has no optical interference layer, so the minimum value of the reflectance exceeds 2%.
- the minimum value of the reflectance exceeds 2% before and after the specific heat treatment.
- the reflectance is increased by the specific heat treatment.
- the minimum value of the reflectance of the laminated film of Comparative Example 6 is small before the specific heat treatment, but greatly exceeds 2% after the specific heat treatment.
- Comparative Example 10 since the thickness of the transparent supporting base material was too thin, the rigidity of the base material was weak, and a molded product could not be obtained.
- this laminated film is particularly preferably used for producing a protective material for a display.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
[1]
透明支持基材と、
前記透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、
前記未硬化のハードコート層上に形成された未硬化の光干渉層と、を備える積層フィルムであって、
前記未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含み、
前記未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含み、
前記透明支持基材の厚さは、50μm以上600μm以下であり、
前記積層フィルムの160℃における延伸率は、50%以上であり、
90℃の温度下で30分間加熱処理された前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RAHは、2%以下である、積層フィルム。
前記反射率の極小値RAHと、前記加熱処理される前の前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RBHとは、
100×|RAH-RBH|/RBH≦20(%)
の関係を満たす、上記[1]に記載の積層フィルム。
前記光干渉層形成組成物は、第1の層形成成分と低屈折粒子とを含み、
前記第1の層形成成分は、1分子中に重合性官能基を2つ以上有する第1反応性成分を含み、
前記第1反応性成分は、重量平均分子量が1万超の第1ポリマー、重量平均分子量が1万以下の第1オリゴマーおよび重量平均分子量が1万以下の第1モノマーよりなる群から選択される少なくとも1つを含み、
前記低屈折粒子の含有量Xと、前記第1オリゴマーおよび前記第1モノマーの合計の含有量Yと、前記第1ポリマーの含有量Zとは、
X+Y+Z=100、
X≧30、
Y≧0、
Z≧0、および、
Z≦1/2X-15
の関係を満たす、上記[1]または[2]に記載の積層フィルム。
前記ハードコート層形成組成物は、第2の層形成成分を含み、
前記第2の層形成成分は、1分子中に重合性官能基を2つ以上有する第2反応性成分を含み、
前記第2反応性成分は、重量平均分子量が1万以下の第2オリゴマーおよび重量平均分子量が1万以下の第2モノマーの少なくとも一方を含む、上記[1]~[3]のいずれかに記載の積層フィルム。
前記第2反応性成分は、さらに、重量平均分子量が1万超の第2ポリマーを含む、上記[4]に記載の積層フィルム。
前記第2オリゴマーおよび前記第2モノマーの合計の含有量は、前記ハードコート層形成組成物の固形分100質量部に対して、25質量部以上65質量部以下である、上記[4]または[5]に記載の積層フィルム。
前記未硬化のハードコート層と前記未硬化の光干渉層との間に、さらに、少なくとも一つの未硬化の機能層を有する、上記[1]~[6]のいずれかに記載の積層フィルム。
前記未硬化の光干渉層側から、ナノインデンテーション法によって測定される硬度HBCは、0.1GPa以上0.5GPa以下である、上記[1]~[7]のいずれかに記載の積層フィルム。
積算光量2000mJ/cm2の活性エネルギー線が照射された前記積層フィルムの前記光干渉層側から、ナノインデンテーション法によって測定される硬度HACは、0.25GPa以上0.7GPa以下である、上記[1]~[8]のいずれかに記載の積層フィルム。
前記未硬化のハードコート層の厚さは、2μm以上30μm以下である、上記[1]~[9]のいずれかに記載の積層フィルム。
前記未硬化の光干渉層の厚さは、15nm以上200nm以下である、上記[1]~[10]のいずれかに記載の積層フィルム。
硬化された上記[1]~[11]のいずれかに記載の積層フィルムを含む、成形体。
前記ハードコート層は、前記透明支持基材の一方の主面に配置されており、
さらに、前記透明支持基材の他方の主面に配置された加飾層を備える、上記[12]に記載の成形体。
さらに、前記加飾層の少なくとも一部を覆う成形樹脂層を備える、上記[13]に記載の成形体。
厚さ50μm以上600μm以下の透明支持基材の一方の面上に、活性エネルギー線硬化型のハードコート層形成組成物を塗布して、未硬化のハードコート層を形成する工程と、
他の支持基材の一方の面上に、活性エネルギー線硬化型の光干渉層形成組成物を塗布して、未硬化の光干渉層を形成する工程と、
前記未硬化のハードコート層の前記透明支持基材とは反対側の面と、前記未硬化の光干渉層の前記他の支持基材とは反対側の面とを貼り合わせて積層フィルムを得るラミネート工程と、を備え、
前記積層フィルムの160℃における延伸率は、50%以上であり、
90℃の温度下で30分間加熱された前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RAHは、2%以下である、積層フィルムの製造方法。
上記[1]~[11]のいずれかに記載の積層フィルムの前記透明支持基材の他方の主面に加飾層を形成する加飾工程と、
前記加飾工程の後、前記積層フィルムに活性エネルギー線を照射する硬化工程と、を備え、
前記加飾工程は、前記積層フィルムを、80℃以上で20分間以上、加熱する加熱工程を含む、成形体の製造方法。
