CN102149779B - Surface protective film - Google Patents
Surface protective film Download PDFInfo
- Publication number
- CN102149779B CN102149779B CN200980135434XA CN200980135434A CN102149779B CN 102149779 B CN102149779 B CN 102149779B CN 200980135434X A CN200980135434X A CN 200980135434XA CN 200980135434 A CN200980135434 A CN 200980135434A CN 102149779 B CN102149779 B CN 102149779B
- Authority
- CN
- China
- Prior art keywords
- polymer
- protective film
- surface protective
- prism
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001681 protective effect Effects 0.000 title claims description 187
- 229920000642 polymer Polymers 0.000 claims abstract description 194
- 229920001577 copolymer Polymers 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 89
- -1 aromatic alkenyl compound Chemical group 0.000 claims abstract description 85
- 230000001070 adhesive effect Effects 0.000 claims abstract description 82
- 239000000853 adhesive Substances 0.000 claims abstract description 80
- 150000001993 dienes Chemical class 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 239000012790 adhesive layer Substances 0.000 claims description 95
- 239000000463 material Substances 0.000 claims description 85
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 81
- 239000010410 layer Substances 0.000 claims description 60
- 239000012744 reinforcing agent Substances 0.000 claims description 34
- 229920000098 polyolefin Polymers 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 13
- 238000009792 diffusion process Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 7
- 229920005604 random copolymer Polymers 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 28
- 238000011156 evaluation Methods 0.000 description 26
- 239000011230 binding agent Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- 230000006866 deterioration Effects 0.000 description 21
- 229920001971 elastomer Polymers 0.000 description 21
- 239000000126 substance Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 239000005060 rubber Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 229920001400 block copolymer Polymers 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 230000008859 change Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003892 spreading Methods 0.000 description 11
- 230000007480 spreading Effects 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 230000002123 temporal effect Effects 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000005048 methyldichlorosilane Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene 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
- 230000000996 additive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NSYRAUUZGRPOHS-BQYQJAHWSA-N (3E)-2-methylocta-1,3-diene Chemical compound CCCC\C=C\C(C)=C NSYRAUUZGRPOHS-BQYQJAHWSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011980 kaminsky catalyst Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000004973 liquid crystal related substance 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
- 230000000873 masking effect Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2453/00—Presence of block copolymer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
- G02F1/133607—Direct backlight including a specially adapted diffusing, scattering or light controlling members the light controlling member including light directing or refracting elements, e.g. prisms or lenses
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
An adhesive composition characterized by containing a polymer (i), which is a copolymer having a structure represented by the following general formula: [A-B]n (wherein n = 1-3) or a hydrogenated product thereof, and a polymer (ii), which is a copolymer having a structure represented by the following general formula: A-B-A or the following general formula: (A-B)x-Y (wherein x >= 1 and Y represents a residue of a coupling agent) or a hydrogenated product thereof. The adhesive composition is also characterized in that the total aromatic alkenyl compound unit content in the polymers (i) and (ii) is 30-50 wt%, and the weight ratio between the total amount of A and the total amount of B contained in the polymers (i) and (ii) is within the range of from 5:95 to 25:75. In this connection, A represents a polymer block mainly composed of aromatic alkenyl compound units, and B represents a polymer block which is an aromatic alkenyl-conjugated diene random copolymer block having an aromatic alkenyl compound unit content of 10-35 wt%.
Description
Technical Field
The present invention relates to a surface protective film.
Background
Conventionally, surface protection films (also referred to as protective tapes, masking tapes, surface protection sheets, and the like in general) formed by laminating an adhesive layer on one surface of a film-like base material have been widely used in order to protect the surfaces of various members such as optical devices, metal plates, coated metal plates, resin plates, and glass plates. In particular, in recent years, a surface protective film has been used for an optical member for a liquid crystal display. The optical member includes a member having a surface with a concavo-convex shape such as a prism sheet, a diffusion film, or the like. In order to prevent damage to the irregularities, the surfaces of these members (particularly, the outer surfaces of the irregularities) are protected with a surface protective film before use, but since a large contact area cannot be obtained when the surface protective film is attached to the surface having the aforementioned irregularities, it is necessary to form an adhesive layer having a strong adhesive force.
Generally, however, an industrially produced surface protective film is usually in the form of a roll, and is obtained by rolling a long film into a roll. It is known that a high force (unwinding force) is required to unwind the roll, and the unwinding force tends to increase with time, i.e., there is a strong demand for easily unwinding the roll.
Further, since the surface protective film is to be peeled and removed after use, the surface protective film is required to have smooth peelability and to be free from adherend contamination or the like due to paste residue of the surface protective film.
On the other hand, polar polymers such as acrylic resins and polycarbonate resins are often used as materials for prism sheets, diffusion films, and the like. These optical sheets are supplied to optical device manufacturers after a surface protective film is attached thereto, and are sometimes exposed to high temperatures during transportation, storage, and the like.
Particularly, when the surface of the adherend has irregularities, there is a problem of so-called deterioration of adhesion (increased adhesion) in which the contact area between the adherend and the adhesive layer increases and the adhesion force increases due to time, temperature, and the like.
In general, an acrylic adhesive is widely used as the adhesive, but the degree of increase in adhesive force with time of the acrylic adhesive is particularly large.
For this reason, particularly for a surface protective film applied to an optical sheet, a rubber-based adhesive is mainly used in the adhesive layer constituting the surface protective film, not an acrylic adhesive. This can prevent the adhesive force from increasing with time, and can achieve smooth peeling of the surface protective film from the surface of the lens portion (prism) of the optical sheet.
However, since the rubber-based adhesive is generally of a solution-coating type, there are problems such as environmental pollution and energy waste at the time of solvent drying, and it is necessary to release the back surface (the surface opposite to the side on which the adhesive layer is laminated) of a commonly used olefin base material layer. In addition, in the case of the hot melt adhesive, although the former problem can be eliminated or reduced, the release treatment of the back surface cannot be avoided.
In order to solve the problem of improving the unwinding property, for example, patent document 1 proposes a method for producing a surface protective film by irradiating an electron beam or γ ray to the surface of a base material layer of a laminate film in which a base material layer made of a polyolefin resin and polyorganosiloxane having a double bond in at least 1 molecule and an adhesive layer are laminated.
In addition, patent document 2 proposes a surface protective film obtained by the following method: a surface layer containing a polyolefin resin and an adhesive layer containing a thermoplastic elastomer are laminated to form a film by a coextrusion method, and then a release layer is formed on the back surface of the surface layer by a coating method.
Further, patent document 3 proposes the following surface protective film: a surface protective film is formed by co-extruding an adhesive layer mainly composed of a styrene elastomer instead of natural rubber and an olefin base material layer, wherein the back surface of the base material layer of the surface protective film is subjected to a rubbing treatment, and the surface protective film has excellent unwinding property.
On the other hand, in order to solve the problem of suppressing the deterioration of adhesion, for example, patent document 4 has made an attempt to: by mixing the polyethyleneimine into which the higher alkyl group has been introduced into the base material layer and allowing the polyethyleneimine to bleed out onto the surface of the adhesive layer, the initial adhesion to the adherend is ensured and the deterioration of adhesion is suppressed.
However, the prism sheet with the surface protective film attached thereto is generally stacked in units of several tens of sheets and stored before being mounted on a product.
In this case, the top of the unevenness of the prism sheet disposed below may be damaged by the load of the prism sheet disposed above, and the optical quality may be deteriorated. It is considered that this is caused by the following reasons: under the load, the tops of the irregularities sink into the adhesive layer of the surface protective film and even reach the base material of the surface protective film, which exceeds the limit of the dispersion and relaxation effect of the adhesive layer on the load. To solve this problem, a method of sufficiently increasing the thickness of the adhesive layer is considered. However, increasing the thickness of the adhesive layer is not only disadvantageous in terms of manufacturing cost, but also may increase the depth of penetration of the lens portion (prism) into the adhesive layer, thereby increasing the degree of increase in adhesive force with time.
For this reason, an example of using a styrene-based elastomer for the surface protective film instead of the natural rubber is proposed. For example, patent document 5 discloses a surface protective film using an adhesive layer having a thickness of 10 μm or more and containing a styrene-based elastomer as a main component. According to the description therein, the surface protective film can satisfy both a sufficient protective function for an adherend and appropriate adhesive properties.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2-252783
Patent document 2: japanese patent laid-open publication No. 2003-41216
Patent document 3: japanese laid-open patent publication No. H07-62311
Patent document 4: japanese laid-open patent publication No. H09-188857
Patent document 5: japanese patent laid-open No. 2000-80336
Disclosure of Invention
Problems to be solved by the invention
However, the following problems still remain in the above-described prior art.
In the surface protective film of patent document 1 or 3, the unwinding force cannot be sufficiently reduced by only the back surface treatment, and the unwinding property of the roll is not sufficient, which may result in a decrease in the handling property.
With the release treatment method of patent document 2, sufficient derivation properties ( - し properties) can be ensured even when the back surface of the base material is rough, but there is a concern that the release agent is transferred to the adhesive layer and the adhesiveness to the adherend is reduced.
The surface protective film disclosed in patent document 4 may not exhibit a sufficient effect of suppressing deterioration of adhesion, unlike the case of storage in a normal environment, in the amount of polyethyleneimine that oozes out to the surface when stored in an extremely high temperature environment (e.g., tropical region or subtropical region).
In the surface protective film disclosed in patent document 5, from the viewpoint of protecting the top shape of the irregularities of the prism section, there is still room for further improvement in a severe state, for example, in the case where the surface protective film is bonded to the prism surface of the prism sheet, and a protrusion such as a so-called fish eye (fish eye) is bonded to the surface opposite to the prism surface (i.e., the outer surface of the surface protective film).
Accordingly, an object of the present invention is to provide a surface protective film which can eliminate the above-mentioned defects of the prior art, can secure an appropriate initial adhesion, has an excellent spreading property, and can prevent the occurrence of paste residue after being peeled from an adherend.
Another object of the present invention is to provide a surface protective film for a prism sheet, which can ensure an appropriate initial adhesive force and can suppress deterioration of adhesion even in an extremely high temperature (e.g., 70 ℃).
Another object of the present invention is to provide a surface protective film that can protect the top surface shape of the prism portion even in a severe state, for example, particularly when the surface protective film is bonded to the prism surface of the prism sheet and a protrusion such as a so-called fish eye is pressed on the surface opposite to the prism surface (i.e., the outer surface of the surface protective film).
Means for solving the problems
The inventors of the present invention have conducted extensive studies and, as a result, found that: by using a specific multiblock copolymer having an aromatic alkenyl polymer block and an aromatic alkenyl-conjugated diene copolymer block in the adhesive layer, a surface protective film which has excellent spreadability and prevents paste residue after peeling from an adherend while securing an appropriate initial adhesive force can be obtained. And further studied to complete the present invention.
The binder composition of the present invention comprises a polymer (i) and a polymer (ii), wherein,
polymer (i): a copolymer (I) containing a polymer block A and a polymer block B and having a structure represented by the general formula [ A-B ] n (wherein A represents the polymer block A, B represents the polymer block B, and n represents an integer of 1 to 3) or a hydrogenated product thereof,
polymer (ii): a copolymer (II) containing the following polymer block A and the following polymer block B and having a structure represented by the general formula A-B-A (wherein the symbols have the same meanings as above) or the general formula (A-B) x-Y (wherein x represents an integer of 2 or more, Y represents a coupling agent residue, and the other symbols have the same meanings as above) or a hydrogenated product thereof,
the total content (St (A + B)) of the aromatic alkenyl compound units in the polymer (i) and the polymer (ii) is 30 to 50% by weight,
the weight ratio (A: B) of the total amount of the polymer block A to the total amount of the polymer block B contained in the polymer (i) and the polymer (ii) is in the range of 5:95 to 25: 75.
Wherein,
polymer block a: a polymer block mainly composed of an aromatic alkenyl compound unit having continuous aromatic alkenyl compound units,
polymer block B: an aromatic alkenyl-conjugated diene copolymer block which contains a conjugated diene unit and an aromatic alkenyl compound unit at random and has a content of the aromatic alkenyl compound unit (St (b)) of 10 to 35 wt%.
The surface protective film of the present invention has a base material layer and an adhesive layer formed from the adhesive composition of the present invention.
By using the adhesive composition of the present invention, the surface protective film of the present invention can be made to have excellent developability and can be prevented from suffering from paste residue after being peeled from an adherend.
Preferably, in the surface protective film, the base material layer is a polyolefin base material layer, the adhesive composition further contains a tackifier, and the temperature at which tan δ is maximized is from-10 ℃ to 20 ℃ when the dynamic viscoelasticity of the adhesive layer is measured at from-50 ℃ to 80 ℃.
This makes it possible to balance the spreadability and the initial adhesion of the surface protective film more favorably.
