KR102618670B1 - laminated film - Google Patents
laminated film Download PDFInfo
- Publication number
- KR102618670B1 KR102618670B1 KR1020187026984A KR20187026984A KR102618670B1 KR 102618670 B1 KR102618670 B1 KR 102618670B1 KR 1020187026984 A KR1020187026984 A KR 1020187026984A KR 20187026984 A KR20187026984 A KR 20187026984A KR 102618670 B1 KR102618670 B1 KR 102618670B1
- Authority
- KR
- South Korea
- Prior art keywords
- hard coat
- component
- laminated film
- coat layer
- group
- Prior art date
Links
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 125000000524 functional group Chemical group 0.000 claims abstract description 33
- 239000011256 inorganic filler Substances 0.000 claims abstract description 31
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 22
- 229920006295 polythiol Polymers 0.000 claims abstract description 22
- 238000005452 bending Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 description 23
- -1 polyethylene Polymers 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 238000000418 atomic force spectrum Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 3
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 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
- 230000003287 optical effect Effects 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ACBOBKJKSFYJML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylpropanoic acid Chemical compound CC(S)C(O)=O.CC(S)C(O)=O.CC(S)C(O)=O.CCC(CO)(CO)CO ACBOBKJKSFYJML-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- SPPFSBMOVFFLIG-UHFFFAOYSA-N 3-tribromosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Br)(Br)Br SPPFSBMOVFFLIG-UHFFFAOYSA-N 0.000 description 1
- NYMTUQZDDVDVHQ-UHFFFAOYSA-N 3-tribromosilylpropyl prop-2-enoate Chemical compound Br[Si](Br)(Br)CCCOC(=O)C=C NYMTUQZDDVDVHQ-UHFFFAOYSA-N 0.000 description 1
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GYZDIJYKJYCVFN-UHFFFAOYSA-N C(C1CO1)OC(C)[Si](Br)(Br)Br Chemical compound C(C1CO1)OC(C)[Si](Br)(Br)Br GYZDIJYKJYCVFN-UHFFFAOYSA-N 0.000 description 1
- VVPYMJPFIGHCLL-UHFFFAOYSA-N C(C1CO1)OCC[Si](Br)(Br)Br Chemical compound C(C1CO1)OCC[Si](Br)(Br)Br VVPYMJPFIGHCLL-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-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
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical class SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- XRLWQTOZMISADO-UHFFFAOYSA-N [diacetyloxy(prop-2-enyl)silyl] acetate Chemical compound CC(=O)O[Si](CC=C)(OC(C)=O)OC(C)=O XRLWQTOZMISADO-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 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 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- BZAROSBWJASVBU-UHFFFAOYSA-N tribromo(ethenyl)silane Chemical compound Br[Si](Br)(Br)C=C BZAROSBWJASVBU-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- LWGHVTHSEFOVRY-UHFFFAOYSA-N trichloro-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound Cl[Si](Cl)(Cl)CCOCC1CO1 LWGHVTHSEFOVRY-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- SJQPASOTJGFOMU-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)C(C)OCC1CO1 SJQPASOTJGFOMU-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DAVVOFDYOGMLNQ-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)C(C)OCC1CO1 DAVVOFDYOGMLNQ-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
Abstract
본 발명은, 기재층과 하드 코트층을 갖는 적층 필름으로서, 상기 하드 코트층이, 하기 (A) 성분, (B) 성분, 및 (C) 성분을 함유하는 하드 코트제를 사용하여 형성된 것이고, 원자간력 현미경을 사용하여 상기 하드 코트층 표면의 영률을 측정했을 때에, 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있는 것을 특징으로 하는 적층 필름이다.
(A) 성분 : 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물
(B) 성분 : 폴리티올 화합물
(C) 성분 : 반응성 관능기를 갖는 무기 필러
본 발명에 의하면, 경도가 높고, 내찰상성 및 내굴곡성이 우수한 하드 코트층을 갖는 적층 필름이 제공된다. The present invention is a laminated film having a base layer and a hard coat layer, wherein the hard coat layer is formed using a hard coat agent containing the following components (A), (B), and (C), When the Young's modulus of the surface of the hard coat layer was measured using an atomic force microscope, the region with a Young's modulus of 1 to 5 GPa constituted a continuous structure, and the region with a Young's modulus of 6 to 10 GPa was isolated and dispersed. It is a laminated film made of.
(A) Component: Organosilicon compound having a reactive functional group and a hydrolyzable group
(B) Component: Polythiol compound
(C) Component: Inorganic filler having a reactive functional group
According to the present invention, a laminated film having a hard coat layer with high hardness and excellent scratch resistance and bending resistance is provided.
Description
본 발명은, 경도가 높고, 내찰상성 및 내굴곡성이 우수한 하드 코트층을 갖는 적층 필름에 관한 것이다. The present invention relates to a laminated film having a hard coat layer with high hardness and excellent scratch resistance and bending resistance.
최근, 각종 디스플레이 등의 표시 장치는, 터치 패널을 구비하여, 데이터 입력 장치로서 사용되는 일도 많아지고 있다.Recently, display devices such as various displays are increasingly equipped with touch panels and are used as data input devices.
이와 같은 터치 패널을 사용할 때는, 통상 펜이나 손가락을 터치 패널의 표면에 접촉시킨다. 따라서, 터치 패널의 표면은, 펜이나 손가락에 의한 접촉이 반복되어도, 흠집이 나지 않을 것이 요구된다.When using such a touch panel, a pen or finger is usually brought into contact with the surface of the touch panel. Therefore, the surface of the touch panel is required to be free from scratches even if contact with a pen or finger is repeated.
이 때문에, 종래 터치 패널을 구성하는 수지 필름에 하드 코트층을 형성하는 것이 실시되어 왔다.For this reason, it has been conventionally practiced to form a hard coat layer on the resin film constituting the touch panel.
예를 들어, 특허문헌 1 에는, 반응성 관능기를 갖는 유기 규소 화합물과, 폴리티올 화합물을 함유하는 투명 피막층 형성용 수지 조성물이나, 이 수지 조성물을 사용하여 투명 피막을 형성하는 방법이 기재되어 있다. 또, 이 문헌에는, 그 수지 조성물을 사용하여 형성된 투명 피막은, 가요성, 경도, 내찰상성 및 내마모성이 우수한 것도 기재되어 있다.For example, Patent Document 1 describes a resin composition for forming a transparent film layer containing an organosilicon compound having a reactive functional group and a polythiol compound, and a method of forming a transparent film using this resin composition. Additionally, this document also describes that a transparent film formed using the resin composition is excellent in flexibility, hardness, scratch resistance, and wear resistance.
상기와 같이, 특허문헌 1 에는, 그 투명 피막이 가요성, 경도, 내찰상성, 및 내마모성 등이 우수한 것이 기재되어 있다. As mentioned above, Patent Document 1 describes that the transparent film is excellent in flexibility, hardness, scratch resistance, and wear resistance.
그러나, 그러한 투명 피막을 형성하기 위해서는 수지 조성물을 충분히 경화시킬 필요가 있고, 경화 조건에 따라서는, 목적의 성능을 갖는 투명 피막을 형성할 수 없는 경우가 있었다. However, in order to form such a transparent film, it is necessary to sufficiently cure the resin composition, and depending on the curing conditions, there are cases where a transparent film with the desired performance cannot be formed.
본 발명은, 상기 실정을 감안하여 이루어진 것으로, 경도가 높고, 내찰상성 및 내굴곡성이 우수한 하드 코트층을 갖는 적층 필름을 제공하는 것을 목적으로 한다.The present invention was made in view of the above-described circumstances, and its purpose is to provide a laminated film having a hard coat layer with high hardness and excellent scratch resistance and bending resistance.
본 발명자들은 상기 과제를 해결하기 위하여, 하드 코트층에 대해 예의 검토하였다. 그 결과, 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물, 폴리티올 화합물, 그리고 반응성 관능기를 갖는 무기 필러를 함유하는 하드 코트제를 사용함으로써, 경도가 높고, 또한 내찰상성이 우수한 하드 코트층을 효율적으로 형성할 수 있는 것을 알 수 있었다. 또한, 하드 코트층에 무기 필러를 첨가하면, 하드 코트층의 내굴곡성이 저하하는 경우도 있지만, 하드 코트층 중에 있어서의 무기 필러의 분산 상태를 제어함으로써, 내굴곡성의 저하를 억제할 수 있는 것도 알 수 있었다.In order to solve the above problems, the present inventors carefully studied the hard coat layer. As a result, by using a hard coat agent containing an organosilicon compound having a reactive functional group and a hydrolyzable group, a polythiol compound, and an inorganic filler having a reactive functional group, a hard coat layer with high hardness and excellent scratch resistance can be efficiently produced. I was able to see what could be formed. In addition, when an inorganic filler is added to the hard coat layer, the bending resistance of the hard coat layer may decrease, but the decrease in bending resistance can be suppressed by controlling the dispersion state of the inorganic filler in the hard coat layer. Could know.
본 발명은 이들 지견에 기초하여 이루어진 것이다.The present invention was made based on these findings.
이와 같이 하여 본 발명에 의하면, 하기 (1) 의 적층 필름이 제공된다.In this way, according to the present invention, the laminated film (1) below is provided.