前記加飾工程の後、金型に前記光干渉層を対向させ、前記加飾層に向かって成形用樹脂を射出する射出成型工程を備える、上記[16]に記載の成形体の製造方法。
前記金型は、前記積層フィルムに立体形状を付与し、
前記加飾工程の後、前記射出成型工程の前に、前記積層フィルムを前記立体形状に沿った形状に成形するプレフォーム工程を備える、上記[17]に記載の成形体の製造方法。
本実施形態に係る積層フィルムは、透明支持基材と、透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、未硬化のハードコート層上に形成された未硬化の光干渉層と、を有する。未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含む。未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含む。
90℃の温度下で30分間の加熱処理(以下、特定加熱処理と称する場合がある。)が施された積層フィルムの、未硬化の光干渉層側から測定した、波長380nmから780nmの間における反射率の極小値RAHは、2.0%以下である。反射率の極小値RAHがこの範囲内であるということは、未硬化のハードコート層と未硬化の光干渉層との間の混相の発生が抑制されており、両層の間に明瞭な界面が形成されていることを示す。反射率の極小値RAHは、1.8%以下が好ましく、1.6%以下がより好ましい。本実施形態に係る積層フィルムの反射率の極小値は、90℃以上120℃以下の温度下で、30分以上90分以下の加熱処理後であっても、2.0%以下であり得る。
透明支持基材の、未硬化のハードコート層とは反対側の面に、黒色塗料(例えば、品名:CZ-805 BLACK(日弘ビックス社製)を、バーコーターを用い、乾燥膜厚が3μm以上6μm以下となるように塗布する。その後、90℃の温度下で30分間加熱処理して、評価サンプルMを作成する。
積層フィルムの160℃における延伸率E160は、50%以上である。この場合、積層フィルムは150℃以上190℃以下の成形温度において十分に延伸する。よって、積層フィルムを、クラックを生じることなく、複雑な立体形状に成形することができる。特に、プレフォーム工程において、積層フィルムの損傷が抑制され易くなる。そのため、ハードコート層および光干渉層の機能を備え、かつ、複雑な立体形状を有する成形体を得ることができる。積層フィルムは、要求される物性、形状等に応じて、例えば、プレフォームおよびインサートモールド法等により立体形状に成型される。
チャック間距離が150mmである引張り試験機、および、長さ200mm×幅10mmに切り出した評価サンプルを準備する。160℃雰囲気下、引張力5.0Kgf、引張速度300mm/分の条件にて、評価サンプルを長辺方向に10%延伸する。延伸された評価サンプルのクラックの有無を目視で確認する。
透明支持基材の厚さは、50μm以上600μm以下である。これにより、積層フィルムを延伸させた場合にも、積層フィルムは剛性を保持できる。また、積層フィルムおよび成形体の反りが抑制され易い。さらに、透明支持基材および積層フィルムをロール状に巻き取ることが可能となるため、ロールtoロール加工を行うことができる。
後工程における損傷が抑制され易い点で、積層フィルムの光干渉層側から測定されたナノインデンテーション法による硬度HBCは、0.1GPa以上が好ましい。硬度HBCが0.1GPa以上であると、スリット形成および裁断の際の凹みや損傷、複数の積層フィルムを積層した際に混入する異物による凹み、スキージ痕あるいは吸引痕等の不具合が抑制されて、歩留まりが向上し易くなる。
視認性の観点から、硬化された積層フィルムは、耐摩耗性に優れることが望ましい。積算光量2000mJ/cm2の活性エネルギー線が照射された積層フィルムの光干渉層の表面を、4cm2あたり垂直荷重19.6Nをかけながら3,000回摩擦したとき、光干渉層に傷が視認されないことが好ましい。この場合、成形体の外観変化による視認性低下が抑制され易くなる。特定加熱処理が施された後、硬化された積層フィルムも、上記を満たす耐摩耗性を有する。
耐擦傷性および耐摩耗性の観点から、硬化された積層フィルムの静摩擦係数は小さいことが望ましい。積算光量2000mJ/cm2の活性エネルギー線が照射された積層フィルムの光干渉層の静摩擦係数μACは、0.3以下が好ましく、0.25以下がより好ましく、0.20以下が特に好ましい。静摩擦係数は、JIS K 7125に準じて測定される。特定加熱処理が施された後、硬化された積層フィルムの静摩擦係数も、上記範囲を満たす。
透明支持基材は、透明である限り特に限定されない。透明であるとは、具体的には、全光線透過率が80%以上であることをいう。透明支持基材の全光線透過率は、80%以上であって、90%以上が好ましい。全光線透過率は、JIS K 7361-1に準拠する方法により測定することができる。透明支持基材としては、当分野において公知のものが、特に制限されることなく用いられる。透明支持基材は、無色であってもよく、有色であってもよい。
未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物(以下、組成物Rと称す場合がある。)を含む。組成物Rは、活性エネルギー線により硬化する。活性エネルギー線の積算光量を調整することにより、光干渉層の硬度および/または延伸率を制御することができる。活性エネルギー線は、紫外線、電子線、α線、β線、γ線等の電離放射線である。組成物Rは、特に紫外線硬化型であることが好ましい。
光干渉層形成組成物(組成物R)は、例えば、第1の層形成成分と低屈折粒子とを含む。低屈折粒子は、低い屈折率を有する粒子であって、光干渉層の屈折率を低下させる。
低屈折粒子としては、例えば、中空状シリカ微粒子、中空樹脂粒子が挙げられる。低屈折粒子は、光干渉層の強度を保持しつつ、その屈折率を下げることができる。低屈折粒子は、内部に気体が充填された構造および/または気体を含む多孔質構造体である。屈折率は、気体の占有率に反比例して低下する。そのため、低屈折粒子は、中空を有さない粒子の屈折率に比べて、低い屈折率を有する。
第1の層形成成分は、1分子中に重合性官能基を2つ以上有する第1反応性成分を含む。第1反応性成分は、第1モノマー、第1オリゴマーおよび第1ポリマーよりなる群から選択される少なくとも1種を含む。第1モノマーおよび第1オリゴマーの重量平均分子量は、1万以下であり、9000以下であってよい。第1ポリマーの重量平均分子量は、1万超であり、2万以上であってよい。第1ポリマーの重量平均分子量は、10万以下であってよい。
100×Z/(X+Z)<40(%)
の関係を満たすように、第1ポリマーを含むことが好ましい。100×Z/(X+Z)≦35(%)の関係を満たすことがより好ましく、100×Z/(X+Z)≦30(%)の関係を満たすことが特に好ましい。