In the surface protective film, the base material layer is a polyolefin base material layer, the adhesive composition further contains a tackifier and a styrene-based block reinforcing agent, and the ratio of the weight of the aromatic alkenyl compound unit in the polymer (i), the polymer (ii), and the styrene-based block reinforcing agent (the content of the aromatic alkenyl compound unit) is preferably 20 to 50% by weight based on the weight of the adhesive layer.
This can more effectively suppress a rapid increase in adhesion force over time (at risk).
Preferably, in the surface protective film, the storage modulus G' of the adhesive layer at 70 ℃ is 4.5X 105Pa～6.0×105Pa。
This can more effectively suppress a rapid increase in the adhesive strength with time.
When the surface protective film is used to protect the surface of the prism sheet, the surface protective film is preferably bonded to the prism surface and is loaded at 0.3N/cm in a gas atmosphere at 70 DEG C2The depth of the prism apex angle of the prism surface into the adhesive is 1% or more and less than 40% of the thickness of the adhesive layer when the load of (2) is applied for 24 hours.
This can effectively prevent the prism from being damaged while ensuring an appropriate adhesive force.
When the surface protective film is used to protect the prism surface of the prism sheet, it is preferable that when the surface protective film is bonded to the prism surface and a projection having a diameter of 400 μm and a height of 12 μm is pressed on the surface opposite to the prism surface side, the depth of depression of the prism apex angle of the prism surface into the adhesive layer is 1% or more and less than 100% of the thickness of the adhesive layer.
This can effectively prevent the prism from being damaged while ensuring an appropriate adhesive force.
When the surface protection film is used to protect the prism surface of the prism sheet, the surface roughness Ra of the outer surface of the base material layer is preferably 0.7 to 2.0 μm, the average height of waviness profile unevenness (average height さ of waviness モチーフ) is preferably 3 μm or more, and the average pitch of waviness profile (average length さ of waviness モチーフ) is preferably 350 μm or more and 600 μm or less.
Accordingly, the top surface of the prism portion can be protected from a protrusion such as a fisheye in a severe state while securing an appropriate adhesive force, for example, particularly when the surface protective film is bonded to the prism surface of the prism sheet and a protrusion such as a fisheye is pressed on the surface opposite to the prism surface (i.e., the outer surface of the surface protective film).
The surface protective film is preferably used to protect the surface of the diffusion film.
ADVANTAGEOUS EFFECTS OF INVENTION
The surface protective film of the present invention has excellent developability and can prevent paste residue from occurring after peeling from an adherend.
In addition, the surface protective film according to one embodiment of the present invention can secure an appropriate initial adhesion and suppress deterioration of adhesion even in an extremely high temperature (e.g., 70 ℃).
In addition, the surface protective film according to the embodiment of the present invention can protect the top surface shape of the irregularities of the prism section even in a severe state, for example, particularly in a case where the surface protective film is bonded to the prism surface of the prism sheet and a protrusion such as a so-called fish eye is pressed on the surface opposite to the prism surface side (i.e., the outer surface of the surface protective film).
Drawings
Fig. 1 is a schematic view showing the waviness of the outer side surface of the base material layer.
Fig. 2 is a perspective view of a prism sheet using a surface protective film according to one embodiment of the present invention.
Fig. 3 shows a structure in which a surface protective film according to one embodiment of the present invention is attached to a prism sheet.
Description of the symbols
1 prism sheet
2 pieces of
3 lens part (prism)
3a Top of lens part (prism apex angle)
4 No. 1 surface protective film
5 base material layer
6 adhesive layer
7 nd 2 nd surface protective film
Detailed Description
< definitions of symbols in the present specification >
Unless otherwise specified, the symbols "to" used in the present specification to represent a numerical range indicate that the numerical range includes both of its ends.
In the present specification, the term "content ratio" of the repeating units of the polymer, which is used in the technical wording "content ratio of aromatic alkenyl compound units" or the like, means a weight ratio of the repeating units in terms of monomers from which the repeating units are derived, that is, a ratio (weight%) of the weight of the monomers from which the repeating units are derived to the total weight of all monomers used for forming the polymer, that is, a content of the aromatic alkenyl compound in the polymer. Wherein "the total weight of all monomers used to form the above polymer" is approximately the weight of the above polymer. Similarly, the "content ratio" of the repeating unit of the polymer block in the present invention means a weight ratio of the repeating unit in terms of the monomer derived therefrom, that is, a ratio (% by weight) of the weight of the monomer derived from the repeating unit to the total weight of all the monomers for forming the polymer block. Wherein "the total weight of all monomers used to form the above-mentioned polymer block" is approximately the weight of the above-mentioned polymer block.
In the present specification, the "content of ethylenic bonds" represents: the total content of 1, 2-ethylenic bonds and 3, 4-ethylenic bonds was calculated by infrared absorption spectroscopy (Morero's method).
< Binder composition >
The adhesive composition of the present invention contains the following polymer (i) and the following polymer (ii).
In the present specification, the "polymer (I)" is a copolymer (I) comprising the following polymer block A and the following polymer block B and having a structure represented by the general formula [ A-B ] n (wherein A represents the polymer block A, B represents the polymer block B, and n represents an integer of 1 to 3) or a hydrogenated product thereof.
In the present specification, the "polymer (II)" is a copolymer (II) or a hydrogenated product thereof, which comprises the following polymer block A and the following polymer block B and has a structure represented by the general formula A-B-A (wherein the symbols are as defined above) or the general formula (A-B) x-Y (wherein x represents an integer of 2 or more, Y represents a coupling agent residue, and the other symbols are as defined above).
In the present specification, a composition containing the polymer (i) and the polymer (ii) may be simply referred to as a "copolymer composition".
In the adhesive composition of the present invention, the total content of the aromatic alkenyl compound units in the polymer (i) and the polymer (ii) is 30 to 50% by weight,
the weight ratio of the total amount of the polymer block A to the total amount of the polymer block B contained in the polymer (i) and the polymer (ii) is in the range of 5:95 to 25: 75.
In the present specification, "polymer block a" is a polymer block having continuous aromatic alkenyl compound units and mainly comprising aromatic alkenyl compound units.
In the present specification, the "polymer block B" is an aromatic alkenyl-conjugated diene copolymer block which contains a conjugated diene unit and an aromatic alkenyl compound unit at random and has a content of the aromatic alkenyl compound unit (St (B)) of 10 to 35% by weight.
< Polymer Block A >
As described above, the "polymer block A" is a polymer block mainly composed of aromatic alkenyl compound units having continuous aromatic alkenyl compound units.
The "aromatic alkenyl compound unit" refers to a repeating unit derived from an aromatic alkenyl compound. Examples of the "aromatic alkenyl compound" include: styrene, t-butylstyrene, α -methylstyrene, p-ethylstyrene, divinylbenzene, 1-diphenylethylene, vinylnaphthalene, vinylanthracene, N-diethylp-aminoethylstyrene, vinylpyridine and the like. Among them, the "aromatic alkenyl compound unit" is preferably a styrene unit from the viewpoint that raw materials are easily industrially available.
The "polymer block A" must have a structure in which an aromatic alkenyl compound unit is a main repeating unit. Specifically, the content of the aromatic alkenyl compound unit in the polymer block a is 80% by weight or more. By increasing the content of the aromatic alkenyl compound unit to 80 wt% or more, the thermoplastic property of the adhesive composition can be improved, and the adhesive composition can be reused more easily. As the repeating unit other than the aromatic alkenyl compound unit which may be contained in an amount within a range of less than 20% by weight, a repeating unit derived from a compound copolymerizable with the aromatic alkenyl compound, for example, a repeating unit derived from a conjugated diene compound or a (meth) acrylate compound, may be cited. Among them, 1, 3-butadiene and isoprene are preferable because they have high copolymerizability with the aromatic alkenyl compound.
< Polymer Block B >
As described above, the "polymer block B" is an aromatic alkenyl-conjugated diene copolymer block containing a conjugated diene unit and an aromatic alkenyl compound unit at random, and the content (St (B)) of the aromatic alkenyl compound unit is 10 to 35% by weight.
The "conjugated diene compound unit" constituting the "polymer block B" refers to a repeating unit derived from a conjugated diene compound. Examples of the "conjugated diene compound" include: 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-octadiene, 1, 3-hexadiene, 1, 3-cyclohexadiene, 4, 5-diethyl-1, 3-octadiene, 3-butyl-1, 3-octadiene, myrcene, chloroprene and the like. Among them, the "conjugated diene compound unit" is preferably at least 1 repeating unit selected from a 1, 3-butadiene unit and an isoprene unit, for the reason that polymerization reactivity is high and raw materials are easily industrially available.
The "polymer block B" must have a structure in which a conjugated diene compound unit is a main repeating unit. In order to exhibit the effects of the present invention, the content of the conjugated diene compound unit is preferably within a range of 65 to 90% by weight.
In order to obtain the effects of the present invention, the content of the aromatic alkenyl compound unit (St (B)) in the "polymer block B" must be in the range of 10 to 35% by weight, preferably in the range of 13 to 33% by weight, and more preferably in the range of 16 to 30% by weight. When the content of the aromatic alkenyl compound unit is less than 10% by weight, the developability may be deteriorated (weight く), and the workability may be poor. On the other hand, when the content of the aromatic alkenyl compound unit exceeds 35% by weight, the flexibility of the adhesive composition may be deteriorated, and a sufficient adhesive force may not be secured, which is important for the surface protective film.
The "polymer block B" may contain repeating units other than the conjugated diene compound unit and the aromatic alkenyl compound unit within a range not to impair the effects of the present invention.
In order to obtain the effects of the present invention, the ethylenic bond content in the "polymer block B" is preferably in the range of 50 to 90%, more preferably in the range of 60 to 80%. In addition, when the content of the ethylenic bond is 50% or more, the following advantages are obtained: an adhesive composition having an excellent balance of tack (tack) and adhesion can be constructed.
< copolymer (I) >
The "copolymer (I)" is a copolymer comprising the following polymer block A and the following polymer block B and having a structure represented by the general formula [ A-B ] n (wherein A represents the polymer block A, B represents the polymer block B, and n represents an integer of 1 to 3).
As the "structure represented by the formula [ A-B ] n", for example, structures represented by A-B, A-B-A-B and A-B-A-B-A-B can be mentioned, as represented by "n" representing an integer of 1 to 3. In these block copolymers, the repeating units of A and B may be the same or different.
In order to reliably exert the effect of the polymer block B, in the structure represented by [ A-B ] n, the polymer block B at the end preferably accounts for 2% by weight or more of the whole copolymer. Even if the partial copolymer (I) has a structure of-A at the terminal, the same effect as that of the copolymer having a polymer block B at the terminal can be exhibited if the content of the polymer block A at the terminal is less than 2% by weight based on the whole copolymer (I). That is, the structure may be considered to be a structure having a polymer block B at the end.
n is an integer of 1 to 3. When n is in this range, good industrial productivity can be obtained. In order to improve the adhesion and the material strength, n is more preferably 1 to 2, and particularly preferably 1. That is, the "copolymer having a structure represented by the general formula [ A-B ] n" is particularly preferably a block copolymer having a structure represented by the general formula A-B.
The content of the aromatic alkenyl compound unit in the copolymer (I) or the hydrogenated product thereof (polymer (I)) is preferably in the range of 30 to 50% by weight, more preferably 33 to 45% by weight. When the content of the aromatic alkenyl compound unit is within this range, an adhesive composition having both appropriate holding power and conformability to irregularities on the surface of an adherend and excellent spreadability can be formed.
The molecular weight of the polymer (i) is not particularly limited, but the weight average molecular weight is preferably 3 to 50 ten thousand, more preferably 8 to 30 ten thousand, and particularly preferably 10 to 20 ten thousand. By setting the weight average molecular weight in the range of 3 to 50 ten thousand, it is possible to realize easy industrial production of the polymer (i) and the copolymer composition comprising the polymer (i) and the copolymer (II) or a hydrogenated product thereof (polymer (II)). When the weight average molecular weight is less than 3 ten thousand, the polymer may adhere to production equipment or the like in the step of removing the solvent and drying the polymer, and the industrial production of the polymer (i) may be difficult. On the other hand, when the weight average molecular weight is 50 ten thousand or more, the hot-melt property and the solubility in a solvent are deteriorated, and the processing of the adherend may become difficult.
In order to obtain excellent heat resistance and weather resistance, it is preferable that the hydrogenated product of the copolymer (I) is a hydrogenated product obtained by hydrogenating an unsaturated bond into a saturated bond by hydrogenation, and in which the double bond derived from the conjugated diene monomer is 80% or more, preferably 90% or more, more preferably 95% or more.
The meaning of the hydrogenation ratio (hydrogenation ratio) in the present specification is as follows: using carbon tetrachloride as solvent at 270MHzlAnd (4) calculating the hydrogenation rate by using an H-NMR spectrum.