(1) 기재층과 하드 코트층을 갖는 적층 필름으로서,(1) A laminated film having a base layer and a hard coat layer,
상기 하드 코트층이, 하기 (A) 성분, (B) 성분, 및 (C) 성분을 함유하는 하드 코트제를 사용하여 형성된 것이고, 원자간력 현미경을 사용하여 상기 하드 코트층 표면의 영률을 측정했을 때에, 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있는 것을 특징으로 하는 적층 필름. The hard coat layer is formed using a hard coat agent containing the following components (A), (B), and (C), and the Young's modulus of the surface of the hard coat layer is measured using an atomic force microscope. A laminated film characterized in that regions with a Young's modulus of 1 to 5 GPa form a continuous structure, and regions with a Young's modulus of 6 to 10 GPa are isolated and dispersed when formed.
(A) 성분 : 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물 (A) Component: Organosilicon compound having a reactive functional group and a hydrolyzable group
(B) 성분 : 폴리티올 화합물 (B) Component: Polythiol compound
(C) 성분 : 반응성 관능기를 갖는 무기 필러(C) Component: Inorganic filler having a reactive functional group
본 발명에 의하면, 경도가 높고, 내찰상성 및 내굴곡성이 우수한 하드 코트층을 갖는 적층 필름이 제공된다. According to the present invention, a laminated film having a hard coat layer with high hardness and excellent scratch resistance and bending resistance is provided.
도 1 은 실시예 1 에서 얻어진 적층 필름 (1) 의 영률 매핑 화상이다.
도 2 는 비교예 1 에서 얻어진 적층 필름 (2) 의 영률 매핑 화상이다.
도 3 은 비교예 2 에서 얻어진 적층 필름 (3) 의 영률 매핑 화상이다.
도 4 는 비교예 3 에서 얻어진 적층 필름 (4) 의 영률 매핑 화상이다.
도 5 는 비교예 4 에서 얻어진 적층 필름 (5) 의 영률 매핑 화상이다.1 is a Young's modulus mapping image of the laminated film 1 obtained in Example 1.
Figure 2 is a Young's modulus mapping image of the laminated film 2 obtained in Comparative Example 1.
Figure 3 is a Young's modulus mapping image of the laminated film 3 obtained in Comparative Example 2.
Figure 4 is a Young's modulus mapping image of the laminated film 4 obtained in Comparative Example 3.
Figure 5 is a Young's modulus mapping image of the laminated film 5 obtained in Comparative Example 4.
본 발명의 적층 필름은, 기재층과 하드 코트층을 갖는 적층 필름으로서, 상기 하드 코트층이, 하기 (A) 성분, (B) 성분, 및 (C) 성분을 함유하는 하드 코트제를 사용하여 형성된 것이고, 원자간력 현미경을 사용하여 상기 하드 코트층 표면의 영률을 측정했을 때에, 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있는 것을 특징으로 한다.The laminated film of the present invention is a laminated film having a base layer and a hard coat layer, and the hard coat layer uses a hard coat agent containing the following components (A), (B), and (C). formed, and when the Young's modulus of the surface of the hard coat layer was measured using an atomic force microscope, the region with a Young's modulus of 1 to 5 GPa constituted a continuous structure, and the region with a Young's modulus of 6 to 10 GPa was isolated and dispersed. It is characterized by having
(A) 성분 : 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물 (A) Component: Organosilicon compound having a reactive functional group and a hydrolyzable group
(B) 성분 : 폴리티올 화합물 (B) Component: Polythiol compound
(C) 성분 : 반응성 관능기를 갖는 무기 필러(C) Component: Inorganic filler having a reactive functional group
본 발명의 적층 필름을 구성하는 기재층은, 하드 코트층을 유지하기 위해 사용된다. The base material layer constituting the laminated film of the present invention is used to maintain the hard coat layer.
기재층의 종류는 특별히 한정되지 않는다. 예를 들어, 합성 수지 필름을 기재층으로서 이용할 수 있다.The type of the base layer is not particularly limited. For example, a synthetic resin film can be used as a base layer.
합성 수지 필름으로는, 예를 들어 폴리에틸렌, 폴리프로필렌, 폴리염화비닐, 폴리염화비닐리덴, 에틸렌-아세트산비닐 공중합체, 에틸렌-비닐알코올 공중합체, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리메타크릴산메틸, 폴리아크릴산메틸, 폴리메타크릴산에틸, 폴리스티렌, 3 아세트산셀룰로오스, 셀로판, 폴리카보네이트 등의 필름을 들 수 있다.Synthetic resin films include, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. , polymethyl methacrylate, methyl polyacrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, and polycarbonate.
본 발명에 있어서, 상기 기재층의 적어도 일방의 면에는 프라이머층이 형성되어 있어도 된다. 상기 프라이머층으로는, 그 위에 형성되는 하드 코트층에 대한 밀착성 및 상기 기재층에 대한 밀착성이 양호한 것이면 되고, 그 종류는 특별히 제한되지 않는다. 프라이머층으로는, 아크릴계 프라이머층, 폴리에스테르계 프라이머층, 폴리우레탄계 프라이머층, 실리콘계 프라이머층, 고무계 프라이머층 등의 종래 공지된 프라이머층을 사용할 수 있다.In the present invention, a primer layer may be formed on at least one side of the base material layer. The primer layer may have good adhesion to the hard coat layer formed thereon and good adhesion to the base material layer, and its type is not particularly limited. As the primer layer, conventionally known primer layers such as an acrylic primer layer, a polyester primer layer, a polyurethane primer layer, a silicone primer layer, and a rubber primer layer can be used.
기재층 (합성 수지 필름) 의 두께는 특별히 한정되지 않고, 적층 필름의 용도 등에 따라 적절히 결정할 수 있다. The thickness of the base layer (synthetic resin film) is not particularly limited and can be determined appropriately depending on the use of the laminated film, etc.
기재층의 두께는, 통상 10 ∼ 500 ㎛, 바람직하게는 20 ∼ 200 ㎛ 이다. The thickness of the base layer is usually 10 to 500 μm, preferably 20 to 200 μm.
본 발명의 적층 필름을 구성하는 하드 코트층은, 하기 (A) 성분, (B) 성분, 및 (C) 성분을 함유하는 하드 코트제 (이하, 「하드 코트제 (α)」라고 하는 경우가 있다.) 를 사용하여 형성된 것이다.The hard coat layer constituting the laminated film of the present invention is a hard coat agent (hereinafter referred to as “hard coat agent (α)”) containing the following components (A), (B), and (C). It is formed using .
하드 코트제 (α) 는, (A) 성분으로서 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물 (이하, 「유기 규소 화합물 (A)」라고 하는 경우가 있다.) 을 함유한다.The hard coat agent (α) contains an organosilicon compound (hereinafter sometimes referred to as “organosilicon compound (A)”) having a reactive functional group and a hydrolyzable group as the (A) component.
유기 규소 화합물 (A) 중의 반응성 관능기란, (B) 성분의 메르캅토기와 반응하여 화학 결합을 형성할 수 있는 기를 말한다.The reactive functional group in the organosilicon compound (A) refers to a group that can form a chemical bond by reacting with the mercapto group of component (B).
이 반응성 관능기로는, 비닐기, 알릴기, 스티릴기, (메트)아크릴로일옥시기 등의 탄소-탄소 불포화 결합을 갖는 기 ; 에폭시기 ; 이소시아네이트기 ; 메르캅토기 ; 등을 들 수 있다. 이들 중에서도, 탄소-탄소 불포화 결합을 갖는 기가 바람직하고, 비닐기가 보다 바람직하다.Examples of this reactive functional group include groups having a carbon-carbon unsaturated bond such as vinyl group, allyl group, styryl group, and (meth)acryloyloxy group; Epoxy group; Isocyanate group; Mercapto group; etc. can be mentioned. Among these, a group having a carbon-carbon unsaturated bond is preferable, and a vinyl group is more preferable.
유기 규소 화합물 (A) 중의 가수분해성기란, 가수분해 반응에 의해 실록산 결합 (Si-O-Si 결합) 을 형성할 수 있는 기를 말한다.The hydrolyzable group in the organosilicon compound (A) refers to a group that can form a siloxane bond (Si-O-Si bond) through a hydrolysis reaction.
이 가수분해성기로는, 메톡시기, 에톡시기, n-프로폭시기 등의 탄소수 1 ∼ 10, 바람직하게는 1 ∼ 5 의 알콕시기 ; 페녹시기 등의 탄소수 6 ∼ 15, 바람직하게는 6 ∼ 10 의 아릴옥시기 ; 포르밀옥시기, 아세톡시기, 프로피오닐옥시기 등의 탄소수 1 ∼ 10, 바람직하게는 1 ∼ 5 의 아실옥시기 ; 염소 원자, 브롬 원자 등의 할로겐 원자 ; 등을 들 수 있다. 이들 중에서도, 탄소수 1 ∼ 10 의 알콕시기 또는 탄소수 1 ∼ 10 의 아실옥시기가 바람직하고, 탄소수 1 ∼ 10 의 아실옥시기가 보다 바람직하다.Examples of this hydrolyzable group include alkoxy groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as methoxy group, ethoxy group, and n-propoxy group; Aryloxy groups having 6 to 15 carbon atoms, such as phenoxy groups, preferably 6 to 10 carbon atoms; Acyloxy groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as formyloxy group, acetoxy group, and propionyloxy group; Halogen atoms such as chlorine atoms and bromine atoms; etc. can be mentioned. Among these, an alkoxy group with 1 to 10 carbon atoms or an acyloxy group with 1 to 10 carbon atoms is preferable, and an acyloxy group with 1 to 10 carbon atoms is more preferable.