X+Y+Z=100、
Y≧0、
Z≧0、および、
Z≦1/2X-15
の関係を満たすことが好ましい。これにより、さらに混相が抑制され易くなる。Z≦1/2X-18の関係を満たすことがより好ましく、Z≦1/2X-20の関係を満たすことが特に好ましい。
組成物Rは、無機酸化物微粒子を含んでもよい。無機酸化物微粒子により、未硬化の光干渉層の体積収縮が抑制されるとともに、剛性が高まり易くなる。そのため、未硬化の光干渉層の製造工程中の外観変化が抑制され易い。さらに、硬化された光干渉層の外観変化やカールの発生も抑制される。加えて、硬化された光干渉層のタック性が低減するとともに耐摩耗性が高まり易い。
組成物Rは、光重合開始剤を含むのが好ましい。これにより、活性エネルギー線硬化型の樹脂成分の重合が進行し易くなる。
組成物Rは、溶媒を含んでもよい。溶媒は特に限定されず、組成物に含まれる成分、透明支持基材の種類および塗布方法等を考慮して、適宜選択される。
組成物Rは、必要に応じて、種々の添加剤を含むことができる。添加剤としては、例えば、帯電防止剤、可塑剤、界面活性剤、酸化防止剤、紫外線吸収剤、表面調整剤、表面改質剤、レベリング剤および光安定剤(例えば、ヒンダードアミン系光安定剤(HALS))が挙げられる。
未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物(以下、組成物HCと称す場合がある。)を含む。組成物HCは、活性エネルギー線により硬化する。活性エネルギー線の積算光量を調整することにより、ハードコート層の硬度および/または延伸率を制御することができる。組成物HCは、組成物Rと同種の活性エネルギー線により硬化することが好ましい。
ハードコート層形成組成物(組成物HC)は、第2の層形成成分を含む。
第2の層形成成分は、1分子中に重合性官能基を2つ以上有する第2反応性成分を含む。第2反応性成分は、第2モノマーおよび第2オリゴマーの少なくとも一方を含むことが好ましい。これにより、第2の層形成成分の架橋密度が高まって、硬化されたハードコート層の硬度が向上し易くなる。第2モノマーおよび第2オリゴマーの重量平均分子量は、1万以下であり、9000以下であってよい。
組成物HCは、無機酸化物微粒子を含んでもよい。無機酸化物微粒子としては、組成物Rに関して例示されたものが同様に挙げられる。無機酸化物微粒子の含有量は、組成物HCの固形分100質量部に対して、20質量部以下が好ましく、18質量部以下がより好ましく、15質量部以下が特に好ましい。無機酸化物微粒子の含有量は、組成物HCの固形分100質量部に対して、0.1質量部以上が好ましく、1質量部以上がより好ましく、3質量部以上が特に好ましい。
組成物HCは、光重合開始剤を含むのが好ましい。これにより、活性エネルギー線硬化型の樹脂成分の重合が進行し易くなる。光重合開始剤として、組成物Rに関して例示されたものが同様に挙げられる。
組成物HCは、溶媒を含んでもよい。溶媒は特に限定されず、組成物に含まれる成分、透明支持基材の種類および塗布方法等を考慮して、適宜選択される。溶媒としては、組成物Rに関して例示されたものが同様に挙げられる。なかでも、エステル系溶媒、エーテル系溶媒、アルコール系溶媒およびケトン系溶媒が好ましい。
組成物HCは、必要に応じて、種々の添加剤を含むことができる。添加剤としては、組成物Rに関して例示されたものが同様に挙げられる。
積層フィルムは、未硬化のハードコート層と、未硬化の光干渉層との間に、さらに、少なくとも1つの未硬化の機能層を有していてもよい。機能層により、積層フィルムの光学的機能が補強されたり、新たな光学的機能が付与されたりする。
積層フィルムは、未硬化の光干渉層の、未硬化のハードコート層とは反対側の面に、保護フィルムを有していてもよい。これにより、積層フィルムをロール状に巻き取ったり、ロールから巻き出したりする際、損傷が抑制され易い。
本実施形態に係る成形体は、上記の積層フィルムが硬化されることにより得られる。成形体は、積層フィルムの完全硬化物である。成形体は、透明支持基材と、硬化されたハードコート層と、硬化された光干渉層と、を有する。成形体は、硬化されたハードコート層と硬化された光干渉層との間に、さらに、少なくとも1つの硬化された機能層を有していてもよい。成形体は、さらに、保護フィルムを有していてもよいし、有していなくてもよい。保護フィルムは、使用目的に応じて、使用される。
成形体は、さらに加飾層を備えていてもよい。本実施形態に係る積層フィルムによれば、加飾層を形成する際に加熱処理が施される場合であっても、低い反射率を維持することができる。成形体がディスプレイの保護材である場合、加飾層は、例えば、ディスプレイを囲むベゼル部分に設けられる。
成形体は、さらに成形樹脂層を備えていてもよい。成形樹脂層は、透明支持基材とともにハードコート層および光干渉層を支持する。成形体は、例えば、透明支持基材と、透明支持基材の一方の主面に配置されたハードコート層および光干渉層と、透明支持基材の他方の主面に配置された成形樹脂層と、を備える。成形樹脂層の形状は制限されない。そのため、成形体のデザインの自由度が高まる。
本実施形態に係る積層フィルムは、厚さ50μm以上600μm以下の透明支持基材の一方の面上に、活性エネルギー線硬化型のハードコート層形成組成物を塗布して、未硬化のハードコート層を形成する工程と、他の支持基材の一方の面上に、活性エネルギー線硬化型の光干渉層形成組成物を塗布して、未硬化の光干渉層を形成する工程と、未硬化のハードコート層の透明支持基材とは反対側の面と、未硬化の光干渉層の他の支持基材とは反対側の面とを貼り合わせて積層フィルムを得るラミネート工程と、を備える方法により製造される。未硬化のハードコート層と未硬化の光干渉層とを、ラミネート法によって積層することにより、混相は抑制され易い。得られる積層フィルムの160℃における延伸率は、50%以上であり、特定加熱処理が施された後の反射率の極小値RAHは、2%以下である。
図3は、本実施形態に係る積層フィルムの製造方法を示すフローチャートである。
未硬化のハードコート層を形成する方法は特に限定されない。未硬化のハードコート層は、透明支持基材の一方の面上に、例えば、組成物HCを塗布することにより形成される。
未硬化の光干渉層を形成する方法は特に限定されない。未硬化の光干渉層は、他の支持基材(代表的には、上記の保護フィルム)の一方の面上に、例えば、組成物Rを塗布することにより形成される。組成物Rの塗布方法は、組成物HCと同様に、当業者において通常行われる手法によって行われる。
他の支持基材上に形成された未硬化の光干渉層と、透明支持基材上に形成された未硬化のハードコート層とが貼り合わされる。これにより、積層フィルムが得られる。両者を貼り合わせた後、他の支持基材は剥離されてもよい。