The polymer (i) may be used alone (1 type), or 2 or more types may be used in combination.
< copolymer (II) >
The "copolymer (II)" is a copolymer comprising the following polymer block A and the following polymer block B and having a structure represented by the general formula A-B-A (wherein the symbols have the same meanings as those in the above formula) or the general formula (A-B) x-Y (wherein x represents an integer of 2 or more, Y represents a coupling agent residue, and the other symbols have the same meanings as those in the above formula).
As is clear from the above general formula, the copolymer (II) has the polymer block A at all the molecular terminals.
The terminal polymer block A preferably accounts for 2% by weight or more of the whole copolymer (II). This is to surely exert the effect of the polymer block A. Even if the partial copolymer (II) has a structure of-B at the terminal, the same effect as that of the copolymer having the polymer block A at the terminal can be exhibited as long as the content of the polymer block B at the terminal is less than 2% by weight based on the whole copolymer (II). That is, the structure may be considered to be a structure having a polymer block a at the end.
In other words, the copolymer having a structure represented by the general formula (A-B) x-Y (wherein x represents an integer of 2 or more, Y represents a coupling agent residue, and the other symbols have the same meanings as above) has a structure obtained by coupling the copolymers (I) together with Y. Therefore, from an industrial point of view, when the copolymer (II) is (A-B) x-Y, the mixture of (I) and (II) can be synthesized using the same reaction vessel, and therefore, it is preferable that the copolymer (II) has a structure represented by the general formula (A-B) x-Y. When x is 3 or more, the copolymer is a so-called star polymer. In view of suppressing the occurrence of side reactions and controlling the physical properties of the copolymer when producing the copolymer, x is preferably 2 to 4.
For the same reason as for the polymer (i), the content of the aromatic alkenyl compound unit in the copolymer (II) or the hydrogenated product thereof (polymer (II)) is preferably in the range of 30 to 50% by weight, more preferably 33 to 45% by weight.
In order to obtain excellent heat resistance and weather resistance, it is preferable that the polymer (ii) is a hydrogenated product obtained by hydrogenating an unsaturated bond into a saturated bond by hydrogenation, and in which the double bond derived from the conjugated diene monomer is 80% or more, preferably 90% or more, more preferably 95% or more.
The molecular weight of the polymer (ii) is not particularly limited, but the weight average molecular weight is preferably 5 to 50 ten thousand, more preferably 5 to 30 ten thousand. By setting the weight average molecular weight in the range of 5 to 50 ten thousand, it is possible to easily carry out industrial production of the polymer (ii) and a copolymer composition comprising the polymer (i) and the polymer (ii). When the weight average molecular weight is less than 3 ten thousand, the polymer may adhere to production equipment or the like in the step of desolvating and drying the polymer, and the industrial production of the copolymer (II) or a hydrogenated product thereof becomes difficult. On the other hand, when the weight average molecular weight is 50 ten thousand or more, the heat-fusion property and the solubility in a solvent may be deteriorated, and the processing of the adherend may be difficult.
The polymer (ii) may be used alone (1 type), or 2 or more types may be used in combination.
< copolymer composition >
As described above, the adhesive composition of the present invention is an adhesive composition containing a copolymer composition containing the polymer (i) and the polymer (ii) as its constituent components. In the copolymer composition, the weight ratio of the polymer (i) to the polymer (ii) must be in the range of 90:10 to 10: 90. When the polymer (i) is contained in an amount of 10 parts by weight or more based on 100 parts by weight of the total amount of the polymer (i) and the polymer (ii), the following advantageous effects can be exhibited: the problem (float (き)) that the film is peeled off due to the separation of the adhesive layer from the surface of the adherend (the float き front り) can be effectively prevented. On the other hand, when the polymer (ii) is contained in an amount of 10 parts by weight or more based on 100 parts by weight of the total amount of the polymer (i) and the polymer (ii), the following advantageous effects can be exhibited: when the film is peeled off from the adherend surface, a defect (paste residue) that the adherend surface is contaminated by the adhesive remaining on the adherend surface can be effectively prevented.
In order to more reliably prevent the floating of the binder layer or the paste residue, the weight ratio of the polymer (i) to the polymer (ii) is preferably within a range of 50:50 to 15: 85.
In order to exert the effect of the present invention, it is necessary that the weight ratio of the total amount of the polymer block a to the total amount of the polymer block B contained in the polymer (i) and the polymer (ii) is in the range of 5:95 to 25: 75. Further, when the polymer block a is contained in an amount of 5 parts by weight or more based on 100 parts by weight of the total amount of the polymer block a and the polymer block B, the following advantageous effects can be exhibited: it is possible to impart an appropriate holding force to the formed adhesive layer. On the other hand, when the polymer block B is contained in an amount of 75 parts by weight or more based on 100 parts by weight of the total amount of the polymer block a and the polymer block B, the following advantageous effects can be exhibited: the adhesive layer thus formed exhibits good conformability to irregularities on the surface of an adherend, and can reliably protect the surface of the adherend. The weight ratio of the total amount of the polymer block A to the total amount of the polymer block B is preferably in the range of 5:95 to 25:75, more preferably in the range of 7:93 to 23:77, and particularly preferably in the range of 10:90 to 21: 79.
< surface protective film >
The surface protective film of the present invention has a base material layer and an adhesive layer formed from the adhesive composition of the present invention described above.
Preferably, the adhesive laminated layer is provided on one surface of the base material layer.
< base Material layer >
The base material layer is preferably a polyolefin base material layer.
Examples of the "polyolefin" include: low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene- α -olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, polypropylene (homopolymer, random copolymer, block copolymer), and the like.
These polyolefins may be used alone, or 2 or more of them may be used in combination. The "polyolefin" may be a polyolefin having a substituent, and a resin other than a polyolefin may be added. In addition, an end material of the polyolefin base material layer or an end material of the surface protective film generated in the process of manufacturing the surface protective film may be added.
The base material layer may be a single layer or a layer having a multilayer structure of 2 or more kinds different in composition.
The thickness of the base material layer can be appropriately adjusted according to the use of the surface protective film and the like. The thickness is preferably about 10 to 100 μm.
The outer surface (i.e., the surface opposite to the adhesive layer) of the base material layer preferably has a surface roughness Ra of 0.7 to 2.0 [ mu ] m, an average height of waviness profile irregularities of 3 [ mu ] m or more, and an average pitch of waviness profile irregularities of 350 [ mu ] m or more and 600 [ mu ] m or less.
Accordingly, even when the surface protective film of the present embodiment is laminated on the surface of the prism sheet and stored in a stacked state, the lens part (prism) of the prism sheet is not easily damaged, and therefore the surface protective film of the present embodiment is suitably used for the purpose of protecting the prism surface of the prism sheet.
In particular, it can be considered that: by setting the surface roughness of the back surface of the base material layer, the average height of the unevenness of the waviness profile, and the average pitch of the waviness profile within the above-described specific ranges, even if minute mixed-in foreign matter exists when a plurality of prism sheets to which the surface protective film is bonded are stacked and stored, the minute mixed-in foreign matter can be caused to enter the valleys of the surface waviness, and therefore, stress concentrated on the lens portions of the prism sheets can be reduced as compared with the case where the surface is smooth.
In the present specification, the "surface roughness Ra" is an "arithmetic average height" defined in JIS B0601: 2001. The average height W of the waviness profile unevenness is an average value of Wj in a pattern diagram (fig. 2) showing waviness of the surface of the polyolefin base material layer, and the average pitch AW of the waviness profile is an average value of Awj, which are respectively found by the following formula.
[ mathematical formula 1]
Average pitch AW of waviness profile
Average pitch W of waviness profile
The "average pitch of waviness profile" and "average height of waviness profile unevenness" in the present specification are "average length of profile curve factor" and "average height of profile curve factor" specified in JIS B0601:2001, respectively.
< adhesive layer >
The adhesive layer is formed from the adhesive composition of the present invention. The adhesive composition may contain, in addition to the polymer (i) and the polymer (ii), a tackifier, a styrene block reinforcing agent, a softening agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a filler, a pigment, an adhesion deterioration inhibitor, an olefin resin, a silicone polymer, a liquid acrylic copolymer, a phosphate ester compound, and other known additives as needed.
Examples of the tackifier used in the present invention include, but are not limited to, petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic/aromatic copolymers, and alicyclic copolymers, rosin resins such as benzofuran-indene resins, terpene phenol resins, and polymerized rosins, (alkyl) phenol resins, xylene resins, and hydrogenated products thereof, which are generally used for adhesives. More preferably, a thickener having a softening point of 90 to 140 ℃ is used. These tackifiers may be used alone or in combination of 2 or more. Among them, in order to improve the peeling property, weather resistance and the like, a hydrogenated thickener is more preferably used. In addition, commercially available tackifiers in the form of a blend with an olefin resin may also be used.
The tackifier in the present invention is an additive which is compatible with the conjugated diene in the aromatic alkenyl block copolymer or the soft segment obtained by hydrogenating the conjugated diene, that is, the rubber layer, and can control the adhesive force.
Wherein "compatible" refers to the following states: the complex obtained by compounding the tackifier into the copolymer composition exhibits a different tan δ peak temperature compared to the tan δ peak temperature of the copolymer composition. The "tan δ peak temperature" in the present specification means a temperature at which tan δ reaches a maximum.
The styrene-based block reinforcing agent is useful for suppressing deterioration of adhesion of the adhesive layer.
Examples of the monomer unit of the styrenic block reinforcing agent used in the present invention include: styrene compounds such as styrene, α -methylstyrene, p-chlorostyrene, chloromethylstyrene, t-butylstyrene, p-ethylstyrene, and divinylbenzene. These styrene block reinforcing agents may be used alone or in combination of 2 or more. That is, the styrene-based block reinforcing agent can be obtained by polymerizing the above-mentioned monomers. The copolymer formed from 2 or more monomers may be a block copolymer or a random copolymer. Among these, the styrene-based block reinforcing agent is preferably a polymer having a softening point of about 100 ℃ or higher, and more preferably a polymer having a softening point of 150 ℃ or higher. Specifically, styrenic block reinforcing agents such as "ENDEX 155" (softening point 155 ℃ C.) and "ENDEX 160" (softening point 160 ℃ C.) under the trade names of "ENDEX 155" (softening point 155 ℃ C.) and "ENDEX 160" (softening point 160 ℃ C.) manufactured by Eastman Chemical are preferably used.
Softeners are generally effective for improving adhesion. As the softening agent, for example, a diene-based polymer of low molecular weight, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, a paraffin-based process oil, a naphthalene-based process oil, an aromatic-based process oil, castor oil, tall oil, a natural oil, a liquid polyisobutylene resin, polybutene, or a hydrogenated product thereof, which can be generally used for the softening agent of the binder, can be used without particular limitation. These softening agents may be used alone, or 2 or more kinds may be used in combination.
The antioxidant is not particularly limited, and examples thereof include: antioxidants generally used in the art, such as phenols (monophenols, bisphenols, and polymeric phenols), sulfur compounds, and phosphorus compounds.
Examples of the light stabilizer include hindered amine compounds.
The ultraviolet absorber is not particularly limited, and examples thereof include: salicylic acids, benzophenones, benzotriazoles, cyanoacrylates, and the like.
Examples of the filler include: calcium carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide, and the like.
Examples of the adhesion deterioration inhibitor include fatty acid amides, long-chain alkyl grafts of polyethyleneimine, soybean oil-modified alkyd resins (for example, those manufactured by seikagawa chemical industries, ltd., trade name "ARAKYD 251" or the like), tall oil-modified alkyd resins (for example, those manufactured by seikagawa chemical industries, ltd., trade name "ARAKYD 6300" or the like), and the like.
The above additives may be used alone, or 2 or more of them may be used in combination.
The thickness of the adhesive layer is not particularly limited, but is usually, for example, about 0.5 to 50 μm, preferably 1 to 40 μm, and more preferably 2 to 30 μm.
In one of the preferred embodiments of the surface protective film of the present invention,
the base material layer is a polyolefin base material layer,
the adhesive composition further contains a tackifier,
when the dynamic viscoelasticity of the adhesive layer is measured at-50 to 80 ℃, the temperature at which tan δ is maximized is-10 to 20 ℃.
Among them, as the thickener, the above-mentioned materials and the like can be used.
The amount of the thickener is preferably an amount that can prevent the occurrence of paste residue when the surface protective film is peeled from the adherend. For example, when used as a surface protective film for a prism sheet, the tackifier is preferably added in an amount of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the rubber-based resin component [ the polymer (i) and the polymer (ii) (hereinafter, they are also collectively referred to as an aromatic alkenyl block copolymer) ].