유기 규소 화합물 (A) 로는, 하기 식 (I) 로 나타내는 화합물을 들 수 있다.Examples of the organosilicon compound (A) include compounds represented by the following formula (I).
[화학식 1][Formula 1]
식 (I) 중, R1 은 반응성 관능기를 갖는 기를 나타내고, R2 는 가수분해성기를 나타내며, R3 은 반응성 관능기를 가지지 않는, 비가수분해성기를 나타낸다. In formula (I), R 1 represents a group having a reactive functional group, R 2 represents a hydrolyzable group, and R 3 represents a non-hydrolyzable group that does not have a reactive functional group.
x 는 1, 2 또는 3, y 는 1, 2 또는 3, z 는 0, 1 또는 2 이고, x, y, z 의 합계는 4 이다.x is 1, 2, or 3, y is 1, 2, or 3, z is 0, 1, or 2, and the sum of x, y, and z is 4.
x, y 또는 z 가 2 이상일 때, 복수의 R1, R2 또는 R3 은, 동일해도 되고, 서로 상이해도 된다.When x, y or z is 2 or more, a plurality of R 1 , R 2 or R 3 may be the same or different from each other.
R1 로는, 반응성 관능기나, 반응성 관능기를 갖는 기를 들 수 있다. 이들의 구체예로는, 비닐기, 비닐옥시메틸기 등의 비닐기를 갖는 기 ; 알릴기, 알릴옥시메틸기 등의 알릴기를 갖는 기 ; 스티릴기, 스티릴메틸기 등의 스티릴기를 갖는 기 ; (메트)아크릴로일기, 3-(메트)아크릴로일옥시프로필기 등의 (메트)아크릴로일기를 갖는 기 ; 에폭시기, 글리시딜기, 3-글리시딜옥시프로필기 등의 에폭시기를 갖는 기 ; 이소시아네이트기, 3-이소시아나토프로필기 등의 이소시아네이트기를 갖는 기 ; 메르캅토기, 3-메르캅토프로필기 등의 메르캅토기를 갖는 기 ; 등을 들 수 있다. 이들 중에서도, 탄소-탄소 불포화 결합을 갖는 기가 바람직하고, 비닐기가 보다 바람직하다. Examples of R 1 include a reactive functional group or a group having a reactive functional group. Specific examples of these include groups having vinyl groups such as vinyl groups and vinyloxymethyl groups; Groups having allyl groups such as allyl groups and allyloxymethyl groups; Groups having styryl groups such as styryl groups and styrylmethyl groups; Groups having (meth)acryloyl groups, such as (meth)acryloyl group and 3-(meth)acryloyloxypropyl group; Groups having epoxy groups such as epoxy groups, glycidyl groups, and 3-glycidyloxypropyl groups; Groups having isocyanate groups such as isocyanate groups and 3-isocyanatopropyl groups; Groups having mercapto groups such as mercapto group and 3-mercaptopropyl group; etc. can be mentioned. Among these, a group having a carbon-carbon unsaturated bond is preferable, and a vinyl group is more preferable.
R1 의 탄소수는, 바람직하게는 2 ∼ 20, 보다 바람직하게는 2 ∼ 10 이다. The carbon number of R 1 is preferably 2 to 20, more preferably 2 to 10.
R2 로는, 상기 가수분해성기를 들 수 있다.Examples of R 2 include the hydrolyzable groups described above.
R2 의 탄소수는 바람직하게는 0 ∼ 15, 보다 바람직하게는 0 ∼ 10 이다. The carbon number of R 2 is preferably 0 to 15, more preferably 0 to 10.
R3 으로는, 메틸기, 에틸기, n-프로필기, 이소프로필기 등의 탄소수 1 ∼ 20, 바람직하게는 1 ∼ 15 의 알킬기 ; 페닐기, 1-나프틸기 등의 탄소수 6 ∼ 20, 바람직하게는 6 ∼ 15 의 아릴기 ; 등을 들 수 있다.R 3 is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as a methyl group, ethyl group, n-propyl group, or isopropyl group; Aryl groups having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, such as phenyl group and 1-naphthyl group; etc. can be mentioned.
유기 규소 화합물 (A) 로는, 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리아세톡시실란, 비닐트리클로로실란, 비닐트리브로모실란 등의 비닐기 함유 실란 화합물 ; 알릴트리메톡시실란, 알릴트리에톡시실란, 알릴트리아세톡시실란, 알릴트리클로로실란, 알릴트리브로모실란 등의 알릴기 함유 실란 화합물 ; γ-아크릴옥시프로필트리메톡시실란, γ-아크릴옥시프로필트리에톡시실란, γ-아크릴옥시프로필트리클로로실란, γ-아크릴옥시프로필트리브로모실란 등의 γ-아크릴옥시알킬기 함유 실란 화합물 ; γ-메타크릴옥시프로필트리메톡시실란, γ-메타크릴옥시프로필트리에톡시실란, γ-메타크릴옥시프로필트리클로로실란, γ-메타크릴옥시프로필트리브로모실란 등의 γ-메타크릴옥시알킬기 함유 실란 화합물 ; α-글리시독시에틸트리메톡시실란, α-글리시독시에틸트리에톡시실란, β-글리시독시에틸트리메톡시실란, β-글리시독시에틸트리에톡시실란, α-글리시독시에틸트리클로로실란, α-글리시독시에틸트리브로모실란, β-글리시독시에틸트리클로로실란, β-글리시독시에틸트리브로모실란 등의 에폭시기 함유 실란 화합물 ; 등을 들 수 있다. Examples of the organosilicon compound (A) include vinyl group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, and vinyltribromosilane; Allyl group-containing silane compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyltriacetoxysilane, allyltrichlorosilane, and allyltribromosilane; silane compounds containing a γ-acryloxyalkyl group such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, and γ-acryloxypropyltribromosilane; Contains γ-methacryloxyalkyl groups such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and γ-methacryloxypropyltribromosilane. Silane compound; α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxyethyl epoxy group-containing silane compounds such as trichlorosilane, α-glycidoxyethyltribromosilane, β-glycidoxyethyltrichlorosilane, and β-glycidoxyethyltribromosilane; etc. can be mentioned.
이들 중에서도, 유기 규소 화합물 (A) 로는, 비닐기 함유 실란 화합물이 바람직하고, 비닐트리아세톡시실란이 보다 바람직하다. Among these, as the organosilicon compound (A), a vinyl group-containing silane compound is preferable, and vinyltriacetoxysilane is more preferable.
유기 규소 화합물 (A) 는, 1 종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다.The organosilicon compound (A) can be used individually or in combination of two or more types.
하드 코트제 (α) 는, (B) 성분으로서 폴리티올 화합물을 함유한다.The hard coat agent (α) contains a polythiol compound as component (B).
상기 유기 규소 화합물에 추가하여, 폴리티올 화합물을 함유하는 하드 코트제를 사용함으로써, 투명성이 우수하고, 연필 경도가 높으며, 내굴곡성이 우수한 하드 코트층을 형성할 수 있다.By using a hard coat agent containing a polythiol compound in addition to the organosilicon compound, a hard coat layer having excellent transparency, high pencil hardness, and excellent bending resistance can be formed.
폴리티올 화합물은, 분자 내에 2 이상의 메르캅토기를 갖는 화합물이다. A polythiol compound is a compound having two or more mercapto groups in the molecule.
폴리티올 화합물로는, 에틸렌비스(메르캅토아세테이트), 에틸렌비스(3-메르캅토프로피오네이트) 등의 메르캅토기수가 2 인 화합물 ; 트리메틸올에탄트리스(메르캅토아세테이트), 트리메틸올에탄트리스(3-메르캅토프로피오네이트), 트리메틸올프로판트리스(메르캅토아세테이트), 트리메틸올프로판트리스(3-메르캅토로프피오네이트) 등의 메르캅토기수가 3 인 화합물 ; 펜타에리트리톨테트라키스(메르캅토아세테이트), 펜타에리트리톨테트라키스(3-메르캅토프로피오네이트), 디펜타에리트리톨헥사키스(메르캅토아세테이트), 디펜타에리트리톨헥사키스(3-메르캅토프로피오네이트) 등의 메르캅토기수가 4 이상인 화합물 ; 등을 들 수 있다.Examples of the polythiol compound include compounds having a mercapto group number of 2, such as ethylenebis(mercaptoacetate) and ethylenebis(3-mercaptopropionate); Mercaps such as trimethylolethanetris(mercaptoacetate), trimethylolethanetris(3-mercaptopropionate), trimethylolpropanetris(mercaptoacetate), trimethylolpropanetris(3-mercaptopropionate), etc. Compounds with a capto group number of 3; Pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate) Compounds having a mercapto group number of 4 or more, such as pionate); etc. can be mentioned.
