CN1215479A - 可贴合可压印的逆向反射片 - Google Patents
可贴合可压印的逆向反射片 Download PDFInfo
- Publication number
- CN1215479A CN1215479A CN97193719A CN97193719A CN1215479A CN 1215479 A CN1215479 A CN 1215479A CN 97193719 A CN97193719 A CN 97193719A CN 97193719 A CN97193719 A CN 97193719A CN 1215479 A CN1215479 A CN 1215479A
- Authority
- CN
- China
- Prior art keywords
- reflective elements
- bead
- rectroreflective sheet
- bead adhesive
- wall
- 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.)
- Pending
Links
- 239000011324 bead Substances 0.000 claims abstract description 107
- 239000010410 layer Substances 0.000 claims abstract description 82
- 238000004132 cross linking Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims description 78
- 230000001070 adhesive effect Effects 0.000 claims description 78
- 239000000126 substance Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 23
- 239000007767 bonding agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 10
- 229920005906 polyester polyol Polymers 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 229920003180 amino resin Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 description 48
- 229920002635 polyurethane Polymers 0.000 description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007639 printing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- -1 aliphatic diols Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 9
- 239000004821 Contact adhesive Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 238000007373 indentation Methods 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 229920003265 Resimene® Polymers 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 150000001541 aziridines Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- 230000002977 hyperthermial effect Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- IEJPPSMHUUQABK-UHFFFAOYSA-N 2,4-diphenyl-4h-1,3-oxazol-5-one Chemical compound O=C1OC(C=2C=CC=CC=2)=NC1C1=CC=CC=C1 IEJPPSMHUUQABK-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229960003574 milrinone Drugs 0.000 description 2
- VWUPWEAFIOQCGF-UHFFFAOYSA-N milrinone lactate Chemical compound [H+].CC(O)C([O-])=O.N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C VWUPWEAFIOQCGF-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920003946 DuPont™ Surlyn® 1706 Polymers 0.000 description 1
- 229920003345 Elvax® Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GSYWJWFOKRBGQB-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O Chemical compound N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O GSYWJWFOKRBGQB-UHFFFAOYSA-N 0.000 description 1
- 229920003298 Nucrel® Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- CSIYEPLOFBQQOZ-MYVZEITOSA-N [(3s,5s,6r,8r,9s,10r,13s,14s)-10-(deuteriomethyl)-6-hydroxy-13-methyl-17-oxo-1,2,3,4,5,6,7,8,9,11,12,14,15,16-tetradecahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@]1(C)C(=O)CC[C@H]1[C@@H]1C[C@H]2O)C[C@@H]1[C@]1(C[2H])[C@@H]2C[C@@H](OC(C)=O)CC1 CSIYEPLOFBQQOZ-MYVZEITOSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- BWHLPLXXIDYSNW-UHFFFAOYSA-N ketorolac tromethamine Chemical compound OCC(N)(CO)CO.OC(=O)C1CCN2C1=CC=C2C(=O)C1=CC=CC=C1 BWHLPLXXIDYSNW-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
- G02B5/126—Reflex reflectors including curved refracting surface
- G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/10—Registration, licensing, or like devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24628—Nonplanar uniform thickness material
- Y10T428/24736—Ornamental design or indicia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
- Y10T428/31862—Melamine-aldehyde
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
一种逆向反射片,它包括基本排列在一个单层中的逆向反射元件(13);所述逆向反射元件至少部分嵌入于其中的间隔层(15);在所述间隔层下面的镜面反射层(16);以及所述逆向反射元件至少部分嵌入于其中的小球粘合剂层(14),其中所述小球粘合剂层包括含有氨基甲酸酯基团的氨基塑料交联的聚合物,在交联前所述聚合物的玻璃化温度(Tg)小于约0℃。
Description
发明的领域
本发明涉及包括部分嵌入小球粘合剂层中的逆向反射元件的逆向反射片结构。
发明的背景
以前已有许多逆向反射片产品在市场上销售。这种逆向反射片的典型例子的特征是嵌入小球聚合物粘合剂层中和嵌入聚合物间隔层中的单层微小的逆向反射元件。间隔层的背面通常有镜面反射层和带有可剥离的保护层(即剥离衬里)的粘合剂。小球粘合剂层的表面通常带有表层膜。已知逆向反射片(如所述逆向反射片)有“嵌入”透镜片(或常称为“包封”透镜片)。嵌入透镜片的第一个例子可参见Palmquist等的美国专利2,407,680。还可参见例如美国专利3,551,025(Bingham等)、3,795,435(Schwab)、4,664,966(Bailey等)、4,530,859(Grunzinger,Jr.)、4,721,649(Belisle等)、4,725,494(Belisle等)和4,808,471(Grunzinger)。
在最终固化前在施加逆向反射元件并将其定位时,这些专利描述的某些小球粘合剂层是粘性的,而其它则是非粘性的。某些层(包括小球粘合剂层)是由交联或未交联的聚氨酯制成的。这种逆向反射片已大量销售了好几年并基本能满足用户的需要。尽管它能基本满足需要,但是由于技术的进步和由于分散制造的发展需要对逆向反射片的某些性能进行改进。例如,需要制得的逆向反射片比本领域已知的逆向反射片具有更高的贴合性(conformability)和压印能力,尤其在高速压印压力的情况下。
发明的概述
本发明提供一种可贴合(conformable)逆向反射片,它在变形时尤其在高速压印条件下不会明显开裂。具体地说,本发明提供一种逆向反射片,它包括基本排列在一个单层中的逆向反射元件;所述逆向反射元件至少部分嵌入于其中的间隔层;在所述间隔层下面的镜面反射层;以及所述逆向反射元件至少部分嵌入于其中的小球粘合剂层,其中所述小球粘合剂层包括含有氨基甲酸酯基团的氨基塑料交联的聚合物。在交联前所述聚合物的玻璃化温度(Tg)小于约0℃。