When the dynamic viscoelasticity of the adhesive layer is measured at-50 ℃ to 80 ℃, the peak temperature of tan delta is preferably in the range of-10 ℃ to 20 ℃. The tan δ peak temperature can be adjusted to a desired range by adjusting the rubber-based resin component in the adhesive layer, for example, the range of the content of the aromatic alkenyl compound unit in the random block of the aromatic alkenyl block copolymer, the blending ratio of the tackifier, or the like, or by selecting the tackifier to be used in consideration of the softening temperature or the like.
Here, tan δ is a loss tangent (= loss modulus/storage modulus) in a dynamic viscoelasticity spectrum measured under the following conditions in a measurement temperature range of-50 ℃ to 80 ℃.
A viscoelastic spectrometer: trade name "DVA-200" (manufactured by IT measurement and control Co., Ltd.)
Sample size of adhesive layer: about 1.5mm by 5mm by 10mm in thickness
Setting a temperature rise speed: 6 ℃/min
Measuring frequency: 10Hz
Measurement mode: shearing
When the tan δ peak temperature measured as described above is within this range, the cohesive force of the adhesive layer can be improved by the action of the thickener. Thus, even when the roll is formed by bonding the adhesive layer to the back surface of the base material layer of the surface protective film, the surface protective film can be easily peeled off from the back surface of the base material layer. That is, the roll body can be smoothly unwound. Further, even when the adhesive is applied to an adherend having irregularities on the surface, the adhesive can follow the irregularities, and the surface of the adherend can be reliably protected.
In another preferred embodiment of the surface protective film of the present invention,
the base material layer is a polyolefin base material layer,
the adhesive composition further contains a tackifier and a styrene block reinforcing agent, and the weight of the aromatic alkenyl compound unit in the polymer (i), the polymer (ii) and the styrene block reinforcing agent accounts for 20 to 50 wt% of the weight of the adhesive layer (the content of the aromatic alkenyl compound unit). When the ratio is less than 20% by weight, the adhesive force tends to increase rapidly with time, and when the ratio exceeds 50% by weight, a high adhesive force may not be obtained.
Among them, the above-mentioned substances and the like can be used as the thickener.
The amount of the thickener is preferably an amount that can prevent the occurrence of paste residue when the surface protective film is peeled from the adherend. For example, the content of the tackifier is preferably about 5 to 50 parts by weight, more preferably about 10 to 40 parts by weight, based on 100 parts by weight of the rubber-based resin component (aromatic alkenyl block copolymer).
In addition, as the styrene-based block reinforcing agent, those listed above and the like can be used.
For example, the amount of styrene-based block reinforcing agent is preferably about 40 parts by weight or less, more preferably about 30 parts by weight or less, based on 100 parts by weight of the aromatic alkenyl block copolymer. The amount to be added may be more than 0 part by weight, but is preferably 1 part by weight or more.
By using the styrene-based block reinforcing agent, compatibility with the styrene (St) phase in the styrene-based copolymer block can be achieved, and the cohesive force of the adhesive layer can be improved. This makes it possible to easily peel the bonded surface protective film from the back surface of the polyolefin base material layer, and smoothly unwind the wound body. Further, it is possible to prevent paste residue from occurring when the surface protective film is peeled from the adherend, and to realize peeling with a small force.
In the surface protective film of the present invention, the storage modulus G' of the adhesive layer at 70 ℃ is preferably 4.5X 105Pa～6.0×105Pa。
By making the storage modulus G' 4.5X 105Pa or more, which can suppress the deterioration of undesirable adhesion even under a high-temperature environment; on the other hand, by making the storage modulus G' 6.0X 105And a proper adhesive force can be obtained when Pa is less than.
In order to adjust the storage modulus G' of the adhesive, the content of the aromatic alkenyl compound unit in the adhesive layer in the surface protective film of the present invention may be adjusted so that the cohesive force of the aromatic alkenyl block copolymer is within an appropriate range. The content ratio can be adjusted by the following method: an aromatic alkenyl block copolymer having an appropriate content ratio derived from an aromatic alkenyl monomer component is used; and/or, a styrene block reinforcing agent is added to the adhesive layer. The styrene-based block reinforcing agent is an additive for reinforcing island phases of a sea-island structure formed by the aromatic alkenyl block copolymer, and has a property of being compatible with a domain formed by the aromatic alkenyl block copolymer.
The amount of the styrene-based block reinforcing agent used is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the aromatic alkenyl block copolymer. If the amount is too large, the adhesion is insufficient, and the flowability may deteriorate during extrusion molding. The lower limit of the amount used is not particularly limited, but when the content of the aromatic alkenyl compound unit does not need to be adjusted as described above, the styrene-based block reinforcing agent does not need to be added, but it is preferably added in an amount of 1 part by weight or more.
In another preferred embodiment of the surface protective film of the present invention, which is used for protecting the surface of the prism sheet, the surface protective film is attached to the prism surface, and the surface protective film is loaded at 0.3N/cm in a gas atmosphere at 70 ℃2The depth of the prism apex angle of the prism surface into the adhesive is 1% or more and less than 40% of the thickness of the adhesive layer when the load of (2) is applied for 24 hours.
The depth of the plunge can be determined by the following method.
A2 kg press-fit rubber roller was used to attach the surface protection film to be measured to the surface of the prism sheet at a speed of 300 mm/min in an environment of room temperature 23 ℃ and a relative humidity of 50%. As the prism sheet, a prism sheet having a prism center distance of 50 μm and a height of 25 μm was used. Then, the prism sheet having the surface protective film attached thereto was sandwiched by polycarbonate plates (thickness: 2mm), and 0.3N/cm was applied2Under a pressure of (3), and left to stand in an atmosphere of 70 ℃ for 24 hours in this state. Next, the surface protective film was peeled at a peeling angle of 180 degrees, and the surface of the adhesive layer was observed with a laser microscope, and the depth of the apex angle of the lens portion (prism) of the prism sheet into the adhesive layer was measured.
By making the depth of the indentation to be 1% or more and less than 40% of the thickness of the adhesive layer, deterioration of adhesion in a high-temperature (e.g., 70 ℃) environment can be suppressed without adversely affecting the adhesive properties such as adhesion.
For example, the depth of the indentation may be 1% or more and less than 40% of the thickness of the adhesive layer by controlling the storage modulus G' of the adhesive layer at 70 ℃ to be within the above-described preferred range.
In another preferred embodiment of the surface protective film according to the present invention, the surface protective film is used for protecting a prism surface of a prism sheet, wherein when the surface protective film is bonded to the prism surface and a projection having a diameter of 400 μm and a height of 12 μm is pressed on a surface opposite to the prism surface side, a depth of depression of a prism apex angle of the prism surface into the adhesive layer is 1% or more and less than 100% of a thickness of the adhesive layer.
Wherein, the preferable conditions for pressing the convex objects are as follows: in a gas atmosphere of 50 ℃ at a concentration of 0.8N/cm2Pressure was applied for 24 hours.
Even when the diameter of the projection is 400 μm or less and the height is 12 μm or less, the upper limit of the depression depth is also predicted to be less than 100% of the thickness of the adhesive layer.
Therefore, when the surface protective film of the present invention is bonded to a prism sheet, another surface protective film is bonded to a smooth sheet surface, and, for example, several tens of prism sheets are stacked and stored, even if projections such as FE and foreign matter are present on the surface protective film on the smooth sheet surface, the content of the aromatic alkenyl compound unit in the adhesive of the surface protective film is set to an appropriate amount, so that the adhesive layer can be hardened, and excessive sinking of the lens portion of the prism sheet into the adhesive of the surface protective film can be reliably suppressed. Thus, the lens surface (prism surface) of the prism sheet is less likely to be damaged.
The depth of entrapment is 1% or more and less than 100% of the thickness of the adhesive layer by controlling the content of the aromatic alkenyl compound unit in the aromatic alkenyl block copolymer to 30 to 50% by weight. If the content is less than 30 wt%, the cohesive force of the adhesive is low, and thus the depth of penetration of the prism lens into the adhesive layer may not be suppressed. On the other hand, if the content exceeds 50 wt%, the cohesive force of the adhesive is too high, and thus the prism lens is less likely to be trapped in the adhesive layer, and the adhesive force is too low, and the prism lens cannot be used as a protective film.
The lens portion of the prism sheet using the surface protective film of the present invention has a prism shape substantially composed of triangular prisms. In the present specification, a surface of the lens portion having such a prism shape is referred to as a prism surface. More specifically, as shown in fig. 2, the prism sheet 1 has the following structure: a plurality of triangular prism-shaped lens portions 3 are integrated on one surface of the flat sheet 2. The lens portion 3 has a substantially triangular prism shape. The plurality of lens portions 3 are closely connected and arranged in parallel so that the respective ridge lines of the triangular prism are parallel to each other. The outer surface of the prism-shaped lens portion 3 is protected by the surface protective film of the present invention.
For example, as shown in the cross-sectional view of fig. 3, a 1 st surface protective film 4 (surface protective film of the present invention) is bonded to a portion of the prism sheet 1 where the lens portion 3 is provided. The 1 st surface protection film 4 has a base material layer 5 and an adhesive layer 6 provided on one surface of the base material layer 5, and is bonded to the prism sheet 1 from the side of the adhesive layer 6 on which the plurality of lens portions 3 are provided. Therefore, the surface protective film of the present invention is in contact with the plurality of top portions 3a of the lens portion 3 having a triangular prism shape at the time of bonding. The triangular prism-shaped lens portion 3 has a triangular cross-sectional shape, but the triangular shape is preferably an isosceles triangle having a base side fixed to the sheet.
On the other hand, the 2 nd surface protection film 7 may be bonded as necessary to the flat surface of the prism sheet 1 on the side opposite to the side on which the lens portions 3 are provided. If there are projections such as Fish Eyes (FE) or foreign matter mixed in the surface protective film 7, the top of the lens portion may be broken.
The side surface in the prism shape of the triangular prism means 3 side surfaces of the triangular prism extending in the longitudinal direction.
In a preferred prism sheet using the surface protective film of the present invention, the distance between adjacent prisms, that is, the pitch between prisms, is preferably about 10 to 1000 μm, and more preferably 10 to 500 μm among a plurality of prisms in a triangular prism, but an adherend using the surface protective film of the present invention is not limited thereto.
< production method >
The binder composition of the present invention is prepared by the following method: for example, the binder composition of the present invention can be produced by synthesizing the copolymer (I) and the copolymer (II) by block polymerization, mixing them at a specific mass ratio, and then, if necessary, hydrogenating them to obtain the copolymer (I) or the hydrogenated product thereof and the copolymer (II) or the hydrogenated product thereof, and mixing additives to be blended by a conventional method, if necessary.
As the hydrogenation catalyst, a compound containing any of the metals of groups Ib, IVb, Vb, VIb, VIIb, VIII of the periodic Table of the elements can be used. For example, compounds containing atoms of Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, Pt are exemplified, and more specifically: metallocene compounds such as Ti, Zr, Hf, Co, Ni, Rh, Ru and the like, and supported heterogeneous catalysts in which metals such as pd, Ni, Pt, Rh, Ru and the like are supported on a carrier such as carbon, silica, alumina, diatomaceous earth, basic activated carbon and the like.
Specific examples of the metallocene-based compound include: a Kaminsky catalyst having 2 cyclopentadienyl rings (Cp rings) or a ligand in which hydrogen on the Cp rings is substituted with an alkyl group, an ansa-type (ansa-type) metallocene catalyst, a non-bridged half-metallocene catalyst, a bridged half-metallocene catalyst, or the like.
Specific examples thereof include: catalysts described in Japanese patent laid-open Nos. H1-275605, 5-271326, 5-271325, 5-222115, 11-292924, 2000-37632, 59-133203, 63-5401, 62-218403, 7-90017, 43-19960 and 47-40473. The above-mentioned catalysts may be used alone in 1 kind, or 2 or more kinds may be used in combination.
As another method for producing the adhesive composition of the present invention, in the case where the copolymer (II) has a structure represented by the above general formula (A-B) x-Y (wherein the symbols have the same meanings as above), the adhesive composition of the present invention can also be produced by the following method (coupling method). Since the coupling method enables one-pot synthesis of the copolymer (I) or its hydrogenated product (polymer (I)) and the copolymer (II) or its hydrogenated product (polymer (II)), the production process is simple and the production cost is low, and the ratio of the polymer (I) to the polymer (II) can be controlled by the kind and amount of the coupling agent, and from these viewpoints, the coupling method is preferably used.
The coupling method comprises the following steps:
step 1: a step of synthesizing a copolymer having an [ A-B ] structure by block polymerization;
step 2: using coupling agents Y-Zx(wherein "Y" represents a coupling agent residue, "Z" represents a leaving group, "X" represents an integer of 2 or more.) the above-mentioned compound has the formula [ A-B ]]A part of the copolymer of the structure is coupled to synthesize a copolymer having { [ A-B ]]x-Y } structure;
when obtaining the hydrogenation product, the method also comprises
Step 3: by reacting the above-mentioned compound having [ A-B ]]A copolymer having the structure and the above { [ A-B ]]xA step of hydrogenating the copolymer of the structure-Y to obtain a copolymer composition comprising the copolymer (I) and the copolymer (II) which have been hydrogenated, respectively.