まず、他の未硬化の機能層を、新たな支持基材上に形成する。次いで、未硬化のハードコート層の透明支持基材とは反対側の面と、未硬化の機能層の新たな支持基材とは反対側の面とを貼り合わせる。新たな支持基材を剥離した後、露出した未硬化の機能層に、他の支持基材で支持された未硬化の光干渉層を貼り合わせる。必要に応じて、光干渉層を貼り合わせる前に、未硬化の機能層を未硬化のハードコート層、あるいはこれに積層された未硬化の機能層に貼り合わせる工程を繰り返す。
本実施形態に係る成形体は、例えば、上記の積層フィルムの透明支持基材の他方の主面に加飾層を形成する加飾工程と、加飾工程の後、積層フィルムに、積算光量200mJ/cm2以上の活性エネルギー線を照射する硬化工程と、を備える方法により製造される。加飾工程は、積層フィルムを、80℃以上で20分間以上、加熱する加熱工程を含む。
以下、各工程について説明する。
積層フィルムの透明支持基材の他方の主面に、加飾層(代表的には、印刷層および蒸着層)を形成する。
積層フィルムを、所望の立体形状に沿った形状にプレフォームする。積層フィルムを、予め立体形状に近い形状に賦形することにより、射出成型(代表的には、インサートモールドラミネーション(IML)成型)が可能となる。IML成型では、積層フィルムが金型に挿入され、積層フィルムに向かって成形用樹脂が射出される。プレフォーム工程の後、積層フィルムの不要な部分を除去するトリミング工程を行ってもよい。
積層フィルムの一部が硬化するように、活性エネルギー線を照射する。これにより、半硬化状態の積層フィルムが得られる。半硬化工程により、射出成型工程における積層フィルムの金型への貼り付きが抑制されるとともに、積層フィルムが、射出成型工程に必要な延伸率に調整されて、射出成型工程におけるクラックの発生を抑制することができる。活性エネルギー線の積算光量は、例えば、1mJ/cm2以上200mJ/cm2未満である。半硬化工程の後、積層フィルムの不要な部分を除去するトリミング工程を行ってもよい。
射出成型では、例えば、金型に光干渉層を対向させるとともに、透明支持基材に向かって成形用樹脂が射出される。これにより、積層フィルムが金型の形状に賦形されるとともに、透明支持基材の他方の主面に成形樹脂層が形成される。
積層フィルムに活性エネルギー線を照射して、積層フィルムを完全硬化させる。これにより、成形体が得られる。本硬化工程における活性エネルギー線の積算光量は、200mJ/cm2以上である。活性エネルギー線の積算光量は、5000mJ/cm2以下であってよく、3000mJ/cm2以下であってよい。活性エネルギー線は、半硬化工程と同種であってよく、異なっていてもよい。
(第1、第2ポリマー)
アクリルポリマーA:Mw70,000
アクリルポリマーB:Mw20,000
アクリルポリマーC:Mw100,000
[アクリルポリマーAの調製]
2,3-エポキシプロピルメタクリレート30.0部、メチルメタクリレート70部、t-ブチルペルオキシ-2-エチルヘキサノエート1.5部からなる混合物を調製した。別途、攪拌羽根、窒素導入管、冷却管および滴下漏斗を備えた500ml反応容器に、トルエン40.0部を投入し、110℃に加温した。この反応容器内を撹拌させながら、上記混合物を、窒素雰囲気下で2時間かけて等速で滴下した。滴下終了後、110℃の温度条件下で1時間反応を行った。その後、上記反応容器に、t-ブチルペルオキシ-2-エチルヘキサノエート1.0部とトルエン25.0部との混合溶液を、1時間かけて滴下した。次いで、反応容器内を145℃まで加熱して、さらに2時間反応させた。続いて、反応容器内を110℃以下に冷却し、さらにトルエン59.0部を添加して、前駆体A1を得た。
2,3-エポキシプロピルメタクリレート30.0部、メチルメタクリレート70部、t-ブチルペルオキシ-2-エチルヘキサノエート10.0部からなる混合物を調製した。別途、攪拌羽根、窒素導入管、冷却管および滴下漏斗を備えた500ml反応容器に、トルエン40.0部を投入し、110℃に加温した。この反応容器内を撹拌させながら、上記混合物を、窒素雰囲気下で2時間かけて等速で滴下した。滴下終了後、110℃の温度条件下で1時間反応を行った。その後、上記反応容器に、t-ブチルペルオキシ-2-エチルヘキサノエート1.0部とトルエン25.0部との混合溶液を、1時間かけて滴下した。次いで、反応容器内を145℃まで加熱して、さらに2時間反応させた。続いて、反応容器内を110℃以下に冷却し、さらにトルエン59.0部を添加して、前駆体B1を得た。
2,3-エポキシプロピルメタクリレート30.0部、メチルメタクリレート70部、t-ブチルペルオキシ-2-エチルヘキサノエート0.8部からなる混合物を調製した。別途、攪拌羽根、窒素導入管、冷却管および滴下漏斗を備えた500ml反応容器に、トルエン40.0部を投入し、110℃に加温した。この反応容器内を撹拌させながら、上記混合物を、窒素雰囲気下で2時間かけて等速で滴下した。滴下終了後、110℃の温度条件下で1時間反応を行った。その後、t-ブチルペルオキシ-2-エチルヘキサノエート1.0部とトルエン25.0部との混合溶液を、1時間かけて滴下した。次いで、反応容器内を145℃まで加熱して、さらに2時間反応させた。続いて、反応容器内を110℃以下に冷却し、さらにトルエンを59.0部添加して、前駆体C1を得た。
KRM-8452:ダイセル オルネクス社製、Mw3,884、アクリル当量120g/eq
CN-9893:アルケマ社製
H-7M40:根上工業社製、Mw10,000~15,000、
UN-904M:根上工業社製、Mw4,900
アロニックスM-315:東亞合成社製、Mw450、アクリル当量150g/eq
アロニックスM-402:東亜合成社製、DPHA
アロニックスM-305:東亜合成社製、PETA
スルーリア4320:日揮触媒社製、中空状シリカ微粒子、体積平均粒子径55nm
スルーリア5320:日揮触媒社製、中空状シリカ微粒子、体積平均粒子径75nm
OSCAL 1842:日揮触媒化成工業社製、反応性シリカオルガノゾル、粒子径10nm
NANON5 ZR-010:ソーラー社製、酸化ジルコニウム、体積平均粒子径20nm
オプツール:DAC-HP、ダイキン工業社製
(表面改質剤)
メガファックRS-57:DIC社製
Omnirad 127:IGM RESINS社製、α-ヒドロキシアセトフェノン
Omnirad 184:IGM RESINS社製、α-ヒドロキシアルキルフェノン
TB1-TB5:品名AW-10U、ウェーブロック・アドバンスト・テクノロジー社製、PMMAおよびPCからなる2層(PMMA/PC)フィルム、厚さ300μm(TB1)、200μm(TB2)、500μm(TB3)、30μm(TB4)、100μm(TB5)
トレファン#40-2500、東レ社製、二軸延伸ポリプロピレンフィルム(OPP)、厚さ40μm
