CA2274541C - Retroreflective article having launderably durable bead-bond - Google Patents
Retroreflective article having launderably durable bead-bond Download PDFInfo
- Publication number
- CA2274541C CA2274541C CA 2274541 CA2274541A CA2274541C CA 2274541 C CA2274541 C CA 2274541C CA 2274541 CA2274541 CA 2274541 CA 2274541 A CA2274541 A CA 2274541A CA 2274541 C CA2274541 C CA 2274541C
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- moieties
- retroreflective
- retroreflective article
- polyol
- 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.)
- Expired - Fee Related
Links
- 239000004814 polyurethane Substances 0.000 claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 claims abstract description 64
- 238000004900 laundering Methods 0.000 claims abstract description 42
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 43
- -1 poly(alkoxy) Polymers 0.000 claims description 43
- 229920005862 polyol Polymers 0.000 claims description 35
- 150000003077 polyols Chemical class 0.000 claims description 35
- 239000004005 microsphere Substances 0.000 claims description 29
- 229920001228 polyisocyanate Polymers 0.000 claims description 22
- 239000005056 polyisocyanate Substances 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 125000002837 carbocyclic group Chemical group 0.000 claims description 9
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012080 ambient air Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 33
- 238000001035 drying Methods 0.000 abstract description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 64
- 239000004744 fabric Substances 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 19
- 239000004970 Chain extender Substances 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 150000002009 diols Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 229920013701 VORANOL™ Polymers 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 241000428199 Mustelinae Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- LLROOTQECVJATI-UHFFFAOYSA-N triethoxy(isocyanato)silane Chemical compound CCO[Si](OCC)(OCC)N=C=O LLROOTQECVJATI-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- CMCOFAYLDYIEBR-UHFFFAOYSA-L 2-[carboxymethylsulfanyl(dioctyl)stannyl]sulfanylacetic acid Chemical compound [O-]C(=O)CS.[O-]C(=O)CS.CCCCCCCC[Sn+2]CCCCCCCC CMCOFAYLDYIEBR-UHFFFAOYSA-L 0.000 description 1
- ZLBFMYQIKPWYBC-UHFFFAOYSA-N 2-benzofuran-1,3-dione;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C1=CC=C2C(=O)OC(=O)C2=C1 ZLBFMYQIKPWYBC-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 101100278987 Arabidopsis thaliana ECH2 gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 239000012780 transparent material Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- 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
- 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.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
-
- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/777,718 US5976669A (en) | 1996-12-20 | 1996-12-20 | Retroreflective article having launderably durable bead-bond |
| US08/777718 | 1996-12-20 | ||
| PCT/US1997/023040 WO1998028642A1 (en) | 1996-12-20 | 1997-12-04 | Retroreflective article having launderably durable bead-bond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2274541A1 CA2274541A1 (en) | 1998-07-02 |
| CA2274541C true CA2274541C (en) | 2007-02-06 |
Family
ID=25111044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2274541 Expired - Fee Related CA2274541C (en) | 1996-12-20 | 1997-12-04 | Retroreflective article having launderably durable bead-bond |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5976669A (https=) |
| EP (1) | EP0946889B1 (https=) |
| JP (1) | JP4344865B2 (https=) |
| KR (1) | KR100519884B1 (https=) |
| CN (1) | CN1113252C (https=) |
| CA (1) | CA2274541C (https=) |
| DE (1) | DE69721305T2 (https=) |
| TW (1) | TW386092B (https=) |
| WO (1) | WO1998028642A1 (https=) |