较好的是,本发明提供一种逆向反射片,它包括基本排列在一个单层中的逆向反射元件;所述逆向反射元件至少部分嵌入于其中的间隔层;在所述间隔层下面的镜面反射层;所述逆向反射元件至少部分嵌入于其中的小球粘合剂层,以及置于与逆向反射元件相反的那一小球粘合剂层表面上的热塑性表层膜;其中所述小球粘合剂层包括由聚酯多元醇和多异氰酸酯制得的氨基塑料交联的聚合物。在交联前所述聚合物的玻璃化温度(Tg)小于约0℃。较好的并且要求的是,当粘结在0.8mm厚的铝板上时,本发明逆向反射片(包括表层膜)的耐高速冲击性至少约0.69kgm。
本发明还提供一种制品,它包括支承逆向反射片的基材,其中所述逆向反射片包括基本排列在一个单层中的逆向反射元件;所述逆向反射元件至少部分嵌入于其中的间隔层;在所述间隔层下面的镜面反射层;所述逆向反射元件至少部分嵌入于其中的小球粘合剂层,以及粘合剂层;其中所述小球粘合剂层包括含有氨基甲酸酯基团的氨基塑料交联的聚合物。在交联前所述聚合物的玻璃化温度(Tg)小于约0℃。较好的是,所述粘合剂层位于与间隔层相反的镜面反射层表面上。
最后,提供一种制造逆向反射片的方法。该方法包括:将一层未固化的小球粘合剂组合物涂覆在剥离衬里上,该小球粘合剂组合物包括交联剂和含有氨基甲酸酯基团及未保护的官能团的可交联聚合物,其中所述可交联聚合物的玻璃化温度(Tg)小于约0℃;将逆向反射元件沉积在所述未固化的小球粘合剂组合物层中;加热所述未固化的小球粘合剂组合物,加热的温度和时间能有效地交联聚合物;用间隔层覆盖逆向反射元件的露出部分,使间隔层形成围绕逆向反射元件的凹形外表面;以及向间隔层的凹面(cupped surface)施加镜面反射层。
附图简述
图1是本发明带有嵌入透镜逆向反射片的牌照板的顶视图;
图2是图1牌照板的侧视图;
图3是另一个具有突出边缘的牌照板实例的剖面图;
图4是带有嵌入透镜逆向反射涂层的基材部分放大的剖面图片断。
详细描述
本发明提供一种可贴合的逆向反射片,它在变形时不会明显开裂。因此,该反射片可施加在由例如金属(如铝)或塑料制成的基材上,并随后压印成例如牌照板。这种反射片最好具有下列有利性能:(1)能承受高速压印压力而不明显开裂;(2)在变形区附近能承受变形而不会从基材明显鼓起;以及(3)在应用过程中无需加热。还可在反射片的保护表层膜下和/或保护膜之上印刷图形。尽管该反射片对压印制品特别适用,但是它也可用于非压印制品(有光滑或不规则的表面,如汽车或卡车侧面的标志)上。
业已提出了在各种条件下压印牌照板的需求。在非集中应用反射片的场所,应用设备各不相同。因此,需要能承受各种压印条件的反射片。典型的压印深度约为1.0-2.0mm,压印速度可从瞬间至约5秒钟。压印速度越快,反射片的挠性就必须越高,如本发明反射片那样可在小球粘合剂层中使用较低Tg的材料来达到该要求。
另外,压印后,通常对突出的字符上墨。随后对该结构物进行升温处理或不升温处理。升高的温度能干燥油墨并松弛字符周围的反射片。但是,如果不对结构物进行升温处理,该反射片必须不施加热量就能松弛字符周围的区域。因此,本发明小球粘合剂层形成能用于两种情况(即加热或不加热)的反射片。
本发明小球粘合剂层还形成一种反射片(包括表层膜),在0.8mm厚的铝板上它的耐高速冲击性较好至少约0.69kgm,最好至少约0.92kgm。在本文中术语耐“高速”冲击性指自由落体重物使反射片和铝板变形而该片不明显开裂所用的力的大小。通常,使用自由落体重物,在约不到1秒钟内发生变形。较好的是,在这种高速条件下产生的压印深度至少约2.0mm,最好至少约2.25mm而本发明反射片不明显开裂。
图1和2中的标号1通常表示具有逆向反射片的牌照板,它包括其上面的本发明小球粘合剂层。牌照板1一般包括其中压印字符4的基材3(例如由金属或塑料制成的基材)。通常压印字符4使之突出于(即向外凸起)牌照板1的表面5;也就是说,它们向观察者的方向突出。这可通过参照图2更好地理解。通常,常规压印牌照板带有的字符,相对于基材3的表面5,其压印总量至少约0.15-0.20cm。应注意牌照板1包括向远离观察者方向凹进(deboss)的外缘6。或者,参照图3,牌照板1’包括接近基材3’的外缘6’的突起的边框7’。突起的边框7’的压印高度可与突起的字符4’的高度相等或不相等。尽管本发明主要对于涉及凸印的字符、数字、符号、边框等的用途进行描述,但是应理解当涉及凹印的字符、数字、符号、边框等时也有类似的情况和问题。
一般来说,要求表面5的至少一部分是基本反射的,使得牌照板1即使在晚间和相当远的距离观看时也非常显眼。通常要求牌照板1具有非常强烈的逆向反射性,使之在仅有微弱的光线照射于其上时就能在很远处被看得到。另外,使用嵌入透镜结构,至少部分因为在湿润和干燥的条件下均能获得良好的反射性。
一般来说,在牌照板1的表面5上需要逆向反射片。这种反射片的常用类型是嵌入透镜逆向反射片,它可以容易地施加在或层压在表面5上,随后可将其凸印或凹印以形成所需的字符、符号、数字等。这种反射片是熟知的,并且其剖面示意图示于图4。
参照图4,它表示采用特别的小球聚合物粘合剂层14的嵌入透镜逆向反射片。反射片10的结构包括表层膜12,它通常形成于反射片的前外表面上;嵌入小球粘合剂层14(它最好是透光的)中的单层逆向反射元件13(通常是透光玻璃小球);最好是透光的间隔层15,它以与逆向反射元件背面的曲面相一致的这种方式施涂在逆向反射元件13的背面;通常真空沉积在间隔层15上的镜面反射层16;以及覆盖反射层16的粘合层17,尽管一层粘合剂可代替表层膜12覆盖在小球粘合剂层14上。还可任选地用底涂层18和19。底涂层18有助于增加对贴花纸或其它粘合剂背胶材料以及施涂于反射片表层膜12上的油墨或其它着色剂的粘性。底涂层19有助于增加表层膜12与小球粘合剂层14之间的粘性。任选的底涂层18和19也最好是透光的。在本文中,术语“透光的”是指至少能透过70%以给定波长入射于其上的光。较好的是,透光材料透过大于约80%,最好大于约90%给定波长的入射光。
入射在反射片上的光线透过层12和14以及任选的层18和19,射至逆向反射元件13上,该元件作为透镜使入射光透过间隔层15大致聚焦在适当间距的镜面反射层16上。入射至该反射层上的光线被沿与入射至反射片基本相同的光路反射出反射片。
除了特别的小球粘合剂层14以外,图4所示的结构是常规结构,其制造方法是本领域中已知的。
小球聚合物粘合剂层
对于所说明的逆向反射片,小球粘合剂层14的作用在于该层的独特特性使反射片具有改进的贴合性和压印性,尤其在高速压印压力下。它包括可贴合的和可压印的最好是透光的聚合物材料,从而向逆向反射元件(如微球或小球)提供良好的粘性。逆向反射元件在小球粘合剂层中嵌入的深度通常足以使之被牢牢地固定。但是,它们嵌入的深度不会使反射片的亮度和有角性降低。通常,逆向反射元件嵌入的深度是其直径的约30-50%。
用于制造小球粘合剂层14的聚合物材料是可交联的并可形成厚度可容易地并精确地控制的膜。所述可交联的树脂是聚氨酯。也就是说,聚合物包括氨基甲酸酯基团(-NH-C(O)-O-),尽管也存在其它基团,如脲基(-NH-C(O)-NH-)。较好的是,可交联的聚氨酯的数均分子量小于约30,000,重均分子量小于约75,000(由凝胶渗透色谱法测定)。
这种聚合物材料是玻璃化温度(Tg)约小于0℃,较好小于约-5℃,最好约为-5~-25℃的可交联聚氨酯。这种低Tg可交联聚氨酯具有足够的柔顺性以致于交联后,它具有合适的伸长率和拉伸强度,使反射片能承受高速压印压力而不会对反射片有不利影响。通常,加入逆向反射元件降低了独立(free-standing)的小球粘合剂试样(即不被基材所支承的固化的小球粘合剂层)的伸长率。这是因为每个小球都充当从中可扩展裂缝的疵点。显然,这种结果在用于本发明小球粘合剂层中的低Tg聚氨酯的情况下通常未观察到。较好的是,带有单层逆向反射元件的本发明独立小球粘合剂试样的伸长率至少约100%,较好约200-1000%。同样,显然用于本发明小球粘合剂层的低Tg聚氨酯能形成更耐冲击性的小球粘合剂层。较好的是,粘合在0.8mm厚的铝板上的本发明小球粘合剂试样的耐高速冲击性(如上所定义)至少约0.92kg·m,较好至少约1.6kg·M。
聚氨酯可以是各种由一种或多种多元醇与一种或多种多异氰酸酯结合而制成的可交联聚氨酯中的任何一种,只要交联前其Tg小于约0℃即可。在本文中,术语“可交联”指聚合物具有可与交联剂反应的官能团。较好的是,聚氨酯具有不与交联剂反应的侧接羟基,尽管其它官能团(如异氰酸酯基和羧基)可以进行交联。在本发明方法中,官能团是未保护的(即未封闭的)。
可使用各种多元醇制造聚氨酯。同样,也可使用多元醇的混合物。本文中术语“多元醇”指含有两个或多个羟基的多元醇。多元醇的羟基官能度较好为2-4(即二元醇、三元醇、四元醇)。最好的是,多元醇是二元醇,尽管更多元醇(如三元醇和四元醇)可与二元醇一起组合使用。最好的是,多元醇是二元醇或二元醇的混合物并且不使用更多元醇来制备聚氨酯。
多元醇可以是聚醚多元醇,如聚1,4-丁二醇和聚丙二醇;聚酯多元醇,如己二酸与新戊二醇或邻苯二甲酸酐与己二醇的反应产物;丙烯酸类多元醇等。较好的多元醇是聚酯多元醇。
最好的聚酯多元醇是羟基封端的下式多元醇:HO-[-R-O-C(O)-R’-C(O)-O-R-O-]n-H,其中R是具有2-10个碳原子的脂族基团,R’是具有高达14个碳原子的脂族或芳族基团,n至少为2。这种聚酯二醇通常是由一种或多种脂肪或芳香酸/酯和一种或多种脂族二醇制得的。例如,上面通式的聚酯二元醇可由芳香酸或酯(如间苯二酸或间苯二酸二甲酯,或其混合物)和二元醇(如新戊二醇、1,6-己二醇或1,4-环己烷二甲醇,或它们的混合物)制成。如果同时使用芳族化合物和脂族化合物,一般芳族化合物的重量百分数小于脂族化合物的重量百分数。
聚酯二元醇或其它合适的多元醇的羟基当量较好约90-5000,更好约200-3000,优选约250-2000。聚酯二元醇或其它合适的多元醇的酸值较好不大于约1.0,更好不大于约0.7。酸值可根据ASTM D 4662-93测定。
市售的聚酯二元醇的一个例子是购自Witco Corp.,Melrose Park,IL的FOMREZ 8056-146。据信这种树脂含有约26重量%新戊二醇、约29重量%1,6-己二醇、约33重量%己二酸/酯和约12重量%间苯二酸/酯。其它聚酯二醇是购自Witco Corp.的FOMREZ 55-112(据信含有约47重量%新戊二醇和约53%己二酸/酯)和FOMREZ 8066-120(据信含有约49重量%己二醇、约33重量%己二酸/酯和约18重量%间苯二酸/酯)以及购自Inolex Chemical Company,Philadelphia,PA的LEXOREZ,购自Ruco Polymer CorpHicksville,NY的RUCOFLEX。应理解可使用这些二元醇的掺混物或混合物来制备用于小球粘合剂层14的聚氨酯。
可使用各种三元醇来制备聚氨酯。合适的三元醇包括,但不限于聚醚三醇,如聚环氧丙烷三醇;非聚己内酯三醇的聚酯三醇和简单三元醇如三羟甲基丙烷和丙三醇及其混合物。较好的是三元醇中的羟基是伯羟基以促进生成的聚合物交联。三元醇的例子包括购自Witco Corp.的FOMREZ 1066(三羟甲基丙烷、己二醇和己二酸)、购自Union Carbide Corp.New Milford,CT的TONE 0305(聚己内酯三醇)和购自Ruco Polymer Corp的RUCOFLEX F-2311。应理解这些物质可与其它多元醇掺混或混合在一起使用,以获得约小于0℃的Tg。