이들 중에서도, 폴리티올 화합물로는, 메르캅토기수가 3 인 화합물 또는 메르캅토기수가 4 이상인 화합물이 바람직하고, 트리메틸올프로판트리스(메르캅토프로피오네이트) 가 보다 바람직하다. Among these, as the polythiol compound, a compound with a mercapto group number of 3 or a compound with a mercapto group number of 4 or more is preferable, and trimethylolpropane tris(mercaptopropionate) is more preferable.
폴리티올 화합물은, 1 종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다.Polythiol compounds can be used individually or in combination of two or more types.
폴리티올 화합물의 함유량은 특별히 한정되지 않는다. 폴리티올 화합물의 함유량은 (A) 성분에 대해 통상 50 ∼ 120 질량％, 바람직하게는 60 ∼ 100 질량％, 보다 바람직하게는 60 ∼ 90 질량％ 이다.The content of the polythiol compound is not particularly limited. The content of the polythiol compound is usually 50 to 120% by mass, preferably 60 to 100% by mass, more preferably 60 to 90% by mass, based on component (A).
폴리티올 화합물의 함유량이 지나치게 적은 하드 코트제를 사용하여 하드 코트층을 형성하면, 적층 필름에 컬이 발생할 우려가 있다. 한편, 폴리티올 화합물이 지나치게 많은 하드 코트제를 사용하면, 경도가 높은 하드 코트층을 형성하는 것이 곤란해질 우려가 있다.If a hard coat layer is formed using a hard coat agent with an excessively low polythiol compound content, there is a risk that curl may occur in the laminated film. On the other hand, if a hard coat agent containing too much polythiol compound is used, there is a risk that it will be difficult to form a hard coat layer with high hardness.
하드 코트제 (α) 는, (C) 성분으로서 반응성 관능기를 갖는 무기 필러 (수식 처리에 의해, 표면에 반응성 관능기가 도입된 무기 필러를 말한다. 이하, 이 (C) 성분을 「무기 필러 (C)」라고 하는 경우가 있다.) 를 함유한다.The hard coat agent (α) is an inorganic filler having a reactive functional group as the component (C) (refers to an inorganic filler in which a reactive functional group has been introduced to the surface through modification treatment. Hereinafter, this component (C) is referred to as “inorganic filler (C). )”. It contains).
상기 유기 규소 화합물, 및 폴리티올 화합물에 추가하여, 무기 필러 (C) 를 함유하는 하드 코트제를 사용함으로써, 투명성이 우수하고, 연필 경도가 높으며, 내굴곡성, 내찰상성이 우수한 하드 코트층을 형성할 수 있다.By using a hard coat agent containing an inorganic filler (C) in addition to the above-mentioned organosilicon compound and polythiol compound, a hard coat layer having excellent transparency, high pencil hardness, bending resistance, and scratch resistance is formed. can do.
무기 필러 (C) 에 포함되는 반응성 관능기란, (B) 성분의 메르캅토기와 반응하여 화학 결합을 형성할 수 있는 기를 말한다. 이 반응성 관능기로는, 유기 규소 화합물 (A) 의 반응성 관능기로서 나타낸 것과 동일한 것을 들 수 있다. 그 중에서도, 탄소-탄소 불포화 결합을 갖는 기가 바람직하고, (메트)아크릴로일옥시기가 보다 바람직하다.The reactive functional group contained in the inorganic filler (C) refers to a group that can form a chemical bond by reacting with the mercapto group of component (B). Examples of this reactive functional group include the same ones as those shown as the reactive functional group of the organosilicon compound (A). Among them, a group having a carbon-carbon unsaturated bond is preferable, and a (meth)acryloyloxy group is more preferable.
무기 필러 (C) 를 구성하는 무기 성분 (수식 처리 전의 무기 필러의 구성 성분) 으로는, 금속 산화물, 금속 수산화물, 금속염 등을 들 수 있다.Inorganic components constituting the inorganic filler (C) (constitutive components of the inorganic filler before modification treatment) include metal oxides, metal hydroxides, and metal salts.
금속 산화물로는, 실리카, 산화티탄, 알루미나, 베이마이트, 산화크롬, 산화니켈, 산화구리, 산화티탄, 산화지르코늄, 산화인듐, 산화아연 등을 들 수 있다.Examples of metal oxides include silica, titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, and zinc oxide.
금속 수산화물로는, 수산화알루미늄 등을 들 수 있다. Examples of metal hydroxides include aluminum hydroxide.
금속염으로는, 탄산칼슘, 탄산마그네슘 등의 금속 탄산염 ; 황산칼슘, 황산바륨 등의 금속 황산염 ; 규산알루미늄, 규산칼슘, 규산마그네슘 등의 금속 규산염 ; 등을 들 수 있다.Examples of metal salts include metal carbonates such as calcium carbonate and magnesium carbonate; Metal sulfates such as calcium sulfate and barium sulfate; Metal silicates such as aluminum silicate, calcium silicate, and magnesium silicate; etc. can be mentioned.
이들 중에서도, 무기 필러 (C) 를 구성하는 무기 성분으로는, 금속 산화물이 바람직하고, 실리카가 보다 바람직하다.Among these, as the inorganic component constituting the inorganic filler (C), metal oxide is preferable and silica is more preferable.
무기 필러 (C) 의 형상은, 구상, 쇄상, 침상, 판상, 편상, 봉상, 섬유상 등 중 어느 것이어도 되지만, 구상인 것이 바람직하다. 여기서 구상이란, 진구상 외에, 회전 타원체, 난형, 별사탕상, 고치상 등 구체적으로 근사할 수 있는 다면체 형상을 포함하는 대략 구상을 의미한다.The shape of the inorganic filler (C) may be spherical, chain-shaped, needle-shaped, plate-shaped, flake-shaped, rod-shaped, fibrous, etc., but is preferably spherical. Here, the term spherical means a roughly spherical shape that includes, in addition to a true spherical shape, polyhedral shapes that can be specifically approximated, such as a spheroid, an oval, a star candy shape, and a cocoon shape.
무기 필러 (C) 의 크기는 특별히 한정되지 않는다. 무기 필러 (C) 의 평균 입경은, 통상 5 ∼ 1000 nm, 바람직하게는 10 ∼ 500 nm, 보다 바람직하게는 20 ∼ 100 nm 이다. The size of the inorganic filler (C) is not particularly limited. The average particle diameter of the inorganic filler (C) is usually 5 to 1000 nm, preferably 10 to 500 nm, and more preferably 20 to 100 nm.
무기 필러 (C) 의 평균 입경이 상기 범위 내에 있음으로써, 투명성이 우수하고, 또한 내찰상성이 우수한 하드 코트층을 효율적으로 형성할 수 있다. When the average particle size of the inorganic filler (C) is within the above range, a hard coat layer with excellent transparency and excellent scratch resistance can be efficiently formed.
무기 필러 (C) 의 평균 입경은, BET 법에 의해 얻어진 비표면적을 이용하여 산출할 수 있다.The average particle diameter of the inorganic filler (C) can be calculated using the specific surface area obtained by the BET method.
무기 필러 (C) 는, 1 종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다. The inorganic filler (C) can be used individually or in combination of two or more types.
무기 필러 (C) 의 함유량은 특별히 한정되지 않는다. 무기 필러 (C) 의 함유량은 (A) 성분에 대해 통상 30 ∼ 130 질량％, 바람직하게는 60 ∼ 125 질량％, 보다 바람직하게는 90 ∼ 125 질량％ 이다.The content of the inorganic filler (C) is not particularly limited. The content of the inorganic filler (C) is usually 30 to 130% by mass, preferably 60 to 125% by mass, more preferably 90 to 125% by mass, based on component (A).
무기 필러 (C) 의 함유량이, (A) 성분에 대해 90 ∼ 125 질량％ 인 하드 코트제를 사용하면, 경도가 높은 하드 코트층을 형성하기 쉬워진다. When a hard coat agent containing an inorganic filler (C) content of 90 to 125% by mass relative to component (A) is used, it becomes easy to form a hard coat layer with high hardness.
또, 무기 필러 (C) 의 함유량이, (A) 성분에 대해 90 ∼ 125 질량％ 인 하드 코트제를 사용하면, 내찰상성이 우수한 하드 코트층을 형성하기 쉬워진다.Additionally, if a hard coat agent having an inorganic filler (C) content of 90 to 125% by mass relative to component (A) is used, it becomes easy to form a hard coat layer with excellent scratch resistance.
하드 코트제 (α) 는, 본 발명의 효과를 저해하지 않는 범위에 있어서, (A) 성분, (B) 성분, (C) 성분 이외에 다른 성분을 함유해도 된다. 다른 성분으로는, 용매나 광 중합 개시제를 들 수 있다.The hard coat agent (α) may contain components other than component (A), component (B), and component (C) within the range that does not impair the effect of the present invention. Other components include solvents and photopolymerization initiators.