Examples of the "coupling agent" include: halides such as methyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, tin tetrachloride, butyltin trichloride, germanium tetrachloride, and bis (trichlorosilyl) ethane; epoxy compounds such as epoxidized soybean oil; carbonyl compounds such as diethyl adipate, dimethyl terephthalate, and diethyl terephthalate; polyvinyl compounds such as divinylbenzene; a polyisocyanate; and so on. Among them, methyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, and tetrachlorosilane are preferable for reasons of easy industrial availability and high reactivity.
The surface protective film of the present invention can be produced by the following method: for example, a method in which after a base material sheet (base material layer) is produced by extrusion molding, a melt of the above binder composition or a solution in which the above binder composition is dissolved is applied or sprayed onto the base material sheet; or a method of bonding a base material sheet obtained by blow molding to an adhesive sheet; or a method of co-extruding the base material and the adhesive composition by using a T-die having a multi-layer manifold. Among them, the method for producing the surface protective film of the present invention by coextrusion is preferable because a multilayer sheet in which the base material layer and the adhesive layer are adhered to each other can be obtained. It is to be noted that a melt of the binder composition of the present invention or a solution in which the binder composition of the present invention is dissolved also falls within the scope of the binder composition of the present invention.
< application >
The surface protective film of the present invention is applicable to adherends having irregularities, such as optical sheets, prism sheets, and diffusion films, but is not limited thereto, and can also be applied to surface protection of a sheet having a smooth surface, for example.
The material constituting the sheet to be used as an adherend is not particularly limited, and examples thereof include a resin having light transmittance, such as an acrylic resin and polycarbonate.
Examples
The surface protective film of the present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
(Synthesis example of copolymer composition)
Polymer Block A
Into a reaction vessel purged with nitrogen, 500 parts by mass of dehydrated and degassed cyclohexane, 20 parts by mass of styrene and 5 parts by mass of tetrahydrofuran were charged, and 0.13 part by mass of n-butyllithium was added at a polymerization initiation temperature of 40 ℃ to conduct polymerization at elevated temperature.
Polymer block B
After the polymerization conversion of the polymer A reached substantially 100%, the reaction liquid was cooled to 15 ℃ and then 70 parts by mass of 1, 3-butadiene and 10 parts by mass of styrene were added to continue the polymerization at elevated temperature.
After the polymerization conversion rate substantially reached 100%, 0.06 part by mass of methyldichlorosilane as a coupling agent was added to carry out a coupling reaction. After the coupling reaction was completed, the reaction mixture was left standing for 10 minutes while supplying hydrogen gas at a pressure of 0.4MPa (gauge pressure). The partially withdrawn polymer had a vinyl content of 64%, a weight average molecular weight of about 11 ten thousand, and a coupling ratio of 60%.
Then, 0.03 part by mass of diethylaluminum chloride and 0.06 part by mass of biscyclopentadienylfurfuryloxytitanium chloride were added to the reaction vessel, and stirring was performed. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7MPa (gauge pressure) and a reaction temperature of 80 ℃, and at the time of completion of hydrogen absorption, the reaction solution was returned to normal temperature and normal pressure and discharged from the reaction vessel, thereby obtaining a copolymer composition composed of the polymer (i) and the polymer (ii) (synthesis example 1 in table 1).
The same procedure was followed to obtain desired copolymer compositions (synthetic examples 2 to 24 in Table 1). The properties of these copolymer compositions are shown in table 1.
In table 1, "St (a + B)", "St (a)", and "St (B)" represent numerical values defined as follows. In the following definitions, the "total polymer" represents the entirety of the polymer (i) and the polymer (ii).
"St (A + B)" represents the content of the aromatic alkenyl compound unit in the whole polymer and is a value represented by the following formula. Note that "St (a + B)" is equal to the sum of "St (B)" described below and "St (a)" described below.
Formula (II):
st (a + B) = (weight of aromatic alkenyl compound unit in total polymer)/(weight of total monomer unit in total polymer) × 100 (wt%)
"St (B)" represents a numerical value represented by the following formula.
Formula (II):
st (B) = (weight of aromatic alkenyl compound unit in total polymer block B)/(weight of total monomer unit in total polymer) × 100 (wt%)
"St (A)" represents a numerical value represented by the following formula.
Formula (II):
st (a) = (weight of aromatic alkenyl compound unit in total polymer block a)/(weight of total monomer unit in total polymer) × 100 (wt%)
"St (B)" represents the content of the aromatic alkenyl compound unit in the polymer block B and is a value represented by the following formula.
Formula (II):
st (B) = (weight of aromatic alkenyl compound unit in total polymer block B)/(weight of total monomer unit in total polymer block B) × 100 (weight%)
Further, "A: B" in Table 1 represents the weight ratio of the total amount of the polymer block A to the total amount of the polymer block B.
Further, "(i): (ii)" in Table 1 represents the weight ratio of the polymer (i) to the polymer (ii).
In addition, "conjugated diene content" in table 1 represents the content of conjugated diene units in the polymer block B.
In addition, "ethylenic bond content" in table 1 represents the content of ethylenic bonds in the polymer block B.
(examples 1 to 8 and comparative examples 1 to 7)
To 100 parts by weight of each copolymer composition (Table 2) obtained by each of the above-mentioned synthesis methods, 30 parts by weight of Alcon P100 (manufactured by Mitsukawa chemical Co., Ltd.) as a tackifier and 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant were mixed to obtain each adhesive composition. The composition is shown in table 2 below.
The base material and each adhesive composition were co-extruded by a T-die method using polypropylene (J715M manufactured by Prime Polymer corporation) as the base material, to obtain a roll formed with the surface protective films of examples 1 to 8 and comparative examples 1 to 7, in which the base material layer having a thickness of 34 μm and the adhesive layer having a thickness of 6 μm were laminated and integrated, and wound on a paper core having an inner diameter of 3 inches.
(evaluation)
The surface protective films obtained by the above methods were evaluated for the following items. The results are shown in Table 3.
(1) Film forming property
The appearance of each surface protective film formed by the above coextrusion was evaluated by visual observation, and the case where there was no problem in appearance was marked as "o".
(2) Initial adhesion
The surface protective films are bonded to the lens surface of the prism sheet having the irregularities, and the lens surface of the prism sheet is covered with the surface protective films. As the prism sheet, a sheet made of an acrylic resin having a thickness of 130 μm, a prism pitch of 50 μm, and a height of 25 μm was prepared. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively, and left for 30 minutes in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237. The peeling direction in this case is the ridge line direction of the prism. The peel strength thus measured was used as the initial adhesion.
(3) Adhesion with time
Each surface protective film was attached to the surface of the prism sheet used for the initial adhesion evaluation in (2) using a 2kg pressure rubber roller at a speed of 300 mm/min in an environment of room temperature 23 ℃ and a relative humidity of 50%. Then, the prism sheet having the surface protective film bonded thereto was sandwiched between polycarbonate plates (thickness: 2mm), and 6.0X 10 was applied-3MPa, and left in an environment of 60 ℃ and a relative humidity of 90% for 48 hours in this state. The sheet was taken out to room temperature and left to stand for 30 minutes, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237.
The peel strength thus measured was used as the temporal adhesion, and the rate of change of the temporal adhesion with respect to the initial adhesion (adhesion deterioration rate) was calculated from the following equation.
Rate of change (deterioration rate of adhesion) = (adhesion with time/initial adhesion) × 100
(4) Spreading force
The wound bodies of 50mm width of each surface protection film of examples and comparative examples were unwound, and the unwinding force was measured at an unwinding speed of 15 m/min based on JIS Z0237 standard, except that the unwinding speed was changed, and was used as the unwinding force.
[ Table 3]
< decision criteria >
Adhesion (initial stage)
O (good): 0.1N/25mm or more
X (bad): less than 0.1N/25mm
Adhesion (rate of change)
Excellent: less than 200 percent
O (good): 200% to 500% inclusive
X (bad): over 500 percent
Spreading force
Excellent: less than 2.0N/50mm
O (good): 2.0N/50mm or more and 3.5N/50mm or less
X (bad): more than 3.5N/50mm
(example 9)
An adhesive composition was obtained by mixing and kneading 18 parts by weight of Alcon P100 (manufactured by Mitsukawa chemical Co., Ltd.) as a tackifier, 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant, and 0.5 part by weight of Tinuvin326 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber with 100 parts by weight of the copolymer composition of Synthesis example 4.
A wound body was obtained by using polypropylene (J715M, manufactured by Prime Polymer) as a base material and co-extruding the base material and the adhesive composition by a T-die method, wherein a surface protection film was formed by laminating and integrating a base material layer having a thickness of 34 μm and an adhesive layer having a thickness of 6 μm, and the wound body was wound around a paper core having an inner diameter of 3 inches.
(examples 10, 11 and 13, comparative examples 8 to 10)
Adhesive compositions were mixed as shown in table 4, and a roll of a surface protective film was obtained in the same manner as in example 9.
(example 12)
A roll of a surface protective film was obtained in the same manner as in example 9, except that 40 parts by weight of Clearon P125(クリアロン P125) (manufactured by Yasuhara Chemical) as a tackifier was mixed with 100 parts by weight of the copolymer composition of synthesis example 7, and the thus-obtained adhesive composition was used.
(evaluation)
The surface protective films obtained by the above methods were evaluated for the following items.
The results are shown in Table 5.
(1) tan delta peak temperature
The viscoelastic spectrum of the adhesive layer was measured at a frequency of 10Hz and a temperature rise rate of 6 ℃/min in a range of-50 ℃ to 80 ℃ by a dynamic viscoelastic spectrum measuring apparatus (product model: DVA-200, manufactured by IT measurement and control Co., Ltd.), and the temperature at which tan delta was maximized (tan delta peak temperature) was determined.
(2) Initial adhesion
Each of the surface protective films of examples and comparative examples was attached to the lens surface of a prism sheet having irregularities, and the lens surface of the prism sheet was covered with these surface protective films. As the prism sheet, a sheet made of an acrylic resin having a thickness of 130 μm and having a prism pitch of 50 μm and a height of 30 μm was prepared. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively, and left for 30 minutes in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237 standard. The peeling direction in this case is the ridge line direction of the prism. The peel strength thus measured was used as the initial adhesion.
(3) Spreading force
A50 mm wide roll of each of the surface protective films of examples and comparative examples was unwound, and a high-speed unwinding force was measured at an unwinding speed of 20 m/min as an unwinding force in accordance with JIS Z0237 except that the unwinding speed was changed.
[ Table 4]
[ Table 5]
< decision criteria >
Initial adhesion
O (good): 0.1N/25mm or more
X (bad): less than 0.1N/25mm
Spreading force
Excellent: 2.5N/50mm or less
O (good): 3.5N/50mm or less
X (bad): more than 3.5N/50mm
(example 14)
Adhesive layer:
to 100 parts by weight of the copolymer composition of synthetic example 4, 50 parts by weight of Alcon P100 (manufactured by Mitsukawa Chemical Co., Ltd.) as a tackifier, 10 parts by weight of ENDEX155 (manufactured by Eastman Chemical Co., Ltd.) as a styrene block reinforcing agent, and 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant were mixed and kneaded, thereby obtaining an adhesive composition.
Base material layer:
a base material made of polypropylene (J715M, manufactured by Prime Polymer) and the adhesive composition obtained above were co-extruded by a T-die method, and a surface-protecting adhesive sheet obtained by laminating and integrating a polypropylene base material layer having a thickness of 34 μm and an adhesive having a thickness of 6 μm was wound around a paper core having an inner diameter of 3 inches, thereby obtaining a wound body.
(examples 15 to 19 and comparative examples 11 to 14)
A roll of a surface protective film was obtained in the same manner as in example 14, except that the adhesive composition was mixed as shown in table 6 below.
In table 6, "St/binder layer (% by weight)" represents the ratio of the total weight of all the aromatic alkenyl compound units in the copolymer composition and the styrene-based block reinforcing agent to the weight of the binder (content of the aromatic alkenyl compound unit). In addition, "St/binder layer (-TF) (wt%)" represents a ratio of the total weight of all the aromatic alkenyl units in the copolymer composition and the styrene-based block reinforcing agent to the total weight of the copolymer composition and the styrene-based block reinforcing agent.
(evaluation)
The surface protective films obtained by the above methods were evaluated for the following items. The results are shown in Table 7.
(1) tan delta peak temperature
The viscoelastic spectrum of the adhesive layer was measured at a frequency of 10Hz and a temperature rise rate of 6 ℃/min in a range of-50 ℃ to 80 ℃ by a dynamic viscoelastic spectrum measuring apparatus (product model: DVA-200, manufactured by IT measurement and control Co., Ltd.), and the temperature at which tan. delta. is maximized was determined.