アクリルポリマーB(第1ポリマー)3.1部、アロニックスM-402(第1モノマー)27.7部、オプツール DAC-HP(表面調整剤)11.6部、メガファックRS-57(表面改質剤)8.0部、および、Omnirad127(光重合開始剤)3.5部を混合した。さらに、スルーリア4320(低屈折粒子)46.1部を配合した。この混合物をプロピレングリコールモノメチルエーテルにより希釈して、固形分濃度3%の乳白色の組成物LR1を調整した。組成物LR1により形成される層の屈折率は、1.20以上1.55以下であった。
表1Aに示す配合にしたこと以外は、組成物LR1と同様にして、固形分濃度3%の、乳白色の組成物LR2-LR11、LR13-LR15および透明な組成物LR12を調整した。組成物LR2からLR15により形成される層の屈折率は、いずれも1.20以上1.55以下であった。
表1Bに示す配合にしたこと以外は、組成物LR1と同様にして、固形分濃度3%の乳白色の機能層形成組成物HR1を調整した。組成物HR1により形成される層の屈折率は、1.55超2.00以下であった。
アクリルポリマーA(第2ポリマー)32.0質量部、KRM-8452(第2オリゴマー、多官能ウレタンアクリレートオリゴマー)36.3質量部、アロニックスM-402(第2モノマー)21.3部、OSCAL 1842(無機酸化物微粒子)4.1質量部、および、Omnirad184(光重合開始)6.3質量部を混合した。この混合物をメチルイソブチルケトンにより希釈して、固形分濃度35%の透明な組成物HC1を調整した。
表1Cに示す配合にしたこと以外は、組成物HC1と同様にして、固形分濃度35%の透明な組成物HC2-HC5を調整した。
(1)積層フィルムの製造
(1-1)未硬化の光干渉層の形成
OPPフィルム(保護フィルム)に、組成物LR1を、グラビアコーターにより、乾燥後の厚さが120nmになるよう塗布した。その後、80℃で1分間乾燥させて溶媒を揮発させて、未硬化の光干渉層を形成した。未硬化の光干渉層が形成された保護フィルムを、ロール状に巻き取った。
以下、組成物LR1-LR15により形成された光干渉層を「LR層」と表記する場合がある。
透明支持基材TB1のPMMAの面に、グラビアコーターにより、組成物HC1を乾燥後の厚さが12μmになるよう塗布した。その後、80℃で1分間乾燥させて溶媒を揮発させて、未硬化のハードコート層を形成した。
以下、組成物HC1-HC5により形成されたハードコート層を「HC層」と表記する場合がある。
ロール状に巻き取られた保護フィルムを巻き出しながら、透明支持基材TB1で支持された未硬化のHC層表面と、保護フィルムで支持された未硬化のLR層表面とを貼り合わせた。これにより、透明支持基材と、未硬化のHC層と、未硬化のLR層と、保護フィルムと、をこの順で有する積層フィルムを製造した。最後に、保護フィルムが内側になるように、積層フィルムをロール状に巻き取った。
(2-1)加飾層の形成
まず、積層フィルムをロールから巻き出して、所望の形状および大きさに裁断した。裁断された積層フィルムの透明支持基材の、未硬化のHC層とは反対側の面に、スクリーン印刷により加飾(印刷)層を形成し、乾燥温度80℃で10分間乾燥させた。この加飾工程を5回繰り返し、その後、90℃で1時間乾燥させた。印刷層の形成には、黒色塗料(RIMインキ 極黒、十条ケミカル社製)を用いた。
次いで、保護フィルムを未硬化のLR層から5.0mm/秒の速度で剥離した。
印刷層を備える積層フィルムを190℃で30秒間加熱し、最大深さが6mmの立体形状の型を用いて、真空圧空成型法によりプレフォームを実施した。
プレフォームされた積層フィルムに、積算光量2000mJ/cm2の活性エネルギー線を照射した。続いて、トリミングを実施した。
最後に、射出成型を行って、透明支持基材の印刷層側に成形樹脂層(ポリカーボネート)を備える成形体を得た。なお、実施例において、特に言及のない限り、活性エネルギー線として、紫外線を使用している。
積層フィルムおよび成形体に対して、以下の評価を行った。結果を表2Aに示す。
積層フィルムから、10mm×10mmの評価サンプルを切り出した。評価サンプルの断面を、ミクロト-ム(LEICA RM2265)にて析出させた。析出させた断面を、レーザー顕微鏡(VK8700、KEYENCE社製)または透過型電子顕微鏡(JEM2100、日本電子社製)にて観察し、HC層およびLR層の各10点の厚みを測定した。その平均値をそれぞれ、HC層およびLR層の厚さとした。
積層フィルムの透明支持基材における、未硬化のHC層とは反対側の面に対し、黒色塗料(品名:CZ-805 BLACK(日弘ビックス社製)を、バーコーターを用い、乾燥膜厚が3μm以上6μm以下となるように塗布した。次いで、黒色塗料を塗布した積層フィルムを、室温環境下で5時間放置し、乾燥を行うことにより、未硬化の評価サンプルを作製した。
積層フィルムから長さ200mm×幅10mmの試験片を切り出した。この試験片を、チャック間距離が150mmである引張り試験機にセットして、160℃雰囲気下、引張力5.0Kgf、引張速度300mm/分の条件にて、評価サンプルを長辺方向に10%延伸した。延伸後の評価サンプルのクラックの有無を、目視で確認した。
積層フィルムの未硬化のLR層側と、成形体のLR層側とから、それぞれ硬度HBCおよび硬度HACを測定した。
硬度は、NANOMECHANICS,INC.製のiMicro Nanoindenterを用いて、連続剛性測定法(使用メソッド:Advanced Dynamic E and H.NMT)により測定した。
成形体の光干渉層側の表面に蛍光灯の光を反射させ、外光の映り込みを、目視により評価した。
評価基準は以下のとおりである。
良:外光の映り込みがほとんど感じられない
可:外光の映り込みが僅かに感じられる
不良:外光の映り込みがはっきりと感じられる
最大深さが3mmおよび6mmの2種類の型を用いて、積層フィルムにそれぞれプレフォームを行い、立体形状への追従性を評価した。
評価基準は以下のとおりである。
良:深い立体形状に成形してもクラックや白化が視認されない
可:深い立体形状に成形した場合はクラックや白化が視認されるが、
浅い立体形状に成形した場合はクラックや白化が視認されない
不良:浅い立体形状に成形した場合でもクラックや白化が視認される
プレフォームした積層フィルムに積算光量2000mJ/cm2の活性エネルギー線を照射して評価サンプルとした。評価サンプルを射出成型の金型にセットする際のハンドリング性を評価した。
評価基準は以下のとおりである。
良:評価サンプルにコシがあり、射出成型の金型に容易に設置できる
可:評価サンプルのコシが弱く、取り扱いに若干の難があるが、金型に設置できる
不良:評価サンプルのコシが弱く、金型に設置できない
積層フィルムから、200mm×200mmの評価サンプルを切り出し、積算光量2000mJ/cm2の活性エネルギー線を照射した。次いで、評価サンプルを水平面に載置して、その四隅の水平面からの浮き上がり量(反り量)を定規を用いて計測し、平均化した。