용매를 함유하는 하드 코트제는 도공성이 우수하기 때문에, 용매를 함유하는 하드 코트제를 사용함으로써, 얇은 하드 코트층을 효율적으로 형성할 수 있다.Since a hard coat agent containing a solvent has excellent coatability, a thin hard coat layer can be efficiently formed by using a hard coat agent containing a solvent.
용매로는, 헥산, 헵탄, 시클로헥산 등의 지방족 탄화수소계 용매 ; 톨루엔, 자일렌 등의 방향족 탄화수소계 용매 ; 염화메틸렌, 염화에틸렌 등의 할로겐화탄화수소계 용매 ; 메탄올, 에탄올, 프로판올, 부탄올, 1-메톡시-2-프로판올 등의 알코올계 용매 ; 아세톤, 메틸에틸케톤, 2-펜탄온, 메틸이소부틸케톤, 이소포론 등의 케톤계 용매 ; 아세트산에틸, 아세트산부틸 등의 에스테르계 용매 ; 에틸셀로솔브 등의 셀로솔브계 용매 ; 등을 들 수 있다. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, and cyclohexane; Aromatic hydrocarbon-based solvents such as toluene and xylene; Halogenated hydrocarbon-based solvents such as methylene chloride and ethylene chloride; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; Ketone-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and isophorone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve-based solvents such as ethyl cellosolve; etc. can be mentioned.
용매는, 1 종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다. Solvents can be used individually or in combination of two or more types.
하드 코트제 (α) 가 용매를 함유할 때 용매의 함유량은, 하드 코트제 (α) 의 고형분 농도가 30 ∼ 95 질량％ 이상이 되는 양이 바람직하고, 35 ∼ 90 질량％ 가 되는 양이 보다 바람직하며, 40 ∼ 85 질량％ 가 되는 양이 더욱 바람직하다.When the hard coat agent (α) contains a solvent, the solvent content is preferably an amount such that the solid content concentration of the hard coat agent (α) is 30 to 95% by mass or more, and is more preferably 35 to 90% by mass. It is preferable, and an amount of 40 to 85% by mass is more preferable.
광 중합 개시제를 함유하는 하드 코트제를 사용함으로써, 하드 코트제를 도공한 후, 얻어진 도막을 효율적으로 경화시킬 수 있다. By using a hard coat agent containing a photopolymerization initiator, the obtained coating film can be cured efficiently after applying the hard coat agent.
광 중합 개시제로는, 예를 들어 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인-n-부틸에테르, 벤조인이소부틸에테르, 아세토페논, 디메틸아미노아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 1-하이드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온, 4-(2-하이드록시에톡시)페닐-2(하이드록시-2-프로필)케톤, 벤조페논, p-페닐벤조페논, 4,4'-디에틸아미노벤조페논, 디클로로벤조페논, 2-메틸안트라퀴논, 2-에틸안트라퀴논, 2-터셔리부틸안트라퀴논, 2-아미노안트라퀴논, 2-메틸티오크산톤, 2-에틸티오크산톤, 2-클로로티오크산톤, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 벤질디메틸케탈, 아세토페논디메틸케탈, p-디메틸아미노벤조산에스테르 등을 들 수 있다.Photopolymerization initiators include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl Phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2- Propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl anthraquinone, 2-ethy anthraquinone, 2-tertiary buty anthraquinone, 2- Aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone Dimethyl ketal, p-dimethylaminobenzoic acid ester, etc. are mentioned.
광 중합 개시제는, 1 종 단독으로, 혹은 2 종 이상을 조합하여 사용할 수 있다.The photopolymerization initiator can be used individually by one type or in combination of two or more types.
하드 코트제 (α) 가 광 중합 개시제를 함유할 때 광 중합 개시제의 함유량은, 하드 코트제 (α) 의 고형분 전체량에 대해 통상 0.01 ∼ 10 질량％, 바람직하게는 0.5 ∼ 10 질량％ 이다.When the hard coat agent (α) contains a photopolymerization initiator, the content of the photopolymerization initiator is usually 0.01 to 10% by mass, preferably 0.5 to 10% by mass with respect to the total solid content of the hard coat agent (α).
본 발명의 적층체 필름을 구성하는 하드 코트층의 두께는, 통상 0.1 ∼ 50 ㎛, 바람직하게는 0.5 ∼ 20 ㎛ 이다. The thickness of the hard coat layer constituting the laminated film of the present invention is usually 0.1 to 50 μm, preferably 0.5 to 20 μm.
본 발명의 적층체 필름을 구성하는 하드 코트층은, 원자간력 현미경을 사용하여 그 표면의 영률을 측정했을 때에, 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있는 것이다.When the Young's modulus of the surface of the hard coat layer constituting the laminate film of the present invention is measured using an atomic force microscope, the region with a Young's modulus of 1 to 5 GPa constitutes a continuous structure, and the Young's modulus is 6 to 6 GPa. The 10 GPa region is isolated and dispersed.
「영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성한다」란, 영률이 1 ∼ 5 GPa 인 영역이 연속하여 큰 하나의 상 (相) 을 형성하고 있는 (이른바 해도 (海島) 구조에 있어서의 해 부분의 구조와 동일한 것을 형성하고 있다) 것을 말한다.“A region with a Young’s modulus of 1 to 5 GPa constitutes a continuous structure” means that regions with a Young’s modulus of 1 to 5 GPa are continuous and form one large phase (in the so-called sea-island structure). It forms the same structure as the solution part).
「영률이 6 ∼ 10 GPa 인 영역이 고립 분산된다」란, 영률이 6 ∼ 10 GPa 인 영역이 전체 중에서 분산되어 있는 (이른바 해도 구조에 있어서의 도 부분의 구조와 동일한 것을 형성하고 있다) 것을 말한다.“The region with a Young’s modulus of 6 to 10 GPa is isolated and dispersed” means that the region with a Young’s modulus of 6 to 10 GPa is dispersed throughout the whole (forming the same structure as the island portion of the so-called sea-island structure). .
영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하는 하드 코트층은, 굴곡 시의 응력을 효율적으로 완화할 수 있어, 내굴곡성이 우수한 것이 된다. 또, 그 한편으로, 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있음으로써, 그 하드 코트층은, 연필의 끝 등의 밀리미터 스케일의 것의 접촉에 대해 충분한 경도를 갖는다.A hard coat layer in which a region with a Young's modulus of 1 to 5 GPa constitutes a continuous structure can efficiently relieve stress during bending and has excellent bending resistance. On the other hand, since the regions with a Young's modulus of 6 to 10 GPa are isolated and dispersed, the hard coat layer has sufficient hardness for contact with a millimeter-scale object such as the tip of a pencil.
하드 코트층 표면의 영률은, 실시예에 기재된 방법에 따라 측정할 수 있다.The Young's modulus of the surface of the hard coat layer can be measured according to the method described in the Examples.
영률이 6 ∼ 10 GPa 인 영역의 하나하나는, 나노 사이즈인 것이 바람직하다. 예를 들어, 그 영역이 내접하는 정방형 또는 장방형을 그렸을 때에, 그 변의 길이는, 바람직하게는 10 ∼ 100 nm, 보다 바람직하게는 40 ∼ 60 nm 이다.It is preferable that each region where the Young's modulus is 6 to 10 GPa is nano-sized. For example, when a square or rectangle is drawn with the area inscribed, the side length is preferably 10 to 100 nm, more preferably 40 to 60 nm.
이들 구조를 갖는 하드 코트층은, 이하에 설명하는 바와 같이 하드 코트제 (α) 에 포함되는 (A) 성분, (B) 성분, 및 (C) 성분의 양을 조절함으로써 효율적으로 형성할 수 있다.A hard coat layer having these structures can be formed efficiently by controlling the amounts of component (A), component (B), and component (C) contained in the hard coat agent (α), as described below. .
먼저, 하드 코트제 (α) 를 구성하는 (A) 성분이나 (C) 성분에 포함되는 반응성 관능기는, (B) 성분의 메르캅토기와 반응할 수 있는 것임과 함께, 이들 반응성 관능기끼리에서도 반응할 수 있는 것이다.First, the reactive functional groups contained in component (A) or component (C) constituting the hard coat agent (α) can react with the mercapto group of component (B), and these reactive functional groups also react with each other. It can be done.
만일, (C) 성분의 반응기끼리에서의 반응이 주로 진행되면, (C) 성분이 일부에 응집하여, 목적의 구조를 갖는 하드 코트층을 형성할 수 없다.If the reaction between the reactors of component (C) proceeds mainly, component (C) aggregates in some parts, making it impossible to form a hard coat layer with the desired structure.
따라서, (B) 성분에 포함되는 메르캅토기와 (A) 성분이나 (C) 성분에 포함되는 반응성 관능기의 반응이 충분히 진행되는 양의 (B) 성분을 사용함으로써, (C) 성분의 분산성을 높일 수 있다.Therefore, by using component (B) in an amount that sufficiently allows the reaction between the mercapto group contained in component (B) and the reactive functional group contained in component (A) or component (C) to proceed, the dispersibility of component (C) can be improved. can increase.