四官能的或更多元醇(如季戊四醇)也是适用的多元醇。其它适用的多元醇公开在E.N.Doyle的“The Development and Use of Polyurethane Products”McGraw-Hill,1971。如果使用三元或更多元醇,则NCO∶OH的化学计量应相应地进行调节,尽管本领域的普通技术人员可理解这一点。
可使用各种多异氰酸酯制备聚氨酯。术语“多异氰酸酯”指在单个分子中具有两个或多个活性异氰酸酯基团(-NCO)的任何有机化合物,它可以是脂族的、脂环的、芳族化合物或其混合物。该定义包括二异氰酸酯、三异氰酸酯、四异氰酸酯及其混合物,较好的是,使用二异氰酸酯。这些异氰酸酯基团可连接在芳族或脂环基团上。最好使用脂族异氰酸酯(包括脂环族异氰酸酯)来改进天候老化并消除泛黄。适用的二异氰酸酯包括,但不限于选自二(4-异氰酸酯基环己基)甲烷(H12MDI,购自Bayer CorpPittsburgh,PA)、二苯基甲烷二异氰酸酯(MDI,购自Bayer CorpPittsburgh,PA)、异佛尔酮二异氰酸酯(IPDI,购自Huels America,Piscataway,NJ),甲苯2,4-二异氰酸酯(TDI,购自Aldrich Chemical CoMilwaukee,WI)、六亚甲基二异氰酸酯(HDI,购自Aldrich Chemical CoMilwaukee,WI)、间-四甲基二甲苯二异氰酸酯(TMXDI,购自Aldrich ChemicalCoMilwaukee,WI)、和1,3-亚苯基二异氰酸酯的二异氰酸酯。应注意还可使用这些二异氰酸酯的混合物。
聚氨酯反应的化学计量取决于异氰酸酯的当量和多元醇的当量的比例。对于聚氨酯较好的NCO∶OH的总比例小于1∶1,以便在形成的聚氨酯中有残余的羟基。较好的是,NCO∶OH之比约为0.8-0.99比1。最好的是,NCO∶OH之比约为0.91-0.96比1。本领域的普通技术人员可理解当使用三元醇和/或四元醇时该比例将随合成次序的不同而不同。这通常可以通过改变异氰酸酯的量来完成,以防止凝胶并获得可溶性产物。
可向多元醇和多异氰酸酯的反应混合物中加入催化剂以促进反应。使多异氰酸酯与含活性氢的化合物反应的催化剂是本领域中已知的。例如可参见Mayer等的美国专利4,495,061。较好的催化剂包括有机金属化合物和胺。有机金属化合物可以是有机锡化合物,如二月桂酸二甲基锡、二月桂酸二丁基锡和二硫醇二丁基锡。较好的催化剂是二月桂酸二丁基锡。催化剂的用量要能有效地促进反应。较好的是,按固体总重量计用量约为0.01-2重量%。更好的是,催化剂的用量约占固体量的0.01-0.03重量%。
可在溶剂的存在或不存在下制备聚合物。较好的是,在一种或多种有机溶剂的存在下进行制备。合适的溶剂的例子包括,但不限于乙酸戊酯、芳烃及其混合物、丁酮、乙酸丁氧基乙氧基乙酯、乙酸2-乙氧基乙酯、环己酮、二噁烷、4-甲基-2-戊酮、四氢呋喃、甲苯、二甲苯和/或其混合物。较好的溶剂是二甲苯、4-甲基-2-戊酮及其混合物。聚氨酯反应混合物的固体总量较好约占30-75重量%,最好约占40-55重量%。
制造聚氨酯的某些适用技术的进一步描述可参见J.H.Saunders和K.C.Frisch“Polyurethanes:Chemistry and Technology”Part Ⅱ,Interscience (New York1964),pages 8-49及其所引用的各种参考文献。可使组份多元醇与多异氰酸酯同时或分步进行反应。
小球粘合剂层包括由可交联的聚氨酯和交联剂制得的交联聚氨酯。可使用各种交联剂与本发明可交联的聚氨酯进行反应。一般来说,所需的交联剂应能容易地与聚氨酯的活性部分进行反应,所述活性部分最好是羟基,并且它将形成大量交联。交联剂至少是二官能的。较好的是,它能在较低的温度(如90-180℃)但不是室温(即25-30℃)进行反应,尽管使用在线混合时(即在制造过程中将交联剂和可交联的聚氨酯混合后立即进行涂覆)这不是必须的。因此,可制得含有可交联聚氨酯和交联剂的储存稳定的组合物,而不需要对聚氨酯的可交联部分进行保护。
而且较好的是在较短的时间(常小于约3分钟)内交联剂能与可交联的聚氨酯基本完成反应。本文中术语“完成”指聚氨酯固化至这样的状态,即较少再发生导致体积或结构变化的反应。也就是说,聚氨酯被固化至凝胶部分约大于50%,较好凝胶部分大于约80%。因此,有利并较好的是,可交联的聚氨酯包括未保护的官能团(较好是羟基),并能在较低的温度在较短的时间内通过交联而固化。
较好的是,相对于交联剂可交联的聚氨酯明显过量。通常,聚氨酯树脂与交联剂之比(按固体计)根据交联剂的不同而在约2∶1-20∶1之间变化。较好的是,聚氨酯树脂与交联剂之比约为5∶1-6.5∶1。
具有上述较好性能的交联剂包括氨基塑料树脂(即醛与胺或脲的反应产物),如脲醛树脂、蜜胺-甲醛树脂、甘脲(glycouril)-甲醛树脂;含有丙烯酰胺和甲醛的反应产物的醚化加成物的丙烯酸类共聚物;多官能氮丙啶;环氧树脂;醛;吖内酯;和/或其官能团能与可交联的聚氨酯的官能团发生反应的任何其它多官能物质。氨基塑料树脂是较好的,蜜胺-甲醛树脂是最好的。尽管本发明人不想与任何理论相联系,但是相信这些树脂能使在小球粘合剂层中的交联聚氨酯具有高的耐冲击性和耐天候老化性。市售的蜜胺-甲醛树脂的例子是至少部分丁基化的醚胺-甲醛树脂,购自Monsanto,St.Louis,MO的RESIMENE 881、RESIMENE BM5901、RESIMENE 750和RESIMENE 7512,以及购自Dutch State Mine Resins,The Netherlands的URAMEX CP 1132 MF。其它蜜胺-甲醛树脂的生产厂可参见Ullmann’s Encyclopedia of Industrial Chemistry,Fifth,Completely Revised EdVolume A2,VCH Publishers的136页表2。在本文中,术语“树脂”是指单体、低聚物和/或聚合物的混合物。
另外,可向小球粘合剂中加入防天候老化添加剂,如UV吸收剂、位阻胺光稳定剂、抗氧剂等,以改进本发明逆向反射片的总耐久性。
表层膜
表层膜12通常是耐磨的聚合物涂层,它向逆向反射片提供一层硬的耐候性的外层。表层膜12最好由基本上热塑性的并且无弹性的,最好可挤出的透光聚合物材料制成。合适的这种材料的例子包括聚乙烯,或者较好的是下列单体的一种或多种共聚物,该单体包括按重量计,主要部分的至少一种乙烯或丙烯,和次要部分的至少一种极性单体(如含氧、氮或其混合物的单体)。这种极性单体的合适例子包括丙烯酸、甲基丙烯酸、丙烯酸乙酯和乙酸乙烯酯。或者,表层膜可以由占主要重量的一种或多种这些含乙烯或丙烯的共聚物与聚乙烯和/或其它聚合物(如乙酸乙烯酯和/或甲基丙烯酸聚合物)或共聚物的共混物制成。适合于制造表层膜的聚合物材料的熔体指数通常小于约500,较好约小于150,最好约小于20。具有较低熔体指数的聚合物材料通常更容易挤出并在升温下更不易软化。
许多合适的聚合物可市售购得,包括购自Dow Chemical CoMidland,MI的PRIMACOR 3440(乙烯与9重量%丙烯酸的共聚物,熔体指数=10)以及购自E.I.DuPont de Nemours,Wilmington,DE的NUCREL 035(含20重量%甲基丙烯酸,熔体指数=35)、ELVAX 230(含28重量%乙酸乙烯酯)和SURLYN 1706(含甲基丙烯酸)。在低至-40℃的温度下这些聚合物中的每一种均具有优良的挠性、强度和韧性。
最好通过例如挤出或溶剂流延预制成表层膜12,随后用各种技术(如热层压,或用已知的表面改进处理如电晕处理进行底涂和/或施加化学底涂层等)将其粘合在小球粘合剂层14上。或者,可通过挤出或溶剂流延(尽管挤出是较好的)将表层膜12直接形成于小球粘合剂层14上。通常,表层膜约0.025-0.05mm厚,最好约0.031-0.036mm厚。
底涂层
如上所述,可例如通过电晕处理和/或施加化学底涂层对表层膜12和/或小球粘合剂层14进行底涂,以改进它们之间的粘性,即使表层和小球粘合剂层属于不同的聚合物种类。同样,可对表层膜12进行底涂,以改进油墨、其它着色剂、贴花纸、其它粘合剂背胶的材料等对逆向反射片外表面的粘性。这种底涂处理通常是本领域的普通技术人员已知的。
例如,可将氮丙啶加入作为烯烃基表层膜的内表面的聚氨酯基底涂层中,以形成与聚氨酯基小球粘合剂层良好的粘性和表面接受能力。含氮丙啶的底涂层能很好地粘合在烯烃基表层膜上并形成一种可接受的表面,而聚氨酯基小球粘合剂对这种烯烃基表面通常不能很好地粘合,从而在表层膜和小球粘合剂层之间形成所需的高的粘性。
逆向反射元件
逆向反射元件13通常是玻璃小球状的(也称之为微球或微球透镜),并最好是透光的。对本发明嵌入透镜的逆向反射片,逆向反射元件的折射率较好约2.2-2.3,最好约2.23。
一般来说,逆向反射元件的直径不超过约200微米。较好的是,逆向反射元件的直径约20-120微米,最好的直径约60-90微米。直径的范围越窄,反射片的性能越一致并且越好。平均直径的较好的尺寸分布应为±10微米。平均直径最好的尺寸分布为±7.5微米。
如本领域中已知的那样可对小球表面进行化学处理(如用有机铬化合物进行处理),以增强树脂与玻璃小球的粘性。另外,如美国专利3,222,204(Weber等)公开的那样,用含氟烃处理玻璃小球有助于获得半球状的小球下沉并获得均匀的小球下沉。
反射层
如图4所示,反射层16位于间隔层15之下。合适的下层反射方式包括厚度均匀的金属(如银、铝等)沉积层。但是,可使用Bingham的美国专利3,700,305公开的绝缘涂层代替从金属形成反射层。反射层16的厚度取决于具体使用的金属,较好约80-100nm。作为形成单独的反射层16的另一种方法,可向例如粘结层17施加镜面反射或珠光颜料。
间隔层
间隔层15通常由具有合适流变性的聚合物材料制成,以便按照逆向反射元件背面的曲面形成涂层。通常,这要求聚合物的数均分子量大于约30,000,通常大于约50,000。间隔层15较好包括交联聚合物材料,最好是尺寸稳定的交联活性聚合物与非活性的可萃取(extractable)的塑性聚合物的共混物。活性聚合物的例子包括聚乙烯醇缩乙醛、丙烯酸类共聚物、聚氨酯、聚酯、聚酰胺、聚酯-酰胺以及丙烯酸类嵌段和接枝共聚物。交联剂的例子包括与活性聚合物发生反应的至少二官能的物质,该交联剂也可包括其它交联聚合物,例如氨基塑料树脂,包括脲醛树脂、蜜胺-甲醛树脂和甘脲(glycouril)-甲醛树脂;环氧树脂;异氰酸酯;醛;多官能氮丙啶;和吖内酯。非活性的可萃取的塑性聚合物的例子包括聚酯、聚醚、聚酰胺、聚氨酯和某些烯键不饱和单体的聚合物。较好的是这种间隔层包括氨基塑料交联的树脂,如聚乙烯醇缩丁醛、丙烯酸类树脂或聚酯树脂。这些较好的间隔层的例子公开在例如Wilson等的美国专利5,262,225中。但是,应该理解也可使用其它材料作为本发明逆向反射片的间隔层。
较好的间隔层15包括掺有聚酯增塑剂用脲醛树脂交联剂交联的聚乙烯醇缩丁醛。合适的聚乙烯醇缩丁醛包括购自Monsanto,St.Louis,MO的BUTVAR B-76(乙烯醇、乙烯基缩丁醛和乙酸乙烯酯的无规共聚物)。合适的脲醛交联剂是购自Reichold Chemicals,Research Triangle Park,NC的BECKAMINE 21-510。合适的聚酯增塑剂是购自Reichold Chemicals的AROPLAZ 1351。较好的是,聚乙烯醇缩丁醛的用量约为55-70重量%,脲醛树脂的用量约为10-35重量%,聚酯增塑剂的用量约为5-20重量%。这些值是按组合物固体总重量计的固体重量百分数。