評価基準は以下のとおりである。
最良:反り量の平均が10mm以下
良:反り量の平均が10以上15mm未満
可:反り量の平均が15mm以上20mm未満
不良:反り量の平均が20mm以上
保護フィルムの剥離(2-2)後、プレフォーム(2-3)前の積層フィルムを評価サンプルとした。評価サンプルの加飾工程に起因するスキージ痕および吸引痕の有無を、目視により確認した。
評価基準は、以下のとおりである。
最良:スキージ痕および吸引痕無し
良:スキージ痕および吸引痕が僅かにあるが、90℃以上に加熱することでレベリングし、消失する
可:スキージ痕および吸引痕が僅かにあるが、150℃以上に加熱することでレベリングし、消失する
不良:スキージ痕および吸引痕有り
(1-1)で作成された保護フィルムと未硬化の光干渉層との積層体と、(1-2)で作成された透明支持基材と未硬化のハードコート層との積層体とを、各層が対向するようにハンドローラーで押し付けながら貼り合わせて、貼り付きの程度を評価した。
評価基準は、以下のとおりである。
良:積層体同士が貼り付いている
可:積層体同士が貼り付いているが、密着が弱い
成形体のLR層の鉛筆硬度を評価した。
測定は、JIS K5600-5-4(1999)、ひっかき硬度(鉛筆法)に従って行った。
成形体のLR層の表面を、積層フィルム表面4cm2あたり垂直荷重19.6Nをかけながら、綿布を固定した摩擦子により3,000回摩擦した。成形体のLR層の表面を目視により観察した。評価基準は次のとおりである。
最良:3,000回の摩擦後にも傷は視認されなかった
良:1,000回の摩擦後に傷は視認されなかったが、3,000回の摩擦後に傷が視認された
可:1,000回の摩擦後、5本以下の傷が視認された
不良:1,000回の摩擦後、傷が多数視認された
成形体から、10cm×10cmの評価サンプルを切り出した。評価サンプルのLR層の一面全体に、ニュートロジーナ サンスクリーンSPF45(ジョンソン&ジョンソン社製)2gを、指で均一になるように塗布した。次いで、80℃×4時間加温した。その後、室温まで冷却し、水洗いを行って、LR層の外観を目視で評価した。
評価基準は以下のとおりである。
最良:外観異常無し
良:塗布した痕が確認できるがリフティングは確認されない
不良:リフティングが発生している
実施例1と同様にして、表1Aおよび表1Cに示す配合で調製された組成物を用いて、表2Aから表2Cに示す構成を有する積層フィルムおよび成形体を作成した。得られた積層フィルムおよび成形体を、実施例1と同様にして評価した。結果を表2Aから表2Cに示す。
実施例1の(1-1)および(1-2)と同様にして、未硬化のハードコート層および未硬化の光干渉層をそれぞれ形成した。
別途、未硬化の光干渉層の形成工程(1-1)と同様にして、表1Bに示された組成を有する未硬化の機能層(HR層)が形成された保護フィルムを得た。未硬化のHR層が形成された保護フィルムを、ロール状に巻き取った。この保護フィルムを巻き出しながら、保護フィルムで支持された未硬化のHR層表面と、透明支持基材で支持された未硬化のHC層表面とを貼り合わせた。
組成物HC4を用いたこと以外は実施例1と同様にして、未硬化のHC層を透明支持基材TB1上に形成した。次いで、HC層に積算光量2000mJ/cm2の活性エネルギー線を照射し、HC層を硬化させた。
硬化されたHC層に組成物LR11を塗布した。続いて、組成物LR11を乾燥させて、乾燥厚さ120nmのLR層を形成した。最後に、積算光量2000mJ/cm2の活性エネルギー線を照射して、プレキュア型の積層フィルムを得た。この積層フィルムを用いて、実施例1と同様にして成形体を作成し、評価した。結果を表2Cに示す。
組成物LR11に替えて組成物LR1を用いたこと、および、組成物HC4に替えて組成物HC5を用いたこと以外は比較例1と同様にして、プレキュア型の積層フィルムを得た。この積層フィルムを用いて、実施例1と同様にして成形体を作成し、評価した。結果を表2Cに示す。
11 透明支持基材
12 未硬化のハードコート層
13 未硬化の光干渉層
14 他の支持基材
20 成形体
22 硬化されたハードコート層
23 硬化された光干渉層
24 加飾層
25 成形樹脂層
30 ローラ
Claims (18)
- 透明支持基材と、
前記透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、
前記未硬化のハードコート層上に形成された未硬化の光干渉層と、を備える積層フィルムであって、
前記未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含み、
前記未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含み、
前記透明支持基材の厚さは、50μm以上600μm以下であり、
前記積層フィルムの160℃における延伸率は、50%以上であり、
90℃の温度下で30分間加熱処理された前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RAHは、2%以下である、積層フィルム。 - 前記反射率の極小値RAHと、前記加熱処理される前の前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RBHとは、
100×|RAH-RBH|/RBH≦20(%)
の関係を満たす、請求項1に記載の積層フィルム。 - 前記光干渉層形成組成物は、第1の層形成成分と低屈折粒子とを含み、
前記第1の層形成成分は、1分子中に重合性官能基を2つ以上有する第1反応性成分を含み、
前記第1反応性成分は、重量平均分子量が1万超の第1ポリマー、重量平均分子量が1万以下の第1オリゴマーおよび重量平均分子量が1万以下の第1モノマーよりなる群から選択される少なくとも1つを含み、
前記低屈折粒子の含有量Xと、前記第1オリゴマーおよび前記第1モノマーの合計の含有量Yと、前記第1ポリマーの含有量Zとは、
X+Y+Z=100、
X≧30、
Y≧0、
Z≧0、および、
Z≦1/2X-15
の関係を満たす、請求項1または2に記載の積層フィルム。 - 前記ハードコート層形成組成物は、第2の層形成成分を含み、
前記第2の層形成成分は、1分子中に重合性官能基を2つ以上有する第2反応性成分を含み、
前記第2反応性成分は、重量平均分子量が1万以下の第2オリゴマーおよび重量平均分子量が1万以下の第2モノマーの少なくとも一方を含む、請求項1~3のいずれか一項に記載の積層フィルム。 - 前記第2反応性成分は、さらに、重量平均分子量が1万超の第2ポリマーを含む、請求項4に記載の積層フィルム。
- 前記第2オリゴマーおよび前記第2モノマーの合計の含有量は、前記ハードコート層形成組成物の固形分100質量部に対して、25質量部以上65質量部以下である、請求項4または5に記載の積層フィルム。