또, 이들 반응성 관능기와 메르캅토기의 반응은 부가 반응이고, 이 반응이 일어나도 하드 코트층의 수축이 일어나기 어렵다. 한편, 반응성 관능기끼리의 반응이 필요 이상으로 일어나면, 국소적인 경화 수축이 생겨, 광학 특성이 저하하거나, 컬이 생기거나 할 우려가 있다. Additionally, the reaction between these reactive functional groups and the mercapto group is an addition reaction, and even if this reaction occurs, shrinkage of the hard coat layer is unlikely to occur. On the other hand, if the reaction between reactive functional groups occurs more than necessary, there is a risk that local cure shrinkage may occur, optical properties may deteriorate, or curl may occur.
이 점에서, 상기 반응성 관능기끼리를 반응시키는 경우에는, 통상 자외선이나 전자선 등의 활성 에너지선을 조사하거나, 가열하거나 하는 것이 필요로 되기 때문에, 반응성 관능기와 메르캅토기의 반응이, 반응성 관능기끼리의 반응에 비해 빠르게 진행된다. 따라서, 필요에 따라 자외선이나 전자선 등의 활성 에너지선을 조사하거나, 가열하거나 하는 단계를 검토함으로써, 목적의 특성을 갖는 하드 코트층을 효율적으로 형성할 수 있다.In this regard, when reacting the above-mentioned reactive functional groups, it is usually necessary to irradiate active energy rays such as ultraviolet rays or electron beams or to heat them, so the reaction between the reactive functional groups and the mercapto group is carried out between the reactive functional groups. It progresses quickly compared to the reaction. Therefore, by considering steps such as irradiating active energy rays such as ultraviolet rays or electron beams or heating as necessary, a hard coat layer having the desired properties can be efficiently formed.
이와 같이, 사용하는 (A) 성분이나 (C) 성분에 포함되는 반응성 관능기량에 따라 적당량의 (B) 성분을 사용하여, 반응성 관능기와 메르캅토기의 반응을 충분히 실시시킴으로써, 상기 구조를 가져, 광학 특성, 내굴곡성이 우수하고, 컬이 생기기 어려운 하드 코트층을 형성할 수 있다.In this way, by using an appropriate amount of component (B) depending on the amount of reactive functional group contained in component (A) or component (C) to be used, and sufficiently conducting a reaction between the reactive functional group and the mercapto group, the above structure is obtained, It has excellent optical properties and bending resistance, and can form a hard coat layer that is difficult to curl.
본 발명의 적층 필름은, 예를 들어 기재층이 되는 합성 수지 필름 상에, 직접 또는 기타 층을 개재하여, 하드 코트제 (α) 를 도포하고, 얻어진 도막을 경화시킴으로써 제조할 수 있다.The laminated film of the present invention can be produced, for example, by applying a hard coat agent (α) directly or through another layer onto a synthetic resin film serving as a base layer, and curing the obtained coating film.
합성 수지 필름 상에 하드 코트제를 도공하는 방법으로는, 특별히 제한은 없고 공지된 방법을 채용할 수 있다. 예를 들어, 롤 코트법, 커튼 플로우 코트법, 메이어 바 코트법, 리버스 코트법, 그라비어 코트법, 그라비어 리버스 코트법, 에어 나이프 코트법, 키스 코트법, 블레이드 코트법, 스무드 코트법, 롤 나이프 코트법 등을 들 수 있다. There is no particular limitation as a method for coating the hard coat agent on the synthetic resin film, and a known method can be adopted. For example, roll coat method, curtain flow coat method, Meyer bar coat method, reverse coat method, gravure coat method, gravure reverse coat method, air knife coat method, kiss coat method, blade coat method, smooth coat method, roll knife method. Examples include the coat method.
도막을 경화시키는 방법은 특별히 한정되지 않는다. 예를 들어, 도막에 대해 자외선, 전자선 등의 활성 에너지선을 조사함으로써 도막을 경화시킬 수 있다. The method of curing the coating film is not particularly limited. For example, the coating film can be cured by irradiating the coating film with active energy rays such as ultraviolet rays or electron beams.
자외선 조사는, 고압 수은 램프, 퓨전 H 램프, 크세논 램프 등에 의해 실시할 수 있다. 자외선의 조사량은, 조도 50 ∼ 1000 mW/㎠, 광량 50 ∼ 1000 mJ/㎠ 정도가 바람직하다. 한편, 전자선 조사는, 전자선 가속기 등에 의해 실시할 수 있다. 전자선의 조사량은, 10 ∼ 1000 krad 정도가 바람직하다. Ultraviolet irradiation can be performed using a high-pressure mercury lamp, fusion H lamp, xenon lamp, etc. The irradiation amount of ultraviolet rays is preferably approximately 50 to 1000 mW/cm2 and 50 to 1000 mJ/cm2. On the other hand, electron beam irradiation can be performed using an electron beam accelerator or the like. The irradiation amount of the electron beam is preferably about 10 to 1000 krad.
하드 코트층을 형성할 때는, 필요에 따라 도막의 경화 전 또는 도막의 경화 후에 건조 처리를 실시해도 된다. When forming a hard coat layer, drying treatment may be performed before or after curing the coating film, as needed.
건조 처리 조건은 특별히 한정되지 않는다. 건조 온도는, 예를 들어 40 ∼ 150 ℃, 바람직하게는 60 ∼ 140 ℃ 이고, 건조 시간은, 예를 들어 30 초 내지 1 시간, 바람직하게는 1 ∼ 30 분이다. Drying treatment conditions are not particularly limited. The drying temperature is, for example, 40 to 150°C, preferably 60 to 140°C, and the drying time is, for example, 30 seconds to 1 hour, preferably 1 to 30 minutes.
하드 코트층은, 경도가 높고, 또한 내찰상성이 우수하다. The hard coat layer has high hardness and is excellent in scratch resistance.
본 발명의 적층 필름을 구성하는 하드 코트층은, 실시예에 기재된 방법에 따라 연필 긁기 경도 시험을 실시하면, 통상 F 이상의 경도를 나타내고, H 이상이 바람직하다.When the hard coat layer constituting the laminated film of the present invention is subjected to a pencil scratch hardness test according to the method described in the Examples, it usually exhibits a hardness of F or higher, and H or higher is preferable.
본 발명의 적층 필름을 구성하는 하드 코트층은, 실시예에 기재된 방법에 따라 내찰상성을 평가한 경우, 통상은 흠집이 관찰되지 않는다. When the hard coat layer constituting the laminated film of the present invention is evaluated for scratch resistance according to the method described in the Examples, scratches are usually not observed.
본 발명의 적층 필름은 투명성이 우수한 것이 바람직하다. 본 발명의 적층 필름은, 전광선 투과율을 측정했을 때에, 89 ％ 이상이 바람직하고, 90 ％ 이상이 보다 바람직하다. 상한값은 특별히 없지만, 통상은 95 ％ 이하이다. It is preferable that the laminated film of the present invention has excellent transparency. When the total light transmittance of the laminated film of the present invention is measured, the total light transmittance is preferably 89% or more, and more preferably 90% or more. There is no particular upper limit, but it is usually 95% or less.
본 발명의 적층 필름은 내굴곡성이 우수한 것이 바람직하다. 본 발명의 적층 필름은, JIS K5600-5-1 에 준해, 맨드릴 굴곡 시험을 실시했을 때에, 4 mmΦ 이하가 바람직하고, 2 mmΦ 이하가 보다 바람직하다. It is preferable that the laminated film of the present invention has excellent bending resistance. When the laminated film of the present invention is subjected to a mandrel bending test according to JIS K5600-5-1, the thickness is preferably 4 mmΦ or less, and more preferably 2 mmΦ or less.
본 발명의 적층 필름은 휨이 적은 것이 바람직하다. 본 발명의 적층 필름은, 실시예에 기재된 방법에 따라 컬성을 평가하면, 통상은 75 mm 이하, 바람직하게는 50 mm 이하이다. 하한값은 특별히 없지만, 통상은 3.5 mm 이상이다. It is preferable that the laminated film of the present invention has little warpage. When the curl properties of the laminated film of the present invention are evaluated according to the method described in the Examples, the curl properties are usually 75 mm or less, and preferably 50 mm or less. There is no particular lower limit, but it is usually 3.5 mm or more.
본 발명의 적층 필름은, 경도가 높고, 또한 내찰상성 및 내굴곡성이 우수한 하드 코트층을 갖는 것이고, 터치 패널의 제조 재료로서 바람직하게 사용된다. The laminated film of the present invention has a hard coat layer that is high in hardness and excellent in scratch resistance and bending resistance, and is preferably used as a manufacturing material for a touch panel.
실시예Example
이하, 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 단, 본 발명은, 이하의 실시예로 조금도 한정되는 것이 아니다. Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited in any way to the following examples.
각 예 중의 부 및 ％ 는, 특별히 기재하지 않는 한 질량 기준이다.Parts and % in each example are based on mass unless otherwise specified.
실시예 및 비교예에서 사용한 화합물을 이하에 나타낸다. The compounds used in the examples and comparative examples are shown below.