(2) Initial adhesion
Each of the surface protective films of examples and comparative examples was attached to the lens surface of a prism sheet having irregularities, and the lens surface of the prism sheet was covered with these surface protective films. As the prism sheet, a sheet made of an acrylic resin having a thickness of 130 μm and having a prism pitch of 50 μm and a height of 30 μm was prepared. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively, and left for 30 minutes in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237 standard. The peeling direction in this case is the ridge line direction of the prism. The peel strength thus measured was used as the initial adhesion.
(3) Adhesion with time
Each surface protective film was attached to the surface of the prism sheet used for the initial adhesion evaluation in (2) using a 2kg pressure rubber roller at a speed of 300 mm/min in an environment of room temperature 23 ℃ and a relative humidity of 50%. Then, the prism sheet having the surface protective film bonded thereto was sandwiched between polycarbonate plates (thickness: 2mm), and 6.0X 10 was applied-3MPa, and left in an environment of 60 ℃ and a relative humidity of 90% for 48 hours in this state. The sheet was taken out to room temperature and left to stand for 30 minutes, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237.
The peel strength thus measured was used as the temporal adhesion, and the rate of change of the temporal adhesion with respect to the initial adhesion (adhesion deterioration rate) was calculated from the following equation.
Rate of change (deterioration rate of adhesion) = (adhesion with time/initial adhesion) × 100
(4) Spreading force
A50 mm wide roll of each of the surface protective films of examples and comparative examples was unwound, and a high-speed unwinding force was measured at an unwinding speed of 20 m/min as an unwinding force in accordance with JIS Z0237 except that the unwinding speed was changed.
< decision criteria >
Adhesion (initial stage)
O (good): 0.1N/25mm or more
Δ (optional): 0.05N/25mm or more and less than 0.1N/25mm
X (not): less than 0.05N/25mm
Adhesion (rate of change)
Excellent: less than 200 percent
O (good): 200% to 500% inclusive
X (bad): over 500 percent
Spreading force
O (good): 3.5N/50mm or less
X (bad): more than 3.5N/50mm
(example 20)
A surface protective film (width: 700mm) for a prism sheet was formed by coextrusion using a T die method to form a base material layer (thickness: 34 μm)/adhesive layer (thickness: 6 μm), and a roll having a roll length of 100m was obtained. As a material for forming the adhesive layer, the following materials were used: 100 parts by weight of the copolymer composition of Synthesis example 13 was mixed with 30 parts by weight of alicyclic saturated petroleum resin Alcon P125 (manufactured by Mitsukawa Chemical Co., Ltd.) having a softening point of 125 ℃ as a tackifier, 20 parts by weight of ENDEX155 (manufactured by Eastman Chemical Co., Ltd.) as a styrene block reinforcing agent, 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant, and 0.5 part by weight of Tinuvin326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an ultraviolet absorber, and kneaded by a twin-screw extruder and granulated. As a material for forming the base material layer, the following materials were used: the film was prepared by mixing 100 parts by weight of block PP and 10 parts by weight of portions trimmed at both ends of the film to adjust the winding state of the roll at the time of film formation, and then kneading the mixture by a twin-screw extruder and granulating the mixture, wherein the film contained 100 parts by weight of block polypropylene (block PP) as a base material, and further contained 100 parts by weight of a copolymer composition of synthesis example 13 as a binder, 30 parts by weight of Alcon P125 (manufactured by seikagawa Chemical corporation) as a tackifier, 20 parts by weight of ENDEX155 (manufactured by Eastman Chemical company) as a styrene-based block reinforcing agent, 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant, and 0.5 part by weight of tinuviol 326 (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber as an adhesive layer of a binder.
Examples 21 to 25
A roll of a surface protective film for a prism sheet was obtained in the same manner as in example 20, except that the amount of the tackifier and the amount of the styrene-based block reinforcing agent (also referred to simply as St-based block reinforcing agent in the present specification) were changed as shown in table 8 below.
In table 8, "St/binder (wt%)" represents the ratio of the total weight of all the aromatic alkenyl compound units in the copolymer composition and the styrene-based block reinforcing agent to the weight of the binder (content of the aromatic alkenyl compound unit).
(evaluation)
The surface protective films of examples 20 to 25 were subjected to evaluation tests for the items described in the following (1) to (4). The results are shown in Table 9.
(1) Initial adhesion
Each of the surface protective films of examples and comparative examples was attached to the lens surface of a prism sheet having irregularities, and the lens surface of the prism sheet was covered with these surface protective films. As the prism sheet, a sheet made of an acrylic resin having a thickness of 130 μm, a prism pitch of 50 μm, and a height of 30 μm was used. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively, and left for 1 hour in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237 standard. The peel strength thus measured was used as the initial adhesion.
(2) Adhesion with time
Each of the surface protective films of examples and comparative examples was bonded to the surface of the prism sheet used for (1) the evaluation of initial adhesion at a speed of 300 mm/min using a 2kg pressure-sensitive rubber roller in an environment of room temperature 23 ℃ and a relative humidity of 50%, respectively. Then, the prism sheet having the surface protective film bonded thereto was sandwiched between polycarbonate plates (thickness: 2mm), and applied at 0.3N/cm2And left in this state at 70 ℃ for 24 hours. Subsequently, the sheet was left standing at room temperature of 23 ℃ and a relative humidity of 50% for 1 hour, and then the 180-degree peel strength in a width of 25mm was measured at a rate of 300 mm/min based on JIS Z0237. The peel strength thus measured was used as the temporal adhesion, and the rate of change of the temporal adhesion with respect to the initial adhesion (adhesion deterioration rate) was calculated from the following equation.
Rate of change (deterioration rate of adhesion) = (adhesion with time/initial adhesion) × 100
(3) Storage modulus G'
The storage modulus of the adhesive layer was measured at a frequency of 1Hz and a temperature rise rate of 3 ℃/min in a range of-50 ℃ to +150 ℃ by a dynamic viscoelasticity spectrum measuring apparatus (model number: DVA-200, manufactured by IT measurement and control Co., Ltd.), and the storage modulus G' at 70 ℃ was determined.
(4) Amount of trapping
The surface protective film was attached to the surface of the prism sheet at a speed of 300 mm/min using 2kg of a pressure rubber roller in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively. As the prism sheet, a sheet having a prism pitch of 50 μm and a height of 30 μm was used. Then, the prism sheet having the surface protective film bonded thereto was sandwiched between polycarbonate plates (thickness: 2mm), and applied at 0.3N/cm2And left to stand in this state at an atmosphere of 70 ℃ for 24 hours. Then, the surface protective film was peeled off at a peel angle of 180 degrees, and the surface of the adhesive layer was observed with a laser microscope, and the depth of penetration of the lens portion of the prism sheet into the adhesive layer was measured.
The amount of trapping was determined by the following calculation formula.
Trapping amount (%) = (depth of trapping of lens part of prism sheet in adhesive layer)/(adhesive layer thickness: 6 μm) × 100
< decision criteria >
Amount of trapping
O (excellent): more than 1% and less than 40%
Δ (good): more than 40 percent and less than 80 percent
X (bad): over 80 percent
Adhesion (rate of change)
Excellent: less than 150 percent
O (good): more than 150% and less than 300%
(example 26)
As shown in Table 10 below, 30 parts by weight of Alcon P-125 (manufactured by Mikawa chemical Co., Ltd.) as a tackifier was added to 100 parts by weight of the copolymer composition of Synthesis example 14 to obtain a binder composition.
On the other hand, a surface protective film was produced by laminating and integrating a polypropylene base material having a thickness of 40 μm and an adhesive layer having a thickness of 6 μm by co-extruding an adhesive layer formed of the adhesive composition and a base material formed of a resin composition containing 75 parts by weight of block polypropylene (block PP) and 25 parts by weight of Low Density Polyethylene (LDPE) shown in table 10 by a T-die method.
(examples 27 to 28 and comparative examples 15 to 19)
A surface protective film was produced and evaluated in the same manner as in example 25, except that the composition and thickness of the adhesive layer were changed as shown in table 10 below. Alcon P-125 was used as the whole tackifier.
Among them, comparative example 18 is poor in film-forming property.
(evaluation)
The surface protective films were subjected to the following measurements and evaluations in the following points.
1) In a gas atmosphere of 50 ℃, at a temperature of 0.8N/cm2The protrusions having a diameter of 400 μm and a height of 12 μm were pressed against the prism sheet having the surface protective film adhered thereto, and after 24 hours, the amount of the lens part of the prism sheet trapped in the adhesive,
2) Initial adhesion (to prism surface), and
3) initial adhesion (to smooth surfaces).
In addition, when the evaluation of the sinking of the lens part of the prism sheet of 1) above was performed, the following measurement and evaluation were performed in the following manner.
4) Damage to prism,
5) Adhesion force with time (prism surface)
6) Paste material residue;
the following measurements and evaluations were carried out in accordance with the following points.
7) The deployment force.
The results are shown in table 11 below.
1) Amount of trapping
The surface protective film obtained above was bonded to the lens surface of the prism sheet, and the adhesive layer surface of the surface protective film was brought into contact with the lens surface of the prism sheet, thereby producing a test piece. As the prism sheet, a prism sheet (BEF, Sumitomo 3M) was prepared in which the lens portion was made of acrylic resin, the sheet was made of polyethylene terephthalate having a thickness of 150 μ M, and the prism pitch was 50 μ M and the height was 23 μ M. At the time of bonding, 5.9 × 10 was applied from the outside of the surface protective film (i.e., the side opposite to the adhesive layer side)5The pressure of Pa was adjusted to 2 m/min. In the bonding, the bonding pressure was actually measured by PRESCALE (for ultra low pressure) manufactured by FUJIFILM business supply, ltd.
Laminating machine
The manufacturer: MCK (strain)
The model is as follows: MRK-600
Roller: heat-resistant silicone rubber roller
Roller diameter: phi 80
The obtained test piece was cut into a size of 3cm × 8cm to prepare a sample piece.
In order to prepare a projection for evaluation test, a nylon fiber having a diameter of 0.2mm was cut into a length of 11 to 13 μm with a cryomicrotome, the obtained cut piece was fixed to a glass slide, and the obtained surface protective film was bonded thereto from above with a 2kg roller, whereby the cut piece was fixed between the glass slide and the surface protective film. As a result, the formed convex shape (i.e., the protrusion) was observed with a laser microscope, and the diameter and height thereof were determined.
The diameters and heights of the convex shapes used for the evaluation are shown below.
Diameter: 400 μm
Height: 12 μm
The above glass slide with the surface protective film having a convex shape was set on a sample piece, the sample piece was brought into contact with the surface protective film having a convex shape, and a 200g weight (0.8N/cm) was placed on the glass slide2) And placed in an oven at 50 ℃ for 24 hours. After 24 hours, the sample sheet was taken out, the cross section thereof was cut, the cross section was observed by a Scanning Electron Microscope (SEM), and the depth (μm) of depression of the lens portion of the prism sheet in the adhesive layer was measured.
The trapping amount (%) was obtained from the actually measured trapping depth (. mu.m) by the following equation.
Trapping amount (%) = (depth of trapping of lens part of prism sheet in adhesive layer)/(adhesive layer thickness: 6 μm) × 100
2) Initial adhesion (prism surface)
The obtained surface protective film is bonded to the lens surface of the prism sheet, and the lens surface of the prism sheet is covered with the surface protective film. At the time of bonding, 5.9X 10 of a protective film was applied from the outside of the surface protective film in the same manner as in 1)5The pressure of Pa was adjusted at a rate of 2 m/min, and the resulting assembly was left in a room at 23 ℃ C. + -. 2 ℃ C. for 30 minutes.
Then, the 180-degree peel strength (unit is N) in a width of 25mm was measured in a direction parallel to the prism ridge line at a peel speed of 300 mm/min and 30 m/min, respectively, based on JIS Z0237, and this was used as the initial adhesion (to prism).
3) Initial adhesion (to smooth surface)
At a pressure of 5.9X 105Pa and a speed of 2 m/min, the surface protective film obtained above was bonded to a flat acrylic resin plate in the same manner as in 1), left at 23 ℃. + -. 2 ℃ for 30 minutes in a room, and then the 180-degree peel strength (in N) in a width of 25mm was measured at a peel speed of 30 m/min in accordance with JIS Z0237 standard, and the measured value was used as the initial adhesion (to a smooth surface).
4) Evaluation of prism Damage
In the test of 1), the surface protective film taken out of the oven was peeled off from the prism sheet, and the presence or absence of bright spots due to damage on the lens surface of the prism sheet was visually observed.