- 前記未硬化のハードコート層と前記未硬化の光干渉層との間に、さらに、少なくとも一つの未硬化の機能層を有する、請求項1~6のいずれか一項に記載の積層フィルム。
- 前記未硬化の光干渉層側から、ナノインデンテーション法によって測定される硬度HBCは、0.1GPa以上0.5GPa以下である、請求項1~7のいずれか一項に記載の積層フィルム。
- 積算光量2000mJ/cm2の活性エネルギー線が照射された前記積層フィルムの前記光干渉層側から、ナノインデンテーション法によって測定される硬度HACは、0.25GPa以上0.7GPa以下である、請求項1~8のいずれか一項に記載の積層フィルム。
- 前記未硬化のハードコート層の厚さは、2μm以上30μm以下である、請求項1~9のいずれか一項に記載の積層フィルム。
- 前記未硬化の光干渉層の厚さは、15nm以上200nm以下である、請求項1~10のいずれか一項に記載の積層フィルム。
- 硬化された請求項1~11のいずれか一項に記載の積層フィルムを含む、成形体。
- 前記ハードコート層は、前記透明支持基材の一方の主面に配置されており、
さらに、前記透明支持基材の他方の主面に配置された加飾層を備える、請求項12に記載の成形体。 - さらに、前記加飾層の少なくとも一部を覆う成形樹脂層を備える、請求項13に記載の成形体。
- 厚さ50μm以上600μm以下の透明支持基材の一方の面上に、活性エネルギー線硬化型のハードコート層形成組成物を塗布して、未硬化のハードコート層を形成する工程と、
他の支持基材の一方の面上に、活性エネルギー線硬化型の光干渉層形成組成物を塗布して、未硬化の光干渉層を形成する工程と、
前記未硬化のハードコート層の前記透明支持基材とは反対側の面と、前記未硬化の光干渉層の前記他の支持基材とは反対側の面とを貼り合わせて積層フィルムを得るラミネート工程と、を備え、
前記積層フィルムの160℃における延伸率は、50%以上であり、
90℃の温度下で30分間加熱された前記積層フィルムの、前記未硬化の光干渉層側から測定された、波長380nmから780nmの間における反射率の極小値RAHは、2%以下である、積層フィルムの製造方法。 - 請求項1~11のいずれか一項に記載の積層フィルムの前記透明支持基材の他方の主面に加飾層を形成する加飾工程と、
前記加飾工程の後、前記積層フィルムに活性エネルギー線を照射する硬化工程と、を備え、
前記加飾工程は、前記積層フィルムを、80℃以上で20分間以上加熱する、加熱工程を含む、成形体の製造方法。 - 前記加飾工程の後、金型に前記光干渉層を対向させ、前記加飾層に向かって成形用樹脂を射出する射出成型工程を備える、請求項16に記載の成形体の製造方法。
- 前記金型は、前記積層フィルムに立体形状を付与し、
前記加飾工程の後、前記射出成型工程の前に、前記積層フィルムを前記立体形状に沿った形状に成形するプレフォーム工程を備える、請求項17に記載の成形体の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21900716.8A EP4257355A1 (en) | 2020-12-04 | 2021-12-03 | Laminated film and molded article, and production methods therefor |
US18/039,521 US20240091998A1 (en) | 2020-12-04 | 2021-12-03 | Laminated film and molded article, and production methods therefor |
CN202180080020.2A CN116529049A (zh) | 2020-12-04 | 2021-12-03 | 层叠膜和成型体以及它们的制造方法 |
KR1020237021605A KR20230115312A (ko) | 2020-12-04 | 2021-12-03 | 적층 필름 및 성형체, 및 그들의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020202122A JP2022089600A (ja) | 2020-12-04 | 2020-12-04 | 積層フィルムおよび成形体、ならびにそれらの製造方法 |
JP2020-202122 | 2020-12-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022118967A1 true WO2022118967A1 (ja) | 2022-06-09 |
Family
ID=81853372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/044529 WO2022118967A1 (ja) | 2020-12-04 | 2021-12-03 | 積層フィルムおよび成形体、ならびにそれらの製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20240091998A1 (ja) |
EP (1) | EP4257355A1 (ja) |
JP (1) | JP2022089600A (ja) |
KR (1) | KR20230115312A (ja) |
CN (1) | CN116529049A (ja) |
WO (1) | WO2022118967A1 (ja) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007328284A (ja) * | 2006-06-09 | 2007-12-20 | Bridgestone Corp | ディスプレイ用光学フィルタの製造方法、ディスプレイ用光学フィルタ、これを備えたディスプレイ及びプラズマディスプレイパネル |
JP2015004937A (ja) | 2013-06-24 | 2015-01-08 | 凸版印刷株式会社 | 反射防止フィルム |
WO2020116576A1 (ja) * | 2018-12-06 | 2020-06-11 | 日本ペイント・オートモーティブコーティングス株式会社 | 加飾用積層部材及び加飾成形体の製造方法 |
WO2020189707A1 (ja) * | 2019-03-18 | 2020-09-24 | 三菱瓦斯化学株式会社 | 反射防止フィルム用積層体、反射防止フィルム、及び、反射防止フィルム用積層体の製造方法 |
JP2020202122A (ja) | 2019-06-12 | 2020-12-17 | 三菱電機株式会社 | 過電流引外し装置 |
WO2021020301A1 (ja) * | 2019-07-26 | 2021-02-04 | 日本ペイント・オートモーティブコーティングス株式会社 | 積層フィルムおよび積層部材 |