유기 규소 화합물 (비닐트리아세톡시실란) 의 용액 (A1)(사카이 화학사 제조, 상품명 : SHC-001B, 농도 90 ％) Solution (A1) of organosilicon compound (vinyltriacetoxysilane) (manufactured by Sakai Chemical Company, brand name: SHC-001B, concentration 90%)
폴리티올 화합물 [트리메틸올프로판트리스(3-메르캅토프로피오네이트)] 의 용액 (B1)(사카이 화학사 제조, 상품명 : SHC-001A, 농도 60 ％) Solution (B1) of polythiol compound [trimethylolpropanetris(3-mercaptopropionate)] (manufactured by Sakai Chemical Company, brand name: SHC-001A, concentration 60%)
무기 필러 (아크릴로일옥시기를 갖는 실리카 나노 필러) 분산액 (C1)(닛산 화학 공업사 제조, 상품명 : AC-4130Y, 농도 30 ％, 평균 입경 40 ∼ 50 n)Inorganic filler (silica nanofiller having an acryloyloxy group) dispersion (C1) (manufactured by Nissan Chemical Industries, Ltd., brand name: AC-4130Y, concentration 30%, average particle size 40 to 50 n)
[실시예 1][Example 1]
유기 규소 화합물의 용액 (A1) 110 부, 폴리티올 화합물의 용액 (B1) 150 부, 무기 필러 분산액 (C1) 398 부를 혼합하고, 얻어진 혼합액을 메틸에틸케톤으로 희석하여, 농도 45 ％ 의 하드 코트제 (1) 을 조제하였다. 110 parts of the solution of the organosilicon compound (A1), 150 parts of the solution of the polythiol compound (B1), and 398 parts of the inorganic filler dispersion (C1) were mixed, the resulting mixture was diluted with methyl ethyl ketone, and a hard coat agent with a concentration of 45% was added. (1) was prepared.
편면 프라이머층이 형성된 폴리에틸렌테레프탈레이트 필름 (토요 방적사 제조, 상품명 : PET50A4100, 두께 50 ㎛) 에, 메이어 바 ＃10 을 사용하여 경화 후의 막두께가 5 ㎛ 가 되도록 하드 코트제 (1) 을 프라이머층의 면 상에 도포하고, 자외선을 조사 (광량 : 500 mJ/㎠) 하여 도막을 경화시켰다. 이어서 경화 도막을, 120 ℃ 에서 20 분간 건조시켜 하드 코트층을 형성하여, 적층 필름 (1) 을 얻었다. On a polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd., product name: PET50A4100, thickness 50 ㎛) with a single-sided primer layer, the hard coat agent (1) is applied to the primer layer using Meyer Bar #10 so that the film thickness after curing is 5 ㎛. It was applied on a surface and irradiated with ultraviolet rays (light quantity: 500 mJ/cm2) to cure the coating film. Next, the cured coating film was dried at 120°C for 20 minutes to form a hard coat layer, and laminated film (1) was obtained.
[비교예 1] [Comparative Example 1]
유기 규소 화합물의 용액 (A1) 110 부, 폴리티올 화합물의 용액 (B1) 100 부를 혼합하고, 얻어진 혼합액을 메틸에틸케톤으로 희석하여, 농도 50 ％ 의 하드 코트제 (2) 를 조제하였다. 110 parts of the solution (A1) of the organosilicon compound and 100 parts of the solution (B1) of the polythiol compound were mixed, and the obtained liquid mixture was diluted with methyl ethyl ketone to prepare a hard coat agent (2) with a concentration of 50%.
실시예 1 에 있어서 하드 코트제 (1) 을 사용하는 대신에, 하드 코트제 (2) 를 사용한 것 이외에는, 실시예 1 과 동일하게 하여 적층 필름 (2) 를 얻었다. A laminated film (2) was obtained in the same manner as in Example 1, except that instead of using the hard coat agent (1) in Example 1, the hard coat agent (2) was used.
[비교예 2] [Comparative Example 2]
유기 규소 화합물의 용액 (A1) 110 부, 폴리티올 화합물의 용액 (B1) 100 부, 무기 필러 분산액 (C1) 278 부를 혼합하고, 얻어진 혼합액을 메틸에틸케톤으로 희석하여, 농도 50 ％ 의 하드 코트제 (3) 을 조제하였다.110 parts of the solution of the organosilicon compound (A1), 100 parts of the solution of the polythiol compound (B1), and 278 parts of the inorganic filler dispersion (C1) were mixed, and the resulting mixture was diluted with methyl ethyl ketone to prepare a hard coat agent with a concentration of 50%. (3) was prepared.
실시예 1 에 있어서 하드 코트제 (1) 을 사용하는 대신에, 하드 코트제 (3) 을 사용한 것 이외에는, 실시예 1 과 동일하게 하여 적층 필름 (3) 을 얻었다. A laminated film (3) was obtained in the same manner as in Example 1, except that instead of using the hard coat agent (1) in Example 1, the hard coat agent (3) was used.
[비교예 3] [Comparative Example 3]
유기 규소 화합물의 용액 (A1) 110 부, 폴리티올 화합물의 용액 (B1) 100 부, 무기 필러 분산액 (C1) 333 부를 혼합하고, 얻어진 혼합액을 메틸에틸케톤으로 희석하여, 농도 50 ％ 의 하드 코트제 (4) 를 조제하였다. 110 parts of the solution of the organosilicon compound (A1), 100 parts of the solution of the polythiol compound (B1), and 333 parts of the inorganic filler dispersion (C1) were mixed, and the resulting mixture was diluted with methyl ethyl ketone to prepare a hard coat agent with a concentration of 50%. (4) was prepared.
실시예 1 에 있어서 하드 코트제 (1) 을 사용하는 대신에, 하드 코트제 (4) 를 사용한 것 이외에는, 실시예 1 과 동일하게 하여 적층 필름 (4) 를 얻었다. A laminated film (4) was obtained in the same manner as in Example 1, except that instead of using the hard coat agent (1) in Example 1, the hard coat agent (4) was used.
[비교예 4] [Comparative Example 4]
유기 수식 실리카 미립자와 다관능 아크릴레이트의 혼합물 (JSR 사 제조, 상품명 : 옵스타 Z7530, 농도 73 ％, 광 중합 개시제 함유, 무기 필러 함유량 60 ％) 을 프로필렌글리콜모노메틸에테르로 희석하여, 농도 40 ％ 의 하드 코트제 (5) 를 조제하였다.A mixture of organic modified silica fine particles and multifunctional acrylate (manufactured by JSR, brand name: Opstar Z7530, concentration 73%, containing photopolymerization initiator, inorganic filler content 60%) was diluted with propylene glycol monomethyl ether to obtain a concentration of 40%. Hard coat agent (5) was prepared.
편면 프라이머층이 형성된 폴리에틸렌테레프탈레이트 필름 (토요 방적사 제조, 상품명 : PET50A4100, 두께 50 ㎛) 에, 메이어 바 ＃10 을 사용하여 경화 후의 막두께가 5 ㎛ 가 되도록 하드 코트제 (5) 를 프라이머층의 면 상에 도포하고, 얻어진 도막을 100 ℃ 에서 1 분간 건조시켰다. 이어서, 이 도막에 자외선을 조사 (광량 : 500 mJ/㎠) 하여, 도막을 경화시킴으로써 하드 코트층을 형성하여, 적층 필름 (5) 를 얻었다.To a polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd., product name: PET50A4100, thickness 50 ㎛) on which a single-sided primer layer was formed, the hard coat agent (5) was applied to the primer layer using Meyer Bar #10 so that the film thickness after curing was 5 ㎛. It was applied on cotton, and the obtained coating film was dried at 100°C for 1 minute. Next, this coating film was irradiated with ultraviolet rays (light quantity: 500 mJ/cm2) to cure the coating film to form a hard coat layer, thereby obtaining a laminated film (5).
실시예 1 및 비교예 1 ∼ 4 에서 얻어진 적층 필름 (1) ∼ (5) 에 대해, 이하의 평가를 실시하였다. 결과를 표 1 에 나타낸다. The following evaluation was performed on the laminated films (1) to (5) obtained in Example 1 and Comparative Examples 1 to 4. The results are shown in Table 1.
[막두께 평가] [Film thickness evaluation]
두께계 (니콘사 제조, 상품명 : MH-15) 를 사용하여, JIS K 7130 (1999) 에 준해, 하드 코트층의 막두께를 측정하였다.Using a thickness meter (manufactured by Nikon, brand name: MH-15), the film thickness of the hard coat layer was measured in accordance with JIS K 7130 (1999).
[전광선 투과율] [Total light transmittance]
헤이즈 미터 (닛폰 전색사 제조, 상품명 : N-DH-2000) 를 사용하여, JIS K 7361-1 (1997) 에 준해, 적층 필름의 전광선 투과율을 측정하였다.The total light transmittance of the laminated film was measured according to JIS K 7361-1 (1997) using a haze meter (manufactured by Nippon Densoku Co., Ltd., brand name: N-DH-2000).
[연필 경도] [Pencil hardness]
연필 긁기 경도 시험기 (야스다 정기 제작소사 제조, 상품명 : No.553-M) 를 사용하여, JIS K5600-5-4 (1999) 에 준해, 하중 750 g, 긁기 속도 0.5 mm/초로 연필 긁기 경도 시험을 실시하였다. Using a pencil scratching hardness tester (manufactured by Yasuda Seki Seisakusho, brand name: No. 553-M), a pencil scratching hardness test was conducted in accordance with JIS K5600-5-4 (1999) at a load of 750 g and a scratching speed of 0.5 mm/sec. It was carried out.