In table 10 below, the samples in which much damage was observed were designated as "x", the samples in which only a little damage was observed were designated as "Δ", and the samples in which no damage was observed were designated as "o".
5) Adhesion force with time (prism surface)
At a pressure of 5.9X 105The obtained surface protective film was bonded to the surface of the prism sheet used for the initial adhesion evaluation in 2) under Pa and at a speed of 2 m/min in the same manner as in 1) and left in a gas atmosphere at 60 ℃. + -. 2 ℃ for 1 week, and then the 180-degree peel strength was measured at a peel speed of 300 mm/min in a width of 25mm based on JIS Z0237 standard. The peel strength thus measured was used as an aged bond strength, and the rate of change of aged bond strength with respect to the initial bond strength (peeling speed of 300 mm/min for prism surface) (bond deterioration rate) was calculated from the following equation.
Rate of change (deterioration rate of adhesion) = (adhesive strength with time/initial adhesive strength (peeling speed 300 mm/min on prism surface)) × 100
6) Paste residue
In the test of 5), the peel strength was measured, and the presence or absence of residual paste on the lens surface of the prism sheet after peeling was visually observed. The case where paste residue was observed on the lens surface was marked as X, and the case where no paste residue was observed was marked as O. The results are shown in table 11 below.
7) Spreading force
The wound bodies of the surface protection films of examples and comparative examples, each having a width of 50mm, were unwound, and a high-speed unwinding force was measured at an unwinding speed of 20 m/min based on JIS Z0237 standard, except that the unwinding speed was changed, and this was used as the unwinding force.
[ Table 10]
< decision criteria >
Amount of trapping
O (good): more than 1% and less than 100%
X (bad): less than 1%, or 100%
Initial adhesion (to prism surface) peeling speed: 300 mm/min
O (good): 0.05N/25mm or more
X (bad): less than 0.05N/25mm
Adhesion (rate of change, to prism surface)
Excellent: less than 200 percent
O (good): 200% to 500% inclusive
X (bad): over 500 percent
Evaluation of prism Damage
O: no damage observed to the naked eye
X: damage was observed visually
Evaluation of paste residue
O: no occurrence of paste residue was observed with the naked eye
X: occurrence of paste residue was observed with naked eyes
Spreading force
O (good): 3.5N/50mm or less
X (bad): more than 3.5N/50mm
(example 29)
A surface protective film (width: 700mm) for a prism sheet was formed by coextrusion using a T die method to form a base material layer (thickness: 34 μm)/adhesive layer (thickness: 6 μm), and a roll having a roll length of 100m was obtained.
As a material for forming the adhesive layer, the following materials were used: to 100 parts by weight of the copolymer composition of Synthesis example 13 were added 30 parts by weight of alicyclic saturated petroleum resin Alcon P125 (manufactured by Mitsukawa Chemical Co., Ltd.) having a softening point of 125 ℃ as a tackifier, 10 parts by weight of ENDEX155 (manufactured by Eastman Chemical Co., Ltd.) as a styrene block reinforcing agent, 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant, and 0.5 part by weight of Tinuvin326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an ultraviolet absorber, and the mixture was kneaded by a twin-screw extruder and granulated.
As a material for forming the base material layer, the following materials were used: the film was prepared by mixing 75 parts by weight of block PP, 25 parts by weight of Low Density Polyethylene (LDPR), and 10 parts by weight of portions of both ends of the film trimmed to adjust the winding state of the roll during film formation, and then kneading the mixture by a twin-screw extruder, followed by granulation, wherein the film contained 100 parts by weight of block polypropylene (block PP) as a base material, and further contained 100 parts by weight of the copolymer composition of synthesis example 13 as a binder, 30 parts by weight of Alcon P125 (manufactured by seikagawa chemical industries) as a tackifier, 20 parts by weight of ENDEX155 (manufactured by eastman chemical) as a styrene-based block reinforcing agent, 1 part by weight of Irganox1010 (manufactured by Ciba specialty Chemicals) as an antioxidant, and 0.5 part by weight of Tinuvin326 (manufactured by Ciba specialty Chemicals) as an ultraviolet absorber as an adhesive layer.
In table 12, "St/binder (% by weight)" represents the ratio of the total weight of the aromatic alkenyl compound units in the copolymer composition and the styrene-based block reinforcing agent to the weight of the binder (content of the aromatic alkenyl compound units).
(examples 30 to 31, comparative examples 20 to 22)
A roll of a surface protective film for a prism sheet was obtained in the same manner as in example 29, except that the amount and type of the polyolefin in the base material layer, the adhesive layer, the copolymer composition, the styrene content, the amount of the tackifier, and the amount of the styrene-based block reinforcing agent (i.e., St-based block reinforcing agent) were changed as shown in table 12 below.
(evaluation)
The surface protective films of examples 29 to 31 and comparative examples 20 to 22 were subjected to evaluation tests for the items described in the following (1) to (6). The results are shown in Table 13.
(1) Surface roughness Ra
The surface roughness Ra was measured under the following measurement conditions using SURFTEST SJ-301 (manufactured by Mitsutoyo corporation).
(measurement conditions)
Measuring length: 7.2mm
λc：0.8mm
λs：2.5μm
Measuring speed: 0.5mm/s
The average height of waviness profile irregularities and the average pitch of waviness profiles were calculated from the profile (profile) measured under the measurement conditions in accordance with JIS B0601:2001 standard.
(2) Adhesive force
Each of the surface protective films of examples and comparative examples was attached to the lens surface of a prism sheet having irregularities, and the lens surface of the prism sheet was covered with these surface protective films. As the prism sheet, a sheet made of an acrylic resin having a thickness of 130 μm, a prism pitch of 50 μm, and a height of 30 μm was used. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, and left for 1 hour in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237. The peel strength thus measured was used as the adhesion.
(3) Initial deployment force
The initial deployment force was measured as follows: a50 mm-wide roll of each surface protection film was unwound, and a high-speed unwinding force was measured at an unwinding speed of 15 m/min in accordance with JIS Z0237, except that the unwinding speed was changed. The high-speed unwinding force thus measured was used as the initial unwinding force.
(4) Force of deployment over time
The unfolding force over time was determined as follows: a50 mm-wide roll of each surface protection film was aged ( -produced) in a room at 40 ℃. + -. 2 ℃ for 1 week, and then a high-speed unwinding force at an unwinding speed of 15 m/min was measured in accordance with JIS Z0237, except that the unwinding speed was changed. The high-speed unwinding force thus measured was used as an elapsed unwinding force. In the table, the case where the above-mentioned developing force with time was 3N/50mm or less was evaluated as good derivation property, and it was marked as O; the case where the developing force exceeded 3N/50mm with time was evaluated as poor exportability, and was denoted by X.
(5) Evaluation of prism Damage
The surface protective films of examples and comparative examples were bonded to the lens surface of the prism sheet having irregularities, and the lens surface of the prism sheet was covered with these surface protective films, thereby producing test pieces. As the prism sheet, the same sheet as that used for (2) evaluation of adhesion was used. In the bonding, 5.9X 10 of the adhesive is applied from the outside of the surface protective film5The pressure of Pa was adjusted to 2 m/min. The test piece was cut into a size of 3cm × 8cm to prepare a sample piece.
Further, a nylon fiber having a diameter of 0.2mm was cut into a length of 8 to 10 μm with a cryomicrotome, the cut piece was fixed to a glass slide, and the surface protective film obtained was attached to the glass slide with a 2kg roller, whereby a sample piece was fixed between the glass slide and the surface protective film, and a convex sample having a diameter of 400 μm and a height of 10 μm was prepared.
The convex sample was placed on a sample piece having a lens portion covered with a surface protective film, the convex sample was superimposed on the surface protective film covering the lens portion, a 140g weight was placed on a glass slide, and the slide was allowed to stand in an oven at 50 ℃ for 24 hours. After 24 hours, the test piece was taken out, the surface protective film was peeled off from the prism sheet, and the presence or absence of bright spots due to damage on the lens surface of the prism sheet was visually observed. In table 13 below, the samples in which much damage was observed were indicated as "poor", the samples in which only a little damage was observed were indicated as "Δ (good), and the samples in which no damage was observed were indicated as" good ".
(examples 32 to 38 and comparative examples 23 to 29)
To 100 parts by weight of the copolymer composition obtained by the above-mentioned synthesis method, 5 parts by weight of Alcon P125 (manufactured by Mitsukawa chemical Co., Ltd.) as a tackifier and 1 part by weight of Irganox1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant were mixed to obtain an adhesive composition.
A wound body was obtained by using polypropylene (J715M, manufactured by Prime Polymer) as a base material and co-extruding the base material and the adhesive composition by a T-die method, wherein a surface protection film was formed by laminating and integrating a base material layer having a thickness of 34 μm and an adhesive layer having a thickness of 6 μm, and the wound body was wound around a paper core having an inner diameter of 3 inches.
(evaluation)
The surface protective films obtained by the above methods were evaluated for the following items. The results are shown in Table 15.
(evaluation)
The surface protective films obtained by the above methods were evaluated for the following items. The results are shown in Table 15.
(1) Film forming property
The appearance of the surface protective film produced by coextrusion was visually evaluated, and the case where there was no problem in appearance was evaluated as o.
(2) Initial adhesion
Each of the surface protective films of examples and comparative examples was bonded to a lens surface of a diffusion film (DBEF, manufactured by 3M company), and the lens surface of the diffusion film was covered with the surface protective films. As the bonding conditions, bonding was performed at a speed of 300 mm/min using 2kg nip rubber rollers in an environment of 23 ℃ at room temperature and 50% relative humidity, respectively, and left for 30 minutes in this state, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237. The peeling direction at this time is the MD direction (machine direction) of the surface protective film. The peel strength thus measured was used as the initial adhesion.
(3) Adhesion with time
The surface protective films of examples and comparative examples were bonded to the surface of the diffusion film used for (1) the evaluation of initial adhesion at a speed of 300 mm/min using a 2kg nip rubber roller in an environment of 23 ℃ at room temperature and 50% relative humidity. Then, the diffusion film with the surface protective film bonded thereto was sandwiched between polycarbonate plates (thickness: 2mm), and 6.0X 10 was applied-3MPa, and left in an environment of 60 ℃ and a relative humidity of 90% for 48 hours in this state. The sheet was taken out to room temperature and left to stand for 30 minutes, and then the 180-degree peel strength in a width of 25mm was measured at a speed of 300 mm/min based on JIS Z0237.
The peel strength thus measured was used as the adhesion with time, and the adhesion deterioration rate of the adhesion with time with respect to the initial adhesion was calculated from the following equation.
Rate of change (deterioration rate of adhesion) = (adhesion with time/initial adhesion) × 100
(4) Spreading force
A50 mm wide roll of each of the surface protective films of examples and comparative examples was unwound, and the unwinding force was measured as an unwinding force at an unwinding speed of 5 m/min or 15 m/min in accordance with JIS Z0237, except that the unwinding speed was changed.
[ Table 14]
< decision criteria >
Adhesion (initial stage)
O (good): 0.05N/25mm or more and less than 0.35N/25mm
X (bad): less than 0.05N/25mm or more than 0.35N/25mm
Adhesion (rate of change)
Excellent: less than 200 percent
O (good): 200% to 500% inclusive
X (bad): over 500 percent
Spreading force
Excellent: less than 2.0N/50mm
O (good): 2.0N/50mm or more and 3.5N/50mm or less
X (bad): more than 3.5N/50mm
Industrial applicability
The adhesive composition of the present invention is suitable for an adhesive layer of a surface protective film such as a prism sheet, a diffusion film and the like.
The surface protective film of the present invention is suitable for surface protection of a prism sheet, a diffusion film, and the like.
Claims (9)
1. An adhesive composition comprising a polymer (i) and a polymer (ii), wherein,
polymer (i): a copolymer (I) containing a polymer block A and a polymer block B and having a structure represented by the general formula [ A-B ] n wherein A represents the polymer block A, B represents the polymer block B, and n represents an integer of 1 to 3,
polymer (ii): a copolymer (II) containing a polymer block A and a polymer block B and having a structure represented by the general formula A-B-A or the general formula (A-B) x-Y, wherein in the general formula A-B-A, the symbol A, B has the same meaning as above, in the general formula (A-B) x-Y, x represents an integer of 1 to 4, Y represents a coupling agent residue, and the symbol A, B has the same meaning as above,
the total content (St (A + B)) of the aromatic alkenyl compound units in the polymer (i) and the polymer (ii) is 30 to 50% by weight,
the weight ratio (A: B) of the total amount of the polymer block A to the total amount of the polymer block B contained in the polymer (i) and the polymer (ii) is in the range of 5:95 to 25:75,
wherein,
polymer block a: a polymer block mainly composed of an aromatic alkenyl compound unit having continuous aromatic alkenyl compound units,
polymer block B: an aromatic alkenyl-conjugated diene copolymer block which contains a conjugated diene unit and an aromatic alkenyl compound unit at random and has a content of the aromatic alkenyl compound unit (St (b)) of 10 to 35 wt%.