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| US6159537A (en) * | 1997-08-01 | 2000-12-12 | 3M Innovative Properties Company | Method of making a retroreflective article that has a binder layer containing an epoxy resin and silicone crosslinked polymer |
| DE60031240T2 (de) | 1999-01-14 | 2007-08-23 | Reflec Plc, Winsford | Retroreflektierende tinten |
| GB2347366A (en) * | 1999-03-05 | 2000-09-06 | Reflective Technology Ind Ltd | Reflective tape |
| USD475814S1 (en) | 1999-03-25 | 2003-06-10 | Head Lites Corporation | High visibility, load bearing tactical vest |
| USD440716S1 (en) | 1999-03-25 | 2001-04-17 | Head Lites Corporation | Enhanced visibility safety garment |
| KR100683513B1 (ko) | 1999-06-17 | 2007-02-16 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 중합체에 공유결합되는 염료와 반사성 플레이크를포함하는 착색층이 있는 재귀반사 물품 제조 방법 |
| US6361850B1 (en) | 1999-06-17 | 2002-03-26 | 3M Innovative Properties Company | Retroreflective article having a colored layer containing a dye covalently bonded to a polymer |
| FR2803724B1 (fr) * | 2000-01-18 | 2002-04-12 | T 2 S | Materiau complexe retroreflechissant la lumiere et/ou fluorescent |
| US6676754B1 (en) * | 2000-06-30 | 2004-01-13 | 3M Innovative Properties Company | Coating apparatus and methods of applying a polymer coating |
| US6953624B2 (en) * | 2001-03-02 | 2005-10-11 | 3M Innovative Properties Company | Printable film and coating composition exhibiting stain resistance |
| US6723433B2 (en) * | 2001-03-02 | 2004-04-20 | 3M Innovative Properties Company | Printable film and coating composition exhibiting stain resistance |
| ITMO20010126A1 (it) * | 2001-06-21 | 2002-12-21 | Autoadesivi S R L | Tessuto o termoadesivo rinfrangente o retroriflettente |
| US6820280B1 (en) * | 2002-06-18 | 2004-11-23 | Blaver Manufacturing Company, Inc. | Rip-off, high-visibility, safety vest |
| DE10355318A1 (de) * | 2003-11-27 | 2005-06-23 | Wacker-Chemie Gmbh | Verfahren zur Herstellung von organyloxysilylterminierten Polymeren |
| JP4787173B2 (ja) * | 2003-12-30 | 2011-10-05 | スリーエム イノベイティブ プロパティズ カンパニー | 色シフティング再帰反射体およびその製造方法 |
| US7671144B2 (en) * | 2004-01-30 | 2010-03-02 | Kaneka Corporation | Pressure sensitive adhesive composition |
| US9198156B2 (en) * | 2004-08-23 | 2015-11-24 | Telefonaktiebolaget L M Ericsson (Publ) | Paging mobile stations in a hybrid network |
| CN101039980B (zh) * | 2004-10-15 | 2010-12-08 | 陶氏环球技术公司 | 一种异氰酸酯-封端的预聚物组合物和一种由此生产的聚氨酯或聚脲弹性体 |
| US8232362B2 (en) * | 2005-09-15 | 2012-07-31 | Momentive Performance Materials Inc. | Preparation of amino-silane terminated polymer by using organic bismuth catalyst and cured polymer therefrom by using non-tin catalyst |
| US9248470B2 (en) | 2006-07-31 | 2016-02-02 | Safe Reflections, Inc. | Colorized retroreflective material and method |
| DE102006055739A1 (de) * | 2006-11-25 | 2008-05-29 | Bayer Materialscience Ag | Abformmassen |
| US8292539B2 (en) * | 2007-04-10 | 2012-10-23 | Stoncor Group, Inc. | Agglomerated retroreflective beads for highway marking and methods for fabrication and use thereof |
| US9207373B2 (en) | 2007-04-10 | 2015-12-08 | Stoncor Group, Inc. | Methods for fabrication and highway marking usage of agglomerated retroreflective beads |
| USD588752S1 (en) | 2007-12-21 | 2009-03-17 | Advanced Tactical Fabrication, Inc. | Enhanced visibility safety garment |
| USD590545S1 (en) | 2007-12-21 | 2009-04-14 | Advanced Tactical Fabrication, Inc. | Enhanced visibility safety garment |
| EP2237081A4 (en) * | 2008-01-10 | 2014-07-16 | Kolon Inc | OPTICAL FOILS |
| JP2010131817A (ja) * | 2008-12-03 | 2010-06-17 | Ito Kosan Kk | 再帰反射性シート |
| CN102893188B (zh) | 2010-05-25 | 2016-11-02 | 3M创新有限公司 | 外露透镜逆反射制品 |
| EP2591688A1 (en) | 2011-11-11 | 2013-05-15 | Kinco LLC | High visibility hand covering |
| TW201315598A (zh) * | 2012-10-18 | 2013-04-16 | Cing Wai Kung Mau Company | 反光物品製程 |
| CN103792603B (zh) | 2012-10-26 | 2016-07-06 | 3M创新有限公司 | 回归反射材料及制品 |
| CN103792604B (zh) | 2012-10-26 | 2016-12-21 | 3M创新有限公司 | 回归反射制品和附饰物 |