[내찰상성 평가] [Scratch resistance evaluation]
적층 필름의 하드 코트층을, 스틸울 ＃0000 을 사용하여, 250 g/㎠ 의 하중으로 길이 50 mm 의 범위를 10 왕복 문지르고, 그 후 육안으로 흠집의 유무를 확인하고, 이하의 기준으로 내찰상성을 평가하였다.Using steel wool #0000, the hard coat layer of the laminated film was rubbed back and forth over an area of 50 mm in length with a load of 250 g/cm2 for 10 rounds. Afterwards, the presence or absence of scratches was visually checked, and the scratch resistance was determined based on the following criteria. was evaluated.
○ : 흠집이 없다. ○: No scratches.
× : 흠집이 있다. ×: There is a scratch.
[내굴곡성 평가] [Bending resistance evaluation]
JIS K5600-5-1 (1999) 에 준해, 맨드릴 굴곡 시험을 실시하고, 적층 필름의 내굴곡성을 평가하였다. In accordance with JIS K5600-5-1 (1999), a mandrel bending test was performed to evaluate the bending resistance of the laminated film.
[컬성 평가] [Curlability evaluation]
적층 필름을 1 변 10 cm 의 정방형으로 잘라내고, 이것을 시험편으로 하였다. 이 시험편을 수평의 대 (臺) 상에 가만히 정지시키고, 이때의 네 모서리의 들뜸 (mm) 을 측정하고, 그 합계값을 산출하였다.The laminated film was cut into a square with 10 cm on each side, and this was used as a test piece. This test piece was left still on a horizontal stand, the lift (mm) of the four corners at this time was measured, and the total value was calculated.
[영률 측정] [Young’s modulus measurement]
원자간력 현미경 (AFM) 을 사용하여 포스 커브 측정을 실시하고, 하드 코트층 표면의 국소적인 영률을 이하의 방법으로 산출하였다. Force curve measurement was performed using an atomic force microscope (AFM), and the local Young's modulus of the hard coat layer surface was calculated by the following method.
또한, AFM 은, Bruker AXS 사 제조 MultiMode 8 AFM 을 이용하고, 캔틸레버는, 올림푸스사 제조 OMCL-AC160TS-C2 [스프링 정수 (공칭값 42 N/m, 열요동법에 의한 측정값 32.7 N/m), 탐침 선단 반경 15 nm] 를 사용하였다. In addition, the AFM was MultiMode 8 AFM manufactured by Bruker AXS, and the cantilever was OMCL-AC160TS-C2 manufactured by Olympus [spring constant (nominal value 42 N/m, measured value by thermal fluctuation method 32.7 N/m)] , probe tip radius 15 nm] was used.
먼저, 포스 커브 측정에 의해, 캔틸레버를 하드 코트층에 압입했을 때와, 그 후에 캔틸레버를 하드 코트층으로부터 떼었을 때의, 캔틸레버의 휨량과 피에조 스캐너의 변위량의 관계를 나타내는 그래프가 얻어진다. 그리고, 이것을 변환함으로써, 하중과 시료 변형량의 관계를 나타내는 그래프 (F-δ곡선) 가 얻어진다. First, by force curve measurement, a graph showing the relationship between the amount of deflection of the cantilever and the amount of displacement of the piezo scanner is obtained when the cantilever is press-fitted into the hard coat layer and then when the cantilever is removed from the hard coat layer. Then, by converting this, a graph (F-δ curve) showing the relationship between the load and the amount of sample deformation is obtained.
얻어진 F-δ 곡선 중의 압입 과정에 대해, Derjaguim, Muller, Toporov 등에 의한 DMT 이론식을 이용한 커브 피팅을 실시함으로써, 시료 중의 국소적인 영률 E 를 구할 수 있다. The local Young's modulus E in the sample can be obtained by performing curve fitting using the DMT theoretical formula by Derjaguim, Muller, Toporov, etc. for the indentation process in the obtained F-δ curve.
이번 측정에 있어서는, 각 시료 1 ㎛ × 1 ㎛ 면 내의 128 × 128 점 (합계 16384 점) 에 대해 포스 커브 측정 및 영률 E 의 산출을 실시하였다. In this measurement, force curve measurement and Young's modulus E were calculated for 128 × 128 points (total of 16384 points) within a 1 μm × 1 μm plane of each sample.
측정 결과를 도 1 ∼ 도 5 에 나타낸다. The measurement results are shown in Figures 1 to 5.
도 1 ∼ 5 및 표 1 로부터, 이하의 점을 알 수 있다. From Figures 1 to 5 and Table 1, the following points can be seen.
실시예 1 에서 얻어진 적층 필름 (1) 의 하드 코트층은, 도 1 에서 나타내는 바와 같이 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있다. 적층 필름 (1) 은, 투명성이 우수함과 함께, 경도가 높고, 내찰상성 및 내굴곡성이 우수하다. As shown in FIG. 1, the hard coat layer of the laminated film 1 obtained in Example 1 has a continuous structure in which regions with a Young's modulus of 1 to 5 GPa, and regions with a Young's modulus of 6 to 10 GPa are isolated and dispersed. there is. The laminated film 1 has excellent transparency, high hardness, and excellent scratch resistance and bending resistance.
비교예 1 에서 얻어진 적층 필름 (2) 의 하드 코트층은, 도 2 에서 나타내는 바와 같이 영률이 1 ∼ 5 GPa 인 영역이 전체에 걸쳐서 확산되어 있다. 적층 필름 (2) 는, 내굴곡성이 우수하지만, 경도가 낮고, 내찰상성이 열등하다. As shown in FIG. 2, the hard coat layer of the laminated film 2 obtained in Comparative Example 1 has a region with a Young's modulus of 1 to 5 GPa spread throughout. The laminated film 2 is excellent in bending resistance, but has low hardness and is inferior in scratch resistance.
비교예 2, 3 에서 얻어진 적층 필름 (3), (4) 의 하드 코트층은, 도 3, 도 4 에서 나타내는 바와 같이 영률이 6 ∼ 10 GPa 인 영역이 고립되어 있지 않고, 영률이 6 ∼ 10 GPa 인 영역에 관해서도 연속 구조가 형성되어 있다. 이와 같은 구조의 하드 코트층을 갖는 적층 필름 (3), (4) 는, 무기 필러 함유량이 동등 또는 적은 양이어도, 내굴곡성이 열등하다.As shown in FIGS. 3 and 4, the hard coat layers of the laminated films (3) and (4) obtained in Comparative Examples 2 and 3 do not have isolated regions with a Young's modulus of 6 to 10 GPa, and have a Young's modulus of 6 to 10. A continuous structure is also formed in the GPa region. The laminated films (3) and (4) having a hard coat layer of such a structure are inferior in bending resistance even if the inorganic filler content is the same or in a smaller amount.
비교예 4 에서 얻어진 적층 필름 (5) 의 하드 코트층은, 도 5 에서 나타내는 바와 같이 전체적으로 영률이 높다. 적층 필름 (5) 는, 경도가 높고, 내찰상성이 우수하지만, 내굴곡성이 열등하다. The hard coat layer of the laminated film 5 obtained in Comparative Example 4 has a high Young's modulus as a whole, as shown in FIG. 5 . The laminated film 5 has high hardness and excellent scratch resistance, but is inferior in bending resistance.
Claims (1)
상기 하드 코트층이, 하기 (A) 성분, (B) 성분, 및 (C) 성분을 함유하는 하드 코트제를 사용하여 형성된 것이고,
상기 하드 코트제에 포함되는 (B) 성분의 함유량이, (A) 성분에 대해 90.9 ~ 120 질량%이고,
상기 하드 코트제에 포함되는 (C) 성분의 함유량이, (A) 성분에 대해 30 ~ 130 질량%이고,
원자간력 현미경을 사용하여 상기 하드 코트층 표면의 영률을 측정했을 때에, 영률이 1 ∼ 5 GPa 인 영역이 연속 구조를 구성하고, 또한 영률이 6 ∼ 10 GPa 인 영역이 고립 분산되어 있는 것을 특징으로 하는 적층 필름.
(A) 성분 : 반응성 관능기 및 가수분해성기를 갖는 유기 규소 화합물
(B) 성분 : 폴리티올 화합물
(C) 성분 : 반응성 관능기를 갖는 무기 필러 A laminated film having a base layer and a hard coat layer,
The hard coat layer is formed using a hard coat agent containing the following components (A), (B), and (C),
The content of component (B) contained in the hard coat agent is 90.9 to 120% by mass relative to component (A),
The content of component (C) contained in the hard coat agent is 30 to 130% by mass relative to component (A),
When the Young's modulus of the surface of the hard coat layer was measured using an atomic force microscope, the region with a Young's modulus of 1 to 5 GPa constituted a continuous structure, and the region with a Young's modulus of 6 to 10 GPa was isolated and dispersed. Laminated film made of.
(A) Component: Organosilicon compound having a reactive functional group and a hydrolyzable group
(B) Component: Polythiol compound
(C) Component: Inorganic filler having a reactive functional group
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