JP2021101221A (ja) * | 2019-12-24 | 2021-07-08 | パナソニックIpマネジメント株式会社 | 光学機能樹脂パネルおよびその製造方法 |
JP6941747B1 (ja) * | 2021-03-18 | 2021-09-29 | 大日精化工業株式会社 | 塗料組成物、半硬化膜、加飾成形品、及び加飾成形品の製造方法 |
-
2020
- 2020-12-04 JP JP2020202122A patent/JP2022089600A/ja active Pending
-
2021
- 2021-12-03 KR KR1020237021605A patent/KR20230115312A/ko active Search and Examination
- 2021-12-03 CN CN202180080020.2A patent/CN116529049A/zh active Pending
- 2021-12-03 WO PCT/JP2021/044529 patent/WO2022118967A1/ja active Application Filing
- 2021-12-03 US US18/039,521 patent/US20240091998A1/en active Pending
- 2021-12-03 EP EP21900716.8A patent/EP4257355A1/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007328284A (ja) * | 2006-06-09 | 2007-12-20 | Bridgestone Corp | ディスプレイ用光学フィルタの製造方法、ディスプレイ用光学フィルタ、これを備えたディスプレイ及びプラズマディスプレイパネル |
JP2015004937A (ja) | 2013-06-24 | 2015-01-08 | 凸版印刷株式会社 | 反射防止フィルム |
WO2020116576A1 (ja) * | 2018-12-06 | 2020-06-11 | 日本ペイント・オートモーティブコーティングス株式会社 | 加飾用積層部材及び加飾成形体の製造方法 |
WO2020189707A1 (ja) * | 2019-03-18 | 2020-09-24 | 三菱瓦斯化学株式会社 | 反射防止フィルム用積層体、反射防止フィルム、及び、反射防止フィルム用積層体の製造方法 |
JP2020202122A (ja) | 2019-06-12 | 2020-12-17 | 三菱電機株式会社 | 過電流引外し装置 |
WO2021020301A1 (ja) * | 2019-07-26 | 2021-02-04 | 日本ペイント・オートモーティブコーティングス株式会社 | 積層フィルムおよび積層部材 |
JP2021101221A (ja) * | 2019-12-24 | 2021-07-08 | パナソニックIpマネジメント株式会社 | 光学機能樹脂パネルおよびその製造方法 |
JP6941747B1 (ja) * | 2021-03-18 | 2021-09-29 | 大日精化工業株式会社 | 塗料組成物、半硬化膜、加飾成形品、及び加飾成形品の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP4257355A1 (en) | 2023-10-11 |
JP2022089600A (ja) | 2022-06-16 |
US20240091998A1 (en) | 2024-03-21 |
KR20230115312A (ko) | 2023-08-02 |
CN116529049A (zh) | 2023-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3309228B1 (en) | Flexible plastic film | |
JP4457324B2 (ja) | 成型用ハードコートフィルム | |
TW201012647A (en) | Continuous manufacturing method of acrylic resin sheet | |
JP5434568B2 (ja) | 成型用ハードコートフィルム | |
JP2009263600A (ja) | ハードコート層用組成物およびハードコートフィルム | |
WO2021235493A1 (ja) | 積層フィルムおよび成形体、ならびにこれらの製造方法 | |
JP2011126165A (ja) | 成型用ハードコートフィルム | |
JP6818186B2 (ja) | 加飾用積層部材及び加飾成形体の製造方法 | |
JP5651921B2 (ja) | ハードコート層用組成物 | |
JP6917534B2 (ja) | 積層フィルムおよび積層部材 | |
WO2022118967A1 (ja) | 積層フィルムおよび成形体、ならびにそれらの製造方法 | |
JP2006178276A (ja) | 反射防止積層フィルム | |
JP2011148964A (ja) | 成型用ハードコートフィルム | |
JP6880347B1 (ja) | 積層フィルムの製造方法および積層部材の製造方法 | |
JP2011131408A (ja) | 成型用ハードコートフィルム | |
JP2022151967A (ja) | 積層フィルムおよび成形体、ならびにそれらの製造方法 | |
JP2023006496A (ja) | 積層フィルムおよび成形体、ならびにそれらの製造方法 | |
JP2020090084A (ja) | 加飾用積層部材及び加飾成形体の製造方法 | |
JP2024033400A (ja) | 積層フィルムおよびその製造方法、ならびに成形体 | |
KR20160059920A (ko) | 첨가제를 통한 분산성이 우수한 반사 방지필름 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21900716 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202180080020.2 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18039521 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20237021605 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021900716 Country of ref document: EP Effective date: 20230704 |