间隔层15的厚度通常取决于逆向反射元件的折射率与表层膜12的折射率之比,小球粘合剂层15和逆向反射元件13的直径。间隔层必须足够厚,以便使镜面反射层16位于透过逆向反射元件的光线的聚焦平面附近。在某些情况下,通过适当地组合使用高折射率逆向反射元件和低折射率表层膜层,可无需使用间隔层,此时镜面反射层直接施加在逆向反射元件上。但是,一般存在间隔层15,它的厚度一般约0.005-0.036mm。
粘合剂层
粘合剂层17可以是压敏粘合剂或热或溶剂活化的粘合剂。较好的是,粘合剂17是压敏粘合剂,厚度约0.01-0.06mm。该粘合剂一般是用溶液涂覆在经硅氧烷剥离涂覆的纸背衬(图4中未表示)上,干燥,随后层压在反射层16(或小球粘合剂层14)上。或者,可将粘合剂直接施涂在反射层16(或小球粘合剂层14)上,并将经剥离处理的纸背衬层压在粘合剂层17上,以形成逆向反射产品。
较好的是,所述压敏粘合剂是丙烯酸酯基(acrylic-based)粘合剂。可用于制造压敏粘合剂的丙烯酸酯类聚合物包括由极性单体和丙烯酸酯类单体聚合而成的聚合物。合适的丙烯酸酯类单体包括丙烯酸(C4-C12)烷酯单体和甲基丙烯酸(C6-C12)烷酯单体,例如,丙烯酸异辛酯、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸辛酯、甲基丙烯酸辛酯及其混合物。合适的极性单体包括酸性单体如烯键不饱和的羧酸、烯键不饱和的磺酸和烯键不饱和的磷酸。具体例子包括丙烯酸、甲基丙烯酸、衣康酸、苯乙烯磺酸、马来酸、富马酸、巴豆酸、柠康酸、丙烯酸β-羧乙基酯、甲基丙烯酸磺乙基酯及其混合物。丙烯酸酯和极性单体的重量百分数之比通常为丙烯酸单体∶极性单体约为87.5-95∶5-12.5。
最好使用交联剂对丙烯酸酯基粘合剂进行交联,所述交联剂的选择取决于所使用的单体。可通过辐照(如电子束、紫外光等)、水分或加热对丙烯酸压敏粘合剂进行交联。双酰胺交联剂是利用加热进行化学交联的热交联剂的例子。
着色剂或图形
当表层膜12、小球粘合剂层14和间隔层15是无色透明的时,用本发明方法制得的逆向反射片能将大部分入射光向其光源回射,此时反射片一般呈现银色或灰色的外观,这是由反射层16的金属外观造成的。但是,可将最好是透光的染料或颜料置于间隔层15、小球粘合剂层14、表层膜12和/或任选的底涂层18和19中而制得着色的反射片。或者,可在施加表层膜前将影像,如图形施加在小球粘合剂层14上,或它们也可施加在表层膜的主表面(即内表面或外表面)上。当影像嵌入反射片时,影像一般更耐久些。也可使用Hockert等的美国专利4,634,220和Hockert的美国专利4,688,894所公开的利用激光在反射层16中形成影像。
嵌入透镜反射片的制造方法
图1嵌入透镜结构的较好的制造方法包括如下步骤:
(1)制备含有氨基甲酸酯基团的可交联聚合物,较好是含有氨基甲酸酯基团和未保护的官能团的可交联聚合物,最好是含有羟基封端的聚氨酯用于小球粘合剂层;
(2)将一层可交联的聚合物和交联剂的混合物施涂在表面光滑的剥离衬里(如涂覆丙烯酸类的剥离衬里)上,并任选地将其加热至约45-90℃,以闪干用于制备聚氨酯的溶剂;
(3)向未固化的小球粘合剂层14施加单层逆向反射元件13;
(4)向逆向反射元件施加轻微的压力以有助于树脂的毛细管现象(capillation),并使透镜在小球粘合剂层中嵌入其直径的约30-50%,接着将其加热至约90-180℃,较好约140-175℃,对小球粘合剂层14进行热固化;
(5)用间隔层15覆盖逆向反射元件13的露出部分,该间隔层具有围绕逆向反射元件凹形的外表面;
(6)向间隔层15的凹面施加(一般用真空沉积技术)镜面反射层16;
(7)从小球粘合剂层14上除去剥离衬里;
(8)在典型的实例中,在镜面反射层16上施加粘合剂层17;
(9)任选地,对小球粘合剂表面进行电晕处理和/或施加底涂层;以及
(10)向逆向反射膜的上表面施加表层膜12。
在某些情况下需要向表层膜12的外表面施加底涂层,这种底涂层能接受施加的标记组合物(如油墨),以便将图表符号施加在逆向反射片的表面上。这种底涂层最好是透光的。它的一个例子是带有氮丙啶交联剂的水基聚氨酯。
下列实施例用于进一步说明各种具体的和较好的实例和技术。但是应理解在本发明的范围内还可对其进行各种变化和改进。
实施例
下面说明本发明小球粘合剂聚氨酯组合物的制备。除非另有说明,在全部说明书(包括实施例)中所有份、百分数和比例均是以重量计的。在本文中对于官能度或部分的术语“当量”或“Eq.Wt”指每摩尔或当量官能度的聚合物质量。
试验
比浓对数粘度:测定各组分的比浓对数粘度以相对比较分子量。采用常规方法使用Cannon-Fenske粘度计(购自Jupiter Instrument Company,Jupiter,FL)在控制在25℃的水浴中测定10ml聚合物溶液(聚合物在四氢呋喃溶剂中的浓度为0.8g/dl)的流动时间和四氢呋喃溶剂的流动时间以测定比浓对数粘度。在各次实验中,比浓对数粘度的单位为dl/g。
玻璃化温度:用差示扫描量热法测定本发明材料的玻璃化温度(Tg)。在氮气氛中将少量干膜置于Perkin-Elmer DSC-7(Norwalk,CT)差示扫描量热器的DSC室中。将试样从室温冷却至-100℃,随后以20℃/分钟的扫描速率加热至150℃,最后以40℃/分钟的速率冷却。以玻璃转化区曲线的中点作为Tg(无定形材料由玻璃态转变成延性状态的温度)。
拉伸强度和伸长率:根据ASTM试验方法D882-83(1986)试验某些涂层的拉伸强度和总伸长率。结果列于下表A。
耐冲击性:根据ASTM D2794(1986)在25℃试验小球粘合剂(bead bond)膜、带小球的小球粘合剂膜和成品反射片的耐冲击性。制备小球粘合剂膜和带单层小球的小球粘合剂膜并从涂覆丙烯酸类的剥离衬里上将其取出。随后将这些“独立的”膜用压敏粘合剂层压在0.8mm厚的铝板上,所述压敏粘合剂包括90∶10的丙烯酸异辛酯-丙烯酸共聚物,并用4.0-6.0Mrad的电子束进行固化,在交联前用上述方法测得的比浓对数粘度为0.6-1.0dl/g(下面称之为90∶10 IOA∶AA粘合剂)。使用相同的粘合剂将成品的逆向反射片直接层压在铝上。用直径为15.9mm的冲头对与膜或反射片相反的那一侧的铝板进行冲击。试验使用的冲击力逐渐增加至最大为1.6kg-m。结果列于下表B。
牌照板压印性:将逆向反射片安装在厚度为0.8mm的3003-H12铝合金坯料上,使用阴/阳模头压印各种浮雕的图案,形成一套5个字符(Ω),它为7.06cm高、5.16cm宽、笔划宽度为0.95cm。字符压印在坯料中的深度分别为1.5mm、1.75mm、2.0mm、2.25mm和2.5mm。边缘的斜度由1.5mm时的0.8至2.5mm时的1.3。记录的压印深度为未观察到裂缝时的最大压印深度。记录的耐爆脱性为24天后在字符周围区域未观察到反射片鼓起的最大压印深度。结果列于下表B。
表层膜粘性:将逆向反射片施加在0.8mm铝板上并将其在沸水中浸泡2分钟。使用锋利的剃刀片小心地将表层膜从底部逆向反射片上剥离。在INSTRON或SYNTEX拉伸试验仪上将表层膜以180°的角度从底片上拉下,测定将表层膜从底部逆向反射片上剥离的拉力。结果列于下表B。
模拟耐天候老化:将实施例2的小球粘合剂膜层压在已贴在铝板上的90∶10IOA∶AA压敏粘合剂上。根据ASTM试验方法G23,条件E在天候老化机上试验样板的500、1000和1500小时的天候老化性。结果列于下表C。
材料的制备
表层膜:如下挤出透光的表层膜,所述表层膜包括:97.4份PRIMACOR 3440(挤出级热塑性高分子聚合物,据信包括乙烯单体主要部分和丙烯酸单体次要部分,熔体指数约10,购自DuPont de Nemours)和2.6份稳定体系(1.0份紫外光吸收剂、1.5份位阻胺和0.1份抗氧剂,确信该稳定体系不会影响表层膜的强度及其与其它材料的粘性)。使用压缩比为3∶1的单螺纹螺杆将稳定的共聚物挤出在双轴取向的聚对苯二甲酸乙二醇酯(PET)载体上形成0.033mm厚的膜。挤出温度由约190℃升至275℃。挤出机螺杆速度为30rpm,并调节膜的引出速度以便使膜具有所需的厚度。挤出膜被缠绕成卷状。
制备用作小球粘合剂层的聚氨酯
聚氨酯制备1:将下列物料装入一个1升的三颈圆底烧瓶中:购自Witco CorpMelrose Park,IL商品名为FOMREZ 8056-146的聚酯二醇(220g,0.560当量)和二甲苯(440g)。由于该二元醇溶液的含水量大于500ppm,对总共220g二甲苯进行共沸蒸馏,使含水量小于500ppm。向反应容器中加入二(4-异氰酸酯基环己基)甲烷(67.48g,0.515当量;购自Bayer CorpPittsburgh,PA)、二甲苯(67.5g)和两滴二月桂酸二丁基锡(Aldrich Chemical CoMilwaukee,WI)。将反应物加热回流5小时,随后保持在110℃(约12小时)直至在红外谱图上观察不到游离的异氰酸酯为止。该材料在四氢呋喃中测得的比浓对数粘度为0.44dl/g。计算的羟基当量为6418,Tg为-11.5℃。
聚氨酯制备2:将下列物料装入一个1升的三颈圆底烧瓶中:购自Witco Corp商品名为FOMREZ 55-112的聚酯二醇(150.07g,0.295当量)和FOMREZ8066-120(150.00g,0.326当量)以及二甲苯(381.59g)。由于该二元醇溶液的含水量大于500ppm,对总共153.94g二甲苯进行共沸蒸馏,使含水量小于500ppm。向反应容器中加入二(4-异氰酸酯基环己基)甲烷(74.93g,0.572当量;购自BayerCorpPittsburgh,PA)、二甲苯(147.5g)和三滴二月桂酸二丁基锡。将反应物加热回流4小时,随后保持在110℃(约12小时)直至在红外谱图上观察不到游离的异氰酸酯为止。该材料在四氢呋喃中测得的比浓对数粘度为0.40dl/g。计算的羟基当量为7539,Tg为-21.1℃。
聚氨酯制备3:将下列物料装入一个1升的三颈圆底烧瓶中:聚酯二醇FOMREZ 8056-146(283.5g,0.721当量)和4-甲基-2-戊酮(366g)。由于该二元醇溶液的含水量大于500ppm,对总共306g 4-甲基-2-戊酮进行共沸蒸馏,并用306g干燥4-甲基-2-戊酮代替,使含水量小于500ppm。向反应容器中加入二苯基甲烷二异氰酸酯(82.97g,0.664当量;购自Bayer CorpPittsburgh,PA)和2滴二月桂酸二丁基锡。将反应物加热回流90分钟直至在红外谱图上观察不到游离的异氰酸酯为止。该材料在四氢呋喃中测得的比浓对数粘度为0.29dl/g。计算的羟基当量为6349,Tg为-12.0℃。