| WO2015030770A1 (en) | 2013-08-29 | 2015-03-05 | Safe Reflections, Inc. | Colorized retroreflective material and method of formation |
| CN105940325A (zh) | 2014-01-31 | 2016-09-14 | 3M创新有限公司 | 彩色回射制品 |
| EP3105047B1 (en) | 2014-02-13 | 2020-12-09 | 3M Innovative Properties Company | Flexible microsphere articles having high temperature stability |
| KR102300849B1 (ko) | 2014-02-13 | 2021-09-13 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 이중 경화 내오염성 미소구체 물품 |
| US10545268B2 (en) * | 2014-05-09 | 2020-01-28 | 3M Innovative Properties Company | Retroreflective articles |
| EP3155462B1 (en) * | 2014-06-16 | 2019-10-23 | 3M Innovative Properties Company | Retroreflective articles with wash durable bead bond layers |
| JP6454096B2 (ja) * | 2014-06-27 | 2019-01-16 | 株式会社松井色素化学工業所 | 画像形成方法及び布状繊維製品 |
| US10845514B2 (en) | 2014-09-30 | 2020-11-24 | 3M Innovative Properties Company | Retroreflective colored articles |
| CN104354352A (zh) * | 2014-10-14 | 2015-02-18 | 陈国顺 | 一种带彩色印花型反光织物及制作方法 |
| EP3240682A1 (en) | 2014-12-30 | 2017-11-08 | 3M Innovative Properties Company | Stain resistant retroreflective articles |
| CN105891924B (zh) | 2015-02-13 | 2019-07-09 | 3M创新有限公司 | 具有高温稳定性的柔性微球制品 |
| US11413846B2 (en) | 2016-03-30 | 2022-08-16 | 3M Innovative Properties Company | Article featuring a predetermined pattern of randomly distributed microspheres and methods of making the same |
| ITUA20164500A1 (it) * | 2016-06-20 | 2017-12-20 | Giorgio Corradi | Inserto retro riflettente |
| US20180055124A1 (en) * | 2016-08-26 | 2018-03-01 | Chieh-Yu Chen | Hat |
| EP3701299B1 (en) | 2017-10-27 | 2025-05-28 | 3M Innovative Properties Company | Method of making a retroreflective article comprising locally-laminated reflective layers |
| US11415731B2 (en) | 2017-10-27 | 2022-08-16 | 3M Innovative Properties Company | Retroreflective article comprising retroreflective elements comprising primary reflective layers and secondary reflective layers |
| WO2019084302A1 (en) | 2017-10-27 | 2019-05-02 | 3M Innovative Properties Company | RETROREFLECTIVE ARTICLE COMPRISING INCORPORATED REFLECTIVE LAYERS |
| WO2020240364A1 (en) * | 2019-05-24 | 2020-12-03 | 3M Innovative Properties Company | Radar retroreflective article |
| US20230099542A1 (en) * | 2021-09-29 | 2023-03-30 | Douglas Bradshaw | Traffic Control Safety Gloves |
| DE102024112160A1 (de) * | 2024-04-30 | 2025-10-30 | Valkental Gmbh | Reflektierendes Textilmaterial |
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| CA2061708C (en) * | 1991-05-08 | 2002-04-23 | Wu-Shyong Li | Launderable retroreflective applique with colorant |
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-
1996
- 1996-12-20 US US08/777,718 patent/US5976669A/en not_active Expired - Lifetime
-
1997
- 1997-12-04 DE DE1997621305 patent/DE69721305T2/de not_active Expired - Lifetime
- 1997-12-04 CN CN97180730A patent/CN1113252C/zh not_active Expired - Lifetime
- 1997-12-04 EP EP19970950958 patent/EP0946889B1/en not_active Expired - Lifetime
- 1997-12-04 JP JP52887298A patent/JP4344865B2/ja not_active Expired - Lifetime
- 1997-12-04 CA CA 2274541 patent/CA2274541C/en not_active Expired - Fee Related
- 1997-12-04 WO PCT/US1997/023040 patent/WO1998028642A1/en not_active Ceased
- 1997-12-04 KR KR10-1999-7005594A patent/KR100519884B1/ko not_active Expired - Fee Related
- 1997-12-11 TW TW086118692A patent/TW386092B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0946889A1 (en) | 1999-10-06 |
| DE69721305T2 (de) | 2004-02-12 |
| WO1998028642A1 (en) | 1998-07-02 |
| HK1023408A1 (en) | 2000-09-08 |
| CA2274541A1 (en) | 1998-07-02 |
| US5976669A (en) | 1999-11-02 |
| DE69721305D1 (de) | 2003-05-28 |
| TW386092B (en) | 2000-04-01 |
| EP0946889B1 (en) | 2003-04-23 |
| JP4344865B2 (ja) | 2009-10-14 |
| KR100519884B1 (ko) | 2005-10-12 |
| CN1240516A (zh) | 2000-01-05 |
| KR20000062254A (ko) | 2000-10-25 |
| JP2001507138A (ja) | 2001-05-29 |
| CN1113252C (zh) | 2003-07-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20121204 |