2. A surface protective film having a base material layer and an adhesive layer formed of the adhesive composition of claim 1.
3. The surface protective film according to claim 2,
the base material layer is a polyolefin base material layer,
the adhesive composition also contains a tackifier,
and, when the dynamic viscoelasticity of the adhesive layer is measured at-50 ℃ to 80 ℃, the temperature at which the tan δ is maximized is-10 ℃ to 20 ℃.
4. The surface protective film according to claim 2,
the base material layer is a polyolefin base material layer,
the adhesive composition also contains a tackifier and a styrene block reinforcing agent,
the content of the aromatic alkenyl compound unit in the polymer (i), the polymer (ii) and the styrene-based block reinforcing agent is 20 to 50 wt% based on the weight of the adhesive layer.
5. The surface protective film according to any one of claims 2 to 4, wherein the adhesive layer has a storage modulus G' at 70 ℃ of 4.5 x105Pa～6.0×105Pa。
6. The surface protective film according to claim 5, for protecting a prism face surface of a prism sheet,
bonding the surface protective film on the prism surface, and loading at 70 deg.C in gas atmosphere to obtain a film with a load of 0.3N/cm2The depth of the prism apex angle of the prism surface into the adhesive is 1% or more and less than 40% of the thickness of the adhesive layer when the load is applied for 24 hours.
7. The surface protective film according to any one of claims 2 to 4, which is used for protecting a prism surface of a prism sheet,
when the surface protection film is bonded to the prism surface and a projection having a diameter of 400 μm and a height of 12 μm is pressed on the surface opposite to the prism surface, the depth of depression of the prism apex angle of the prism surface into the adhesive layer is 1% or more and less than 100% of the thickness of the adhesive layer.
8. The surface protective film according to any one of claims 2 to 4, which is used for protecting a prism surface of a prism sheet,
the surface roughness Ra of the outer surface of the base material layer is 0.7 to 2.0 [ mu ] m, the average height of waviness profile unevenness is 3 [ mu ] m or more, and the average pitch of waviness profile is 350 [ mu ] m or more and 600 [ mu ] m or less.
9. The surface protective film according to any one of claims 2 to 4, which is used for protecting the surface of a diffusion film.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008232947 | 2008-09-11 | ||
| JP232947/08 | 2008-09-11 | ||
| JP261605/08 | 2008-10-08 | ||
| JP2008261605 | 2008-10-08 | ||
| JP301519/08 | 2008-11-26 | ||
| JP2008301519 | 2008-11-26 | ||
| JP050842/09 | 2009-03-04 | ||
| JP2009050842 | 2009-03-04 | ||
| JP128249/09 | 2009-05-27 | ||
| JP2009128249 | 2009-05-27 | ||
| PCT/JP2009/004549 WO2010029773A1 (en) | 2008-09-11 | 2009-09-11 | Surface protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102149779A CN102149779A (en) | 2011-08-10 |
| CN102149779B true CN102149779B (en) | 2013-08-14 |
Family
ID=42005037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980135434XA Active CN102149779B (en) | 2008-09-11 | 2009-09-11 | Surface protective film |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP4620806B2 (en) |
| KR (1) | KR101176811B1 (en) |
| CN (1) | CN102149779B (en) |
| TW (1) | TWI382071B (en) |
| WO (1) | WO2010029773A1 (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI382071B (en) * | 2008-09-11 | 2013-01-11 | Sekisui Chemical Co Ltd | Surface protective film |
| US8324309B2 (en) * | 2010-04-27 | 2012-12-04 | Kraton Polymers Us Llc | High melt flow block copolymers for non-woven adhesives |
| JP5753667B2 (en) * | 2010-06-16 | 2015-07-22 | 積水化学工業株式会社 | Adhesive composition and surface protective film |
| JP5623872B2 (en) * | 2010-11-08 | 2014-11-12 | 積水化学工業株式会社 | Adhesive composition and surface protective adhesive film |
| JP5719151B2 (en) * | 2010-11-19 | 2015-05-13 | 積水化学工業株式会社 | Adhesive composition and surface protective adhesive film |
| JP5879111B2 (en) * | 2011-06-15 | 2016-03-08 | 積水化学工業株式会社 | Surface protection film |
| JP2014169347A (en) * | 2011-07-07 | 2014-09-18 | Sekisui Chem Co Ltd | Adhesive composition and surface protecting adhesive sheet |
| JP2013018907A (en) * | 2011-07-13 | 2013-01-31 | Sekisui Chem Co Ltd | Adhesive composition and surface protecting film |
| JP5814036B2 (en) * | 2011-08-05 | 2015-11-17 | 日東電工株式会社 | Adhesive tape |
| JP5879110B2 (en) * | 2011-12-05 | 2016-03-08 | 積水化学工業株式会社 | Adhesive composition and surface protective film |
| WO2013094760A1 (en) * | 2011-12-22 | 2013-06-27 | 積水化学工業株式会社 | Surface protective film |
| JP6182533B2 (en) * | 2012-07-13 | 2017-08-16 | 古河電気工業株式会社 | Current collector foil, electrode structure, lithium secondary battery or electric double layer capacitor |
| JP6026255B2 (en) | 2012-12-07 | 2016-11-16 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | Adhesive composition for protective film for painted surface and method for preparing the same |
| JP5992312B2 (en) | 2012-12-07 | 2016-09-14 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | Adhesive composition for protective film for painted surface and method for preparing the same |
| JP6069004B2 (en) * | 2013-02-04 | 2017-01-25 | 旭化成株式会社 | Adhesive composition and surface protective film |
| KR102335290B1 (en) | 2014-04-11 | 2021-12-03 | 린텍 가부시키가이샤 | Base for back grind tapes, and back grind tape |
| JP6446215B2 (en) * | 2014-09-17 | 2018-12-26 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film |
| JP6416666B2 (en) * | 2015-03-11 | 2018-10-31 | 積水化学工業株式会社 | Surface protective film and prism sheet with surface protective film |
| JP6507009B2 (en) * | 2015-03-27 | 2019-04-24 | 積水化学工業株式会社 | Pressure sensitive adhesive composition, surface protective film, and prism sheet with surface protective film |
| JP6697981B2 (en) * | 2015-08-27 | 2020-05-27 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film for prism sheet |
| JP6863770B2 (en) * | 2016-02-24 | 2021-04-21 | 積水化学工業株式会社 | How to process adhesive film for half-cut processing and adherend |
| JP6628101B2 (en) * | 2016-03-03 | 2020-01-08 | 東レフィルム加工株式会社 | Laminated film |
| WO2017150430A1 (en) | 2016-03-03 | 2017-09-08 | 東レフィルム加工株式会社 | Layered film |
| JP6733358B2 (en) * | 2016-06-24 | 2020-07-29 | Jsr株式会社 | Adhesive composition and adhesive film |
| JP6808998B2 (en) * | 2016-06-24 | 2021-01-06 | Jsr株式会社 | Adhesive film |
| US20210129577A1 (en) * | 2016-12-29 | 2021-05-06 | 3M Innovative Properties Company | Decorative sheet |
| JP7238290B2 (en) * | 2018-08-03 | 2023-03-14 | 東洋紡株式会社 | laminated film. |
| JP2019048981A (en) * | 2018-10-04 | 2019-03-28 | 積水化学工業株式会社 | Surface protective film, and prism sheet with surface protective film |
| JP2019070133A (en) * | 2018-12-03 | 2019-05-09 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film |
| JP2019137867A (en) * | 2019-04-01 | 2019-08-22 | 積水化学工業株式会社 | Adhesive composition, surface protective film, and prism sheet with surface protective film |
| JP2020193348A (en) * | 2020-09-04 | 2020-12-03 | Jsr株式会社 | Composition for adhesive |
| WO2023188545A1 (en) * | 2022-03-31 | 2023-10-05 | リンテック株式会社 | Writing feeling improvement film with protection film |
| JP7323732B1 (en) * | 2022-03-31 | 2023-08-08 | リンテック株式会社 | Protective film attached Film for improving writing quality |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1942313A (en) * | 2005-01-14 | 2007-04-04 | 日绊株式会社 | Surface protective sheet |
| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058604A1 (en) * | 1998-05-13 | 1999-11-18 | Nippon Zeon Co., Ltd. | Poly(aromatic vinyl)/polyisoprene block copolymer composition, process for producing the same, and pressure-sensitive adhesive composition |
| JP2000336323A (en) * | 1999-05-26 | 2000-12-05 | Sekisui Chem Co Ltd | Surface-protection film for metal plate |
| JP4694061B2 (en) | 2001-08-02 | 2011-06-01 | 日東電工株式会社 | Surface protective sheet and manufacturing method thereof |
| EP1597331B1 (en) * | 2003-02-21 | 2006-11-15 | Kraton Polymers Research B.V. | Adhesive composition and tapes and labels derived therefrom |
| WO2007029681A1 (en) * | 2005-09-05 | 2007-03-15 | Nitto Denko Corporation | Adhesive composition, adhesive sheet, and surface protective film |
| KR101288750B1 (en) * | 2006-04-28 | 2013-07-23 | 세키스이가가쿠 고교가부시키가이샤 | Adhesive composition, method for producing the same and adhesive body |
| JP4987361B2 (en) * | 2006-06-19 | 2012-07-25 | 積水化学工業株式会社 | Surface protection film |
| JP5295533B2 (en) * | 2006-10-31 | 2013-09-18 | 日東電工株式会社 | Surface protective film and optical film with surface protective film |
| TWI382071B (en) * | 2008-09-11 | 2013-01-11 | Sekisui Chemical Co Ltd | Surface protective film |
-
2009
- 2009-09-11 TW TW098130714A patent/TWI382071B/en active
- 2009-09-11 JP JP2010528623A patent/JP4620806B2/en active Active
- 2009-09-11 KR KR1020117007076A patent/KR101176811B1/en active IP Right Grant
- 2009-09-11 WO PCT/JP2009/004549 patent/WO2010029773A1/en active Application Filing
- 2009-09-11 CN CN200980135434XA patent/CN102149779B/en active Active
-
2010
- 2010-10-27 JP JP2010240810A patent/JP5127903B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1942313A (en) * | 2005-01-14 | 2007-04-04 | 日绊株式会社 | Surface protective sheet |
| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI382071B (en) | 2013-01-11 |
| JPWO2010029773A1 (en) | 2012-02-02 |
| KR101176811B1 (en) | 2012-08-24 |
| WO2010029773A1 (en) | 2010-03-18 |
| CN102149779A (en) | 2011-08-10 |
| JP2011057992A (en) | 2011-03-24 |
| JP5127903B2 (en) | 2013-01-23 |
| JP4620806B2 (en) | 2011-01-26 |
| KR20110058856A (en) | 2011-06-01 |
| TW201016812A (en) | 2010-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102149779B (en) | Surface protective film | |
| US10519347B2 (en) | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive products | |
| CN102459485B (en) | Stretch releasable pressure-sensitive adhesives | |
| KR101690353B1 (en) | Surface protection film | |
| KR101946322B1 (en) | Laminated film | |
| KR20110010068A (en) | Adhesive tape | |
| JP6507009B2 (en) | Pressure sensitive adhesive composition, surface protective film, and prism sheet with surface protective film | |
| JP2012077244A (en) | Surface protective film | |
| JP5879111B2 (en) | Surface protection film | |
| JP2011042779A (en) | Pressure-sensitive adhesive tape | |
| JP2012117013A (en) | Adhesive composition and surface protection adhesive film | |
| JP5879110B2 (en) | Adhesive composition and surface protective film | |
| JP5753667B2 (en) | Adhesive composition and surface protective film | |
| JP7287863B2 (en) | laminated film | |
| JP6454183B2 (en) | Surface protective film and prism sheet with surface protective film | |
| JP2014208733A (en) | Surface protective film | |
| JP5534878B2 (en) | Surface protection film | |
| JP2011037956A (en) | Resin composition and surface protective film obtained from the same | |
| JP6359243B2 (en) | Surface protection film | |
| JP2011202146A (en) | Surface protective film | |
| JP2009191104A (en) | Surface protective film | |
| JP2004292578A (en) | Pressure-sensitive adhesive sheet and base material therefor | |
| JP2019137867A (en) | Adhesive composition, surface protective film, and prism sheet with surface protective film | |
| JP2016169264A (en) | Surface protective film, and prism sheet with surface protective film | |
| JP2012111047A (en) | Laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220610 Address after: Osaka, Japan Patentee after: SEKISUI CHEMICAL Co.,Ltd. Patentee after: Yinnenshi Materials Co.,Ltd. Address before: Osaka, Japan Patentee before: SEKISUI CHEMICAL Co.,Ltd. Patentee before: Czechoslovakia |