聚氨酯制备4:将下列物料装入一个1升的三颈圆底烧瓶中:聚酯二醇FOMREZ 8056-146(275.00g,0.700当量)和4-甲基-2-戊酮(550g)。由于该二元醇溶液的含水量大于500ppm,对总共275g 4-甲基-2-戊酮进行蒸馏使含水量小于500ppm。向反应容器中加入异佛尔酮二异氰酸酯(84.35g,0.644当量;购自HuelsAmerica,Piscataway,NJ)、4-甲基-2-戊酮(85g)和2滴二月桂酸二丁基锡。将反应物加热回流3小时,随后保持在105℃(约14小时)直至在红外谱图上观察不到游离的异氰酸酯为止。该材料在四氢呋喃中测得的比浓对数粘度为0.29dl/g。计算的羟基当量为6418,Tg为-9.6℃。
聚氨酯比较制备方法1:聚酯多醇用H12MDI扩链成羟基封端的聚氨酯(Tg=27℃),它是用上面制备1所述的方法由聚酯多醇(Tg=2.6℃)制得的。
实施例1
在实验室中,将制备1制得的小球粘合剂树脂用购自DSM Resins,Zwolle,theNetherlands商品名为URAMEX CP 1132 MF的部分丁基化的蜜胺-甲醛树脂交联,树脂与交联剂之比为4.1∶1(按固体计)。用空气混合器将试样混合约5分钟。用刮刀涂覆机将形成的溶液按0.075mm的湿厚度涂覆在涂覆丙烯酸酯的纸剥离衬里上。用这种方法制备三个试样。第一个试样(1A)在空气中干燥1分钟、在90℃烘2分钟随后在150℃烘3分钟。涂层的干厚度为0.025mm。其余两个试样(1B和1C)干燥1分钟,将玻璃小球(直径60±10微米,表面经有机铬配合物和含氟烃处理)成瀑布落在试样上,随后将试样在90℃和150℃分别烘2和3分钟,对嵌入的小球不施加压力。随后在试样1C上涂覆含有63重量%BUTVARB-76聚乙烯醇缩丁醛(Monsanto,St.Louis,MO)和23重量%BACKAMINE21-510脲醛交联树脂(Reichold Chemicals,Research Triangle Park,NC)以及14重量%AROPLAZ 1351聚酯增塑剂(Reichold Chemicals)的间隔层。所述重量百分数是按固体计算的。随后将间隔层在90℃和150℃分别固化2和3分钟,形成0.013mm厚的干涂层。从小球粘合剂表面上除去丙烯酸剥离衬里。在间隔层上层压上述90∶10 IOA∶AA压敏粘合剂。在反射片的小球粘合剂层上热层压0.033mm厚前面制得的表层膜。
实施例2和比较例1
用不同的丁基化蜜胺-甲醛交联剂和不同的聚氨酯树脂与交联剂的比例制备数种小球粘合剂组合物,其组成可参见下表:试样 聚氨酯制备 树脂量 %树脂固体 交联剂量1 %交联剂固体 树脂/交联剂
方法 (g) (g) 比例2A 1 100 48.5 14.26 68 52B 1 50 48.5 4.04 60 102C 1 100 48.5 2.54 95 182D 4 45 51.3 5.22 68 6.52E 3 45 53.1 5.41 68 6.52F 2 45 52.3 5.32 68 6.52G 1 40 37.3 7.06 68 3.1比较 比较制备 44.5 50 5.84 68 5.6例1 法1
1所有试样含有丁基化的蜜胺-甲醛树脂作为交联剂:试样2B含RESIMENE881(部分丁基化的);试样2C含RESIMENE 7512(全丁基化的);剩余的其它均含URAMEX CP 1132 MF(部分丁基化的)。
用空气混合器将各个小球粘合剂组合物试样混合约5分钟。用刮刀涂覆机将形成的溶液按0.05mm的湿厚度涂覆在涂覆丙烯酸酯的纸剥离衬里上。对于各种小球粘合剂组合物用这种方法制备二个试样。每种的第一个试样在空气中干燥1分钟、在90℃烘2分钟随后在150℃烘3分钟。涂层的干厚度为0.025mm。各种组合物的其余试样用空气干燥1分钟,如实施例1那样将玻璃小球成瀑布落在试样上,随后将试样在90℃和150℃分别烘2和3分钟。
实施例3和比较例2
将由制备1制得的聚氨酯树脂(试样3A)和比较制备方法1制得的聚氨酯树脂(比较例2)分别与DSM的URAMEX CP 1132 MF和Monsanto的RESIMENE 881蜜胺-甲醛交联剂混合,树脂与交联剂之比6.36∶1(按固体计)。将溶液用刮刀涂覆机涂覆在涂有丙烯酸酯的纸剥离衬里上,干燥后形成厚度约0.025mm的涂层。将实施例1所述的单层玻璃小球施加在未固化的小球粘合剂组合物上。分别使用10.7m/分钟和15.2m/分钟的线速度将试样3A和比较例2试样分别通过烘炉烘3.3分钟和2.3分钟,烘箱的初始温度为90℃,最终温度升至170℃。
接着,将实施例1所述的间隔层施加在反射片的小球粘合剂层上,形成0.008-0.031mm厚的间隔层。使用15.3m/分钟的线速度将涂覆间隔层的膜通过烘炉中烘2.3分钟,烘箱的初始温度为75℃,最终温度升至170℃。
用真空沉积法向间隔层施加约100nm厚的金属铝反射层。随后从小球粘合剂层上剥去丙烯酸酯剥离衬里。随后向反射层施加0.038mm厚的90∶10 IOA∶AA粘合剂层。接着,向小球粘合剂层的上表面(经0.39千瓦/米/分钟的电晕处理)施涂一层底涂溶液。该底涂溶液包括75.0份购自Zeneca Resins,Wilmington,MA商品名为NEOREZ R960的水基脂族聚氨酯、14.9份水、0.2份购自Witco CorpMelrose Park,IL商品名为WITCO 3056A的消泡剂、7.5份乙醇、0.1份购自美国3M公司商品名为FC-120的含氟烃匀涂剂以及2.3份购自Zeneca Resins,Wilmington,MA商品名为CX-100的100%活性多官能氮丙啶液体交联剂,使用175线四边形滚花涂覆机涂布。随后在65℃干燥涂层,形成干厚度约2微米的底涂层。
随后,将0.033mm厚上面制得的表层膜层压在逆向反射基材的小球粘合剂表面上。层压前,在下列条件下对表层膜的各个表面进行电晕处理:2.4kw/m宽;热罐表面,150℃;热罐直径,61cm;夹辊硬度,70肖氏A;速度,15.3m/分钟;复合物加热长度,60cm。剥去PET载体膜并将形成的逆向反射片缠绕成卷保存。
结果
拉伸强度、伸长率。耐冲击性、压印性、耐天候老化性和表层膜粘性列于下表。
表A
实施例 | 屈服拉伸强度(MPa) | 断裂拉伸强度(MPa) | 伸长率(%) | 耐冲击性1(kg-m) |
1A | nt | 6.32 | 430 | >1.37 |
1B | nt | 0.43 | 710 | >1.37 |
1C | nt | nt | nt | >1.37 |
2A | 0.73 | 0.67 | 490 | >1.6 |
2A带小球 | 1.30 | 0.48 | 536 | >1.6 |
2B | 4.00 | 0.19 | 998 | >1.6 |
2B带小球 | 0.88 | 0.66 | 505 | >1.6 |
2C带小球 | ** | ** | ** | >1.6 |
2D | 1.90 | 1.90 | 217 | >1.6 |
2D带小球 | 2.06 | 2.06 | 236 | >1.6 |
2E | 0.51 | 0.19 | 999 | >1.6 |
2E带小球 | 1.16 | 1.01 | 541 | >1.6 |
2F | 0.26 | 0.14 | 1,008 | >1.6 |
2F带小球 | 0.89 | 0.86 | 581 | >1.6 |
2G | nt | 5.84 | 440 | >1.37 |
2G带小球 | 0.75 | 0.29 | 585 | >1.37 |
比较例1 | nt | 58.23 | 5 | <0.46 |
3A带小球 | nt | nt | nt | >1.6 |
3A成品反射片 | nt | nt | nt | 0.91 |
比较例2带小球 | nt | nt | nt | <0.11 |
比较例2成品逆向反射片 | nt | nt | nt | <0.23 |
1对于列为>1.37或>1.6的数据,在试验的最大的力的情况下未产生失败(即未明显开裂)。
**未能试验,因为未能从剥离衬里上剥下足够的试样,可使用另一种剥离衬里做该试样试验。
nt=未试验。
表B
实施例 | 低速牌照板压印性 | 耐爆脱 | 表层膜粘性 |
1C3A成品的反射片比较例2成品的反射片 | 在2.5mm未失败在2.5mm未失败在1.75mm失败 | 2.5mm凸印字符未爆脱2.25mm凸印字符未爆脱nt | nt未分离未分离 |
表A和表B的结果证实了相对于常规反射片,本发明反射片的耐冲击性和压印性高。所列的压印性是未观察到可见裂缝的最大压印深度。所列的耐爆脱性是24天后在字符周围区域未观察到反射片鼓起的最大压印深度。下表C的结果表明本发明反射片的改进的耐天候老化性。
表C
500小时 | 1000小时 | 500小时 | |||||||
实施例 | 60°光泽%Ret. | 裂缝尺寸 | 颜色 | 60°光泽%Ret. | 裂缝尺寸 | 颜色 | 60°光泽%Ret. | 裂缝尺寸 | 颜色 |
2G比较例1 | 112.8102.0 | 无无 | 透明透明 | 124.897.2 | 无1-3mm | 很淡的黄色淡黄色 | 99.739.6 | 无1-3mm | 淡黄色淡黄色 |
就如单独引用的那样,本文所引用的所有专利、专利文献和出版物均引为参考。上面的详细描述仅用于清楚地进行理解。不应理解为不必要的限定。本发明不限于上述详细描述,对本领域普通技术人员而言的明显的变化均包括在由权利要求限定的本发明范围内。
Claims (14)
1.一种逆向反射片,它包括:
(a)基本排列在一个单层中的逆向反射元件;
(b)所述逆向反射元件至少部分嵌入于其中的间隔层;
(c)在所述间隔层下面的镜面反射层;以及
(d)所述逆向反射元件至少部分嵌入于其中的小球粘合剂层,其特征在于所述小球粘合剂层包括含有氨基甲酸酯基团的氨基塑料交联的聚合物,在交联前所述聚合物的玻璃化温度(Tg)小于约0℃。
2.如权利要求1所述的逆向反射片,它还包括置于与逆向反射元件相反的那一小球粘合剂层表面上的热塑性表层膜。
3.如权利要求2所述的逆向反射片,其特征在于所述表层膜包括透光聚合物材料,该材料包括聚乙烯或含有以重量计为主要部分的至少一种乙烯或丙烯和为次要部分的至少一种极性单体的单体的一种或多种共聚物。
4.如权利要求3所述的逆向反射片,其特征在于所述极性单体选自丙烯酸、甲基丙烯酸、丙烯酸乙酯和乙酸乙烯酯。
5.如权利要求2所述的逆向反射片,它还包括一层置于与间隔层相反的那一镜面反射层表面上的粘合剂。
6.如权利要求1-5中任何一项所述的逆向反射片,其特征在于当粘结在0.8mm厚的铝板上时,它的耐高速冲击性至少约0.69kgm。
7.如权利要求1-6中任何一项所述的逆向反射片,其特征在于所述氨基塑料交联的聚合物是由聚酯多元醇和多异氰酸酯制成的,或者由羟基官能的聚合物和氨基塑料树脂制成的,或者包括蜜胺-甲醛树脂。
8.如权利要求7所述的逆向反射片,其特征在于所述聚酯多元醇是羟基封端的聚酯二醇。
9.一种制品,它包括通过用粘合剂层来支承权利要求1-8中任何一项所述的逆向反射片的基材。
10.如权利要求9所述的制品,它经压印使得基材具有不规则的表面。
11.如权利要求10所述的制品,它是牌照板,其特征在于所述逆向反射片还包括置于与逆向反射元件相反的那一小球粘合剂层表面上的表层膜。
12.一种制造逆向反射片的方法,它包括:
(a)将一层未固化的小球粘合剂组合物涂覆在剥离衬里上,该小球粘合剂组合物包括交联剂和含有氨基甲酸酯基团及未保护的官能团的可交联聚合物,其中所述可交联聚合物的玻璃化温度(Tg)小于约0℃;
(b)将逆向反射元件沉积在所述未固化的小球粘合剂组合物层中;
(c)加热所述未固化的小球粘合剂组合物,加热的温度和时间能有效地交联聚合物;
(d)用间隔层覆盖逆向反射元件的露出部分,使间隔层形成围绕逆向反射元件的凹形外表面;以及
(e)向间隔层的凹面上施加镜面反射层。
13.如权利要求12所述的方法,其特征在于加热所述未固化的小球粘合剂组合物,加热的温度和时间能有效地交联聚合物的步骤包括将组合物加热至约90-180℃的温度。
14.如权利要求12所述的方法,其特征在于所述未保护的官能团包括羟基,可交联的聚合物是由聚酯多元醇和多异氰酸酯制成的,所述聚酯多元醇是羟基封端的聚酯二醇,并且交联剂包括蜜胺-甲醛树脂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/629,495 US5882771A (en) | 1996-04-10 | 1996-04-10 | Conformable embossable retroreflective sheeting |
US08/629,495 | 1996-04-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1215479A true CN1215479A (zh) | 1999-04-28 |
Family
ID=24523223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97193719A Pending CN1215479A (zh) | 1996-04-10 | 1997-03-12 | 可贴合可压印的逆向反射片 |
Country Status (11)
Country | Link |
---|---|
US (1) | US5882771A (zh) |
EP (1) | EP0894274B1 (zh) |
JP (1) | JP2000508434A (zh) |
KR (1) | KR20000005284A (zh) |
CN (1) | CN1215479A (zh) |
AU (1) | AU712673B2 (zh) |
BR (1) | BR9708533A (zh) |
CA (1) | CA2249443A1 (zh) |
DE (1) | DE69703153T2 (zh) |
WO (1) | WO1997038336A1 (zh) |
ZA (1) | ZA972898B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102282483A (zh) * | 2008-11-18 | 2011-12-14 | 艾利丹尼森公司 | 可热成型的三维后向反射制品及其制造方法 |
CN108349445A (zh) * | 2015-11-05 | 2018-07-31 | 埃里希乌奇股份公司 | 具有色彩效果的回归反射体和制造方法 |
CN109901255A (zh) * | 2019-04-22 | 2019-06-18 | 浙江靓鸿新材料有限公司 | 一种复合型面层反光膜及制造方法 |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6156436A (en) * | 1997-04-04 | 2000-12-05 | 3M Innovative Properties Company | Use of a crystalline bead bond layer in a retroreflective article |
DE69925086T2 (de) * | 1998-10-30 | 2006-02-02 | Avery Dennison Corp., Pasadena | Retroreflektierende Folie mit einem Bild zur Echtheitsprüfung und Verfahren zu ihrer Herstellung |
GB9918617D0 (en) * | 1999-08-07 | 1999-10-13 | Epigem Limited | An optical display composite |
US6677028B1 (en) | 1999-09-10 | 2004-01-13 | 3M Innovative Properties Company | Retroreflective articles having multilayer films and methods of manufacturing same |
US6958179B2 (en) | 1999-12-30 | 2005-10-25 | 3M Innovative Properties Company | Segmented sheeting and methods of making and using same |
US6533961B2 (en) * | 2000-02-22 | 2003-03-18 | 3M Innovative Properties Company | Durable fluorescent organic pigments and methods of making |
US6828005B2 (en) * | 2000-06-05 | 2004-12-07 | Rohm And Haas Company | Wear-resistant composite and method for producing the composite |
WO2002021167A1 (en) * | 2000-09-01 | 2002-03-14 | 3M Innovative Properties Company | Sheeting having an optical core laminated to a vinyl film, retroreflective articles, and methods |
TWI241332B (en) * | 2000-12-01 | 2005-10-11 | 3M Innovative Properties Co | Crosslinked pressure sensitive adhesive compositions, and adhesive articles based thereon, useful in high temperature applications |
US6531212B2 (en) | 2001-02-14 | 2003-03-11 | 3M Innovative Properties Company | Retroreflective article and method |
US6586067B2 (en) | 2001-04-02 | 2003-07-01 | Avery Dennison Corporation | Encapsulated lens retroreflective sheeting |
US6861134B1 (en) | 2001-04-02 | 2005-03-01 | Omnova Solutions Inc. | Retroreflective articles of nanoporous construction and method for the manufacture thereof |
US6931665B2 (en) | 2001-07-30 | 2005-08-23 | 3M Innovative Properties Company | Vapor permeable retroreflective garment |
KR20050056914A (ko) * | 2001-11-05 | 2005-06-16 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 필름의 인쇄 방법 및 물품 |
KR100463689B1 (ko) * | 2001-11-21 | 2004-12-29 | 주식회사 엘지화학 | 우수한 내후성과 유연성을 갖는 역반사 시트 및 그의제조방법 |
WO2003066761A2 (en) * | 2002-02-04 | 2003-08-14 | Avery Dennison Corporation | Topcoat compositions, coated substrates and method |
US6517166B1 (en) * | 2002-02-07 | 2003-02-11 | Giant Manufacturing Co., Ltd. | Light-reflective wheel rim |
WO2003107309A2 (en) * | 2002-06-13 | 2003-12-24 | 3M Innovative Properties Company | System of controlled certificate production and management |
ITMI20022069A1 (it) * | 2002-10-01 | 2004-04-02 | I B R Ind Bergamasca Rifrang Enti S R L | Materiale stratiforme retroriflettente. |
ES2217949B1 (es) * | 2002-12-09 | 2005-07-16 | Industrias Samar't, S.A. | Procedimiento para la confeccion de placas acrilicas partiendo de una matricula embutida. |
ES2233175B1 (es) * | 2003-04-10 | 2006-02-01 | Industras Samar't, S.A. | Disposicion de troquelado de placas o letreros embutiendo por rehundido. |
US7504147B2 (en) * | 2004-07-22 | 2009-03-17 | Avery Dennison Corporation | Retroreflective sheeting with security and/or decorative image |
KR100615638B1 (ko) * | 2004-08-20 | 2006-08-25 | 도레이새한 주식회사 | 광확산필름 |
US7453634B2 (en) | 2005-03-07 | 2008-11-18 | Avery Dennison Corporation | Discontinuous or variable thickness gain modification coating for projection film and method for making same |
US20070037960A1 (en) * | 2005-08-15 | 2007-02-15 | General Electric Company | Copolyester stilbene embossed film and methods of making the same |
US20070240585A1 (en) * | 2006-04-13 | 2007-10-18 | Nitin Vaish | Embossing system, methods of use, and articles produced therefrom |
US20070240813A1 (en) * | 2006-04-17 | 2007-10-18 | Yu Hu | Process for forming a multilayer film and the film formed therefrom |
CN100589995C (zh) * | 2008-06-30 | 2010-02-17 | 上海复旦天臣新技术有限公司 | 防伪薄膜及其制备方法 |
CN201302625Y (zh) * | 2008-10-23 | 2009-09-02 | 上海复旦天臣研发中心有限公司 | 在薄片上刻录动感浮点图像的装置 |
US8840956B2 (en) * | 2008-10-31 | 2014-09-23 | Potters Industries, Llc | Retroreflective coating and method for applying a retroreflective coating on a structure |
US20100272962A1 (en) * | 2009-04-22 | 2010-10-28 | Potters Industries Inc. | Reflective substrate surface system, reflective assembly, and methods of improving the visibility of a substrate surface |
US8647013B2 (en) * | 2010-02-09 | 2014-02-11 | Potters Industries, Llc | Reflective substrate surface system, reflective assembly, and methods of improving the visibility of a substrate surface |
JP2014024537A (ja) | 2012-06-19 | 2014-02-06 | 3M Innovative Properties Co | ナンバープレート用シート、ナンバープレート用積層体、ナンバープレートおよびナンバープレート用装飾部材 |
EP3105047B1 (en) * | 2014-02-13 | 2020-12-09 | 3M Innovative Properties Company | Flexible microsphere articles having high temperature stability |
EP3105048B1 (en) | 2014-02-13 | 2021-06-16 | 3M Innovative Properties Company | Dual cure stain resistant microsphere articles |
US8899318B1 (en) | 2014-04-24 | 2014-12-02 | Ronald C. Parsons | Applying an aggregate to expandable tubular |
ES2612727B1 (es) * | 2015-11-16 | 2018-05-08 | Industrias Samar't, S.A. | Placa de matrícula reforzada |
US9864112B1 (en) | 2016-11-16 | 2018-01-09 | 3M Innovative Properties Company | Conformable retroreflective graphic film |
EP3415963A1 (en) * | 2017-06-14 | 2018-12-19 | 3M Innovative Properties Company | Retroreflective sheeting |
KR102069082B1 (ko) * | 2019-09-30 | 2020-02-11 | 해오름 주식회사 | 알루미늄 박판이 베이스층을 형성하는 재귀반사시트 |
KR102657490B1 (ko) | 2019-10-30 | 2024-04-12 | 기와 가가쿠 고교 가부시키가이샤 | 재귀성 반사 시트 |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2407680A (en) * | 1945-03-02 | 1946-09-17 | Minnesota Mining & Mfg | Reflex light reflector |
US3222204A (en) * | 1960-04-20 | 1965-12-07 | Minnesota Mining & Mfg | Process of making beaded coatings and films from glass beads treated with oleophobic sizing agent |
AT307280B (de) * | 1969-05-09 | 1973-05-10 | Swarovski & Co | Reflexfolie und Verfahren zu ihrer Herstellung |
US3551025A (en) * | 1969-03-28 | 1970-12-29 | Minnesota Mining & Mfg | Highly flexible reflex reflecting constructions |
US3700305A (en) * | 1970-12-14 | 1972-10-24 | Minnesota Mining & Mfg | Retroreflective microspheres having a dielectric mirror on a portion of their surface and retroreflective constructions containing such microspheres |
US3954899A (en) * | 1973-04-02 | 1976-05-04 | Ppg Industries, Inc. | Extensible coatings |
US4569857A (en) * | 1979-10-01 | 1986-02-11 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting |
US4511210A (en) * | 1979-10-01 | 1985-04-16 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting |
US4367920A (en) * | 1979-10-01 | 1983-01-11 | Minnesota Mining And Manufacturing Company | Retroflective sheeting |
US4495061A (en) * | 1980-06-16 | 1985-01-22 | Chevron Research Company | Hydrocarbon conversion catalyst and process using said catalyst |
US4530859A (en) * | 1981-12-23 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Method of preparing a polymeric coating composition from a blocked isocyanate-functional polymeric compound and a crosslinking agent which is insoluble in aprotic solvents |
US4725494A (en) * | 1982-09-02 | 1988-02-16 | Minnesota Mining And Manufacturing Co. | Retroreflective sheeting |
US4634220A (en) * | 1983-02-07 | 1987-01-06 | Minnesota Mining And Manufacturing Company | Directionally imaged sheeting |
US4648932A (en) * | 1983-04-11 | 1987-03-10 | Minnesota Mining And Manufacturing Company | High-angularity retroreflective sheeting and method for manufacture |
US4950525A (en) * | 1983-04-11 | 1990-08-21 | Minnesota Mining And Manufacturing Company | Elastomeric retroreflective sheeting |
US4505967A (en) * | 1983-04-11 | 1985-03-19 | Minnesota Mining And Manufacturing Company | High-angularity retroreflective sheeting and method for manufacture |
US4808471A (en) * | 1985-03-01 | 1989-02-28 | Minnesota Mining And Manufacturing Company | Flat transparent top coat for retroreflective sheeting |
US4721649A (en) * | 1985-05-08 | 1988-01-26 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting |
US4691993A (en) * | 1985-05-13 | 1987-09-08 | Minnesota Mining And Manufacturing Company | Transparent sheets containing directional images and method for forming the same |
US4664966A (en) * | 1985-11-18 | 1987-05-12 | Minnesota Mining And Manufacturing Company | Enclosed-lens retroreflective sheeting having tough, weather-resistant, transparent cover film |
US4897136A (en) * | 1985-11-18 | 1990-01-30 | Minnesota Mining And Manufacturing Company | Method of making encapsulated-lens retroreflective sheeting |
US4663213A (en) * | 1985-11-18 | 1987-05-05 | Minnesota Mining And Manufacturing Company | Transparent multi-layer cover film for retroreflective sheeting |
US5064272A (en) * | 1985-11-18 | 1991-11-12 | Minnesota Mining And Manufacturing Company | Encapsulated-lens retroreflective sheeting and method of making |
US4983436A (en) * | 1987-04-15 | 1991-01-08 | Minnesota Mining And Manufacturing Company | Retroreflective sheeting with backing film |
US4896943A (en) * | 1987-05-13 | 1990-01-30 | Minnesota Mining And Manufacturing Company | Encapsulated-lens retroreflective sheeting having improved cover film |
US4919741A (en) * | 1987-09-23 | 1990-04-24 | Minnesota Mining And Manufacturing Company | Method for making embossed information plate having retroreflective sheeting on the surface thereof |
US5262225A (en) * | 1988-09-02 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Embossable sign construction |
US5256721A (en) * | 1988-09-02 | 1993-10-26 | Minnesota Mining And Manufacturing Company | Polymer composition for use as flexible dimensionally stable coating; and method |
US5008142A (en) * | 1988-09-02 | 1991-04-16 | Minnesota Mining And Manufacturing Company | Embedded lens retroreflective sheeting with flexible, dimensionally stable coating |
US5069964A (en) * | 1989-05-23 | 1991-12-03 | Minnesota Mining And Manufacturing Company | Flexible, substrate-insular retroreflective sheeting |
JP3117599B2 (ja) * | 1994-03-18 | 2000-12-18 | 日本カーバイド工業株式会社 | 再帰反射性シート |
-
1996
- 1996-04-10 US US08/629,495 patent/US5882771A/en not_active Expired - Lifetime
-
1997
- 1997-03-12 DE DE69703153T patent/DE69703153T2/de not_active Expired - Fee Related
- 1997-03-12 KR KR1019980707992A patent/KR20000005284A/ko not_active Application Discontinuation
- 1997-03-12 EP EP97914998A patent/EP0894274B1/en not_active Expired - Lifetime
- 1997-03-12 BR BR9708533A patent/BR9708533A/pt unknown
- 1997-03-12 JP JP9536196A patent/JP2000508434A/ja active Pending
- 1997-03-12 WO PCT/US1997/003829 patent/WO1997038336A1/en not_active Application Discontinuation
- 1997-03-12 CN CN97193719A patent/CN1215479A/zh active Pending
- 1997-03-12 AU AU22054/97A patent/AU712673B2/en not_active Ceased
- 1997-03-12 CA CA002249443A patent/CA2249443A1/en not_active Abandoned
- 1997-04-04 ZA ZA972898A patent/ZA972898B/xx unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102282483A (zh) * | 2008-11-18 | 2011-12-14 | 艾利丹尼森公司 | 可热成型的三维后向反射制品及其制造方法 |
CN102282483B (zh) * | 2008-11-18 | 2015-08-05 | 艾利丹尼森公司 | 可热成型的三维后向反射制品及其制造方法 |
CN108349445A (zh) * | 2015-11-05 | 2018-07-31 | 埃里希乌奇股份公司 | 具有色彩效果的回归反射体和制造方法 |
CN109901255A (zh) * | 2019-04-22 | 2019-06-18 | 浙江靓鸿新材料有限公司 | 一种复合型面层反光膜及制造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69703153D1 (de) | 2000-10-26 |
US5882771A (en) | 1999-03-16 |
DE69703153T2 (de) | 2001-05-10 |
AU712673B2 (en) | 1999-11-11 |
JP2000508434A (ja) | 2000-07-04 |
KR20000005284A (ko) | 2000-01-25 |
CA2249443A1 (en) | 1997-10-16 |
AU2205497A (en) | 1997-10-29 |
ZA972898B (en) | 1998-10-05 |
EP0894274A1 (en) | 1999-02-03 |
BR9708533A (pt) | 1999-08-03 |
WO1997038336A1 (en) | 1997-10-16 |
EP0894274B1 (en) | 2000-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1215479A (zh) | 可贴合可压印的逆向反射片 | |
CN101116015B (zh) | 逆反射片 | |
CN1269655C (zh) | 显示出耐沾污性的涂层组合物和含有该组合物的制品 | |
CN1323832C (zh) | 用于保护表面的压敏粘合剂片材及其生产方法 | |
CN1665680A (zh) | 用于层压玻璃的数字颜色-设计复合体 | |
CN1582235A (zh) | 对逆反射片和制品进行印刷的方法 | |
CN1182499C (zh) | 一种标志制品及其制造方法 | |
KR20080096582A (ko) | 엠보스 이형 시트의 원반, 엠보스 이형 시트, 엠보스 이형 시트의 원반의 제조 방법, 엠보스 이형 시트의 제조 방법, 엠보스 이형 시트의 제조 장치, 합성 피혁, 및 합성 피혁의 제조 방법 | |
CN1208470A (zh) | 交联聚氨酯粘合剂在逆向反射片上的应用 | |
CN1219261A (zh) | 提示扰动的多层片材 | |
CN1656396A (zh) | 包含水基丙烯酸面涂层的逆反射制件 | |
EP1481031B1 (en) | Marking film, receptor sheet and marking film for vehicles | |
CN1578729A (zh) | 交联底胶组合物及其在可热成形膜中的应用 | |
CN1244262A (zh) | 在逆向反射制品中使用结晶珠粒粘合层 | |
CN1150276C (zh) | 可辐射交联热塑性组合物及其在制备图象制品中的应用 | |
CN1075197C (zh) | 透镜型定向反光层体 | |
CN1454325A (zh) | 具有层压到乙烯基薄膜的光学芯的片材、逆向反射制品及制造方法 | |
CN1221378C (zh) | 包封透镜的后反射薄片 | |
JP2009286068A (ja) | エンボス離型シートの原反、エンボス離型シート、エンボス離型シートの原反の製造方法、エンボス離型シートの製造方法、及び合成皮革の製造方法 | |
CN1241754C (zh) | 热转印组合物及其制造和使用方法 | |
CN1265958C (zh) | 改进的透明粘合片 | |
US20060063673A1 (en) | Marking film, receptor sheet and marking film for vehicles | |
JP7320937B2 (ja) | 外照看板フィルム | |
JP4006248B2 (ja) | 画像記録媒体及び画像表示シート | |
JP2003326629A (ja) | マーキングフィルム、レセプターシート及び乗り物用マーキングフィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |