EP1003613A1 - Method and compositions for decorating glass - Google Patents
Method and compositions for decorating glassInfo
- Publication number
- EP1003613A1 EP1003613A1 EP98923736A EP98923736A EP1003613A1 EP 1003613 A1 EP1003613 A1 EP 1003613A1 EP 98923736 A EP98923736 A EP 98923736A EP 98923736 A EP98923736 A EP 98923736A EP 1003613 A1 EP1003613 A1 EP 1003613A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid group
- ink
- glass
- oligomer
- ink composition
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 239000011521 glass Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000005855 radiation Effects 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 39
- 239000000049 pigment Substances 0.000 claims description 30
- 239000002318 adhesion promoter Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002518 antifoaming agent Substances 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 239000000976 ink Substances 0.000 description 76
- 239000000376 reactant Substances 0.000 description 29
- -1 beta-carboxy ethyl Chemical group 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 16
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 239000011888 foil Substances 0.000 description 14
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 11
- 235000013361 beverage Nutrition 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 150000004756 silanes Chemical class 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000012952 cationic photoinitiator Substances 0.000 description 9
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 description 7
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000003209 petroleum derivative Substances 0.000 description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000004831 Hot glue Substances 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 235000013799 ultramarine blue Nutrition 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000001054 red pigment Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- FGSFVBRPCKXYDI-UHFFFAOYSA-N 2-triethoxysilylethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C(C)=C FGSFVBRPCKXYDI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000007930 Oxalis acetosella Species 0.000 description 2
- 235000008098 Oxalis acetosella Nutrition 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009500 colour coating Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-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
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- OIETYYKGJGVJFT-UHFFFAOYSA-N 3-[dimethyl-[3-(2-methylprop-2-enoylamino)propyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)CCCS([O-])(=O)=O OIETYYKGJGVJFT-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- GSFXLBMRGCVEMO-UHFFFAOYSA-N [SiH4].[S] Chemical class [SiH4].[S] GSFXLBMRGCVEMO-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003435 aroyl group Chemical group 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical class C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- CAPBXYLOGXJCFU-UHFFFAOYSA-N oxiran-2-ylmethoxysilane Chemical class [SiH3]OCC1CO1 CAPBXYLOGXJCFU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- OMGQCHLJDNJSDG-UHFFFAOYSA-N pentanoic acid Chemical compound C(CCCC)(=O)O.C(CCCC)(=O)O.C(CCCC)(=O)O OMGQCHLJDNJSDG-UHFFFAOYSA-N 0.000 description 1
- XHTWKNPMPDIELI-UHFFFAOYSA-N phenylmethoxysilane Chemical class [SiH3]OCC1=CC=CC=C1 XHTWKNPMPDIELI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VNTPGSZQKARKHG-UHFFFAOYSA-N trimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](C)(C)CCCOCC1CO1 VNTPGSZQKARKHG-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/355—Temporary coating
Definitions
- the invention is in the field of decorating vitreous articles with radiation curable inks.
- the invention relates to decoration of vitreous articles such as glass, with radiation curable inks which, to facilitate recycling, are capable of being chemically removed from the glass upon exposure to alkali for a specified period of time.
- ACL applied ceramic labeling
- VOC's volatile organic solvents
- UV radiation curable organic pigmented inks for the decoration of glass and ceramic ware
- Organic inks generally can be cured by exposure to radiation, such as ultraviolet radiation, thus obviating the need for high temperature baking.
- UV curable organic inks can be formulated to contain little or no VOC's or other nonaqueous solvents.
- Organic inks generally exhibit excellent adherence to glass.
- the invention is directed to a method for decorating a vitreous article comprising the steps of: a) applying to the vitreous article in a predetermined design a radiation curable ink composition which is (i) operable when cured to bond to the vitreous article, and (ii) strippable from the vitreous article upon exposure to alkali, b) curing the ink on the vitreous article by exposing it to the radiation by which it is curable, thereby bonding the ink to the vitreous article.
- the invention is also directed to a method for stripping decorative indicia from a vitreous article decorated with a radiation cured ink composition containing free acid groups which is (i) operable, when cured, to bond to the vitreous article, and (ii) strippable from the vitreous article upon exposure to alkali, comprising contacting the vitreous article with an aqueous alkaline solution containing 2-20% by weight alkali for a period of approximately 1 to 120 minutes.
- the invention is directed to a ink composition comprising, by weight of the total composition:
- the radiation curable ink compositions used in the method of the invention must be operable, when cured, to bond to the vitreous article, which is preferably glass.
- the ink compositions must be capable of adhering to glass to a degree sufficient to permit use as a commercial container used for beverages or other consumable materials.
- the polymerized ink compositions must be capable of being readily stripped or removed from the glass upon exposure of the decorated glass to alkali. Glass containers are filled; then they are decorated with the radiation curable ink compositions. After the beverage in the container is consumed, the container is returned to the filler. The decorative indicia is stripped from the glass upon exposure to alkali. The containers are then cleaned, sterilized, re-filled, redecorated, and shipped again.
- strippable ink compositions are made from radiation curable monomers and/or oligomers having at least one free acid group.
- free acid means an acidic group which is capable of reacting with alkali. Examples of such acidic groups are carboxylic acid groups, phosphoric acid groups, sulfonic acid groups and the like. Preferably, the acid group is a carboxylic acid group.
- the resulting polymerized coating contains free acidic groups which, upon exposure to alkali, react with the alkali to form a salt. As a result, the decorative indicia are much more readily removable from the glass.
- decorative indicia in order for radiation cured glass coatings to be considered "high performance" , decorative indicia must be capable of withstanding exposure to a concentrated aqueous alkali solution for a period of two to four hours.
- the radiation cured ink compositions of the invention must be completely removed from the glass container upon exposure to aqueous alkali before two hours has lapsed; after a period of about ito 120 minutes, preferably about 1 to 60 minutes, more preferably about 5 to 30 minutes.
- the ink compositions used in the method of the invention contain about 5-95 % , preferably about 10-85 % , more preferably about 15-75 % of a monomer, oligomer, or low molecular weight homo- or copolymer having at least one free acid group.
- a variety of such materials are suitable, provided they have at least one free acid group, such as a carboxylic acid, sulfonic acid, or phosphoric acid group.
- the phrase "having at least one free acid group” means that the monomer unit has at least one free acid group, or the oligomer contains at least one monomer unit containing a free acid group, or if a homo- or copolymer, at least one monomer unit thereof contains at least one free acid group.
- the ink composition contains a monomer or oligomer, in particular an ethylenically unsaturated monomer or oligomer having at least one free acid group.
- a monomer or oligomer in particular an ethylenically unsaturated monomer or oligomer having at least one free acid group.
- preferred monomers or oligomers include those having carboxylic acid functional groups such as:
- R ⁇ is H, a C ⁇ _ 30 straight or branched chain, substituted or unsubstituted, saturated or unsaturated alkyl, aryl, aralkyl, a pyrrolidone, or a substituted or unsubstituted aromatic, alicyclic, or bicyclic ring where the substituents are C ⁇ Q straight or branched chain alkyl, or halogen.
- R ! is as defined above
- R 2 is X-COOH wherein X is a C,. 30 straight or branched chain alkyl, aryl, arylalkyl, or - CH 2 CH 2 -O-)- n Y-COOH or - CH 2 CH 2 CH 2 - O-HY-GOOH wherein Y is a C,. 10 straight or branched chain alkyl and n is 1-10,000.
- the monomer or oligomer is of Formula II wherein R, is H or CH 3
- R 2 is X-COOH wherein X is a C,. 10 straight or branched chain alkyl, more preferably ethyl.
- R 2 is beta-carboxy ethyl, e.g. as in beta-carboxy ethyl acrylate, which is sold under the tradename B-CEA by UCB Radcure, Inc.
- B-CEA is a reactive monomer which contains both acrylate and carboxylic acid functionality, predominantly as the acrylic acid dimer, and, in particular, is a mixture of about 40% by weight B-carboxyethylacrylate, about 40% by weight higher homologs of acrylic acid, and about 20% by weight of acrylic acid.
- the B-carboxyethylacrylate component of this mixture has the following formula:
- carboxylic acid functional oligomers such as aromatic acid methacrylate half esters and aromatic acid acrylate half esters
- carboxylic acid functional oligomers are also suitable acid functional oligomers for use in the method of the invention.
- oligomers are partial esters of anhydride-containing copolymers such as those disclosed in U.S. patent no. 4,722,947 which is hereby incorporated by reference. These copolymers correspond to the following formula:
- R, and R 2 are each independently hydrogen, C]. 20 alkyl, aryl, alkaryl, cycloalkyl, or halogen; R 3 , R 4 , and R 5 (see below) are each independently hydrogen, C,_ 20 alkyl, or aryl; and R 6 is the same or different and is alkyl, aralkyl, or an alkyl substituted aralkyl radical containing about 1 to 20 carbon atoms as well as oxyalkylated derivatives thereof; and the subscripts x, y, z, and p are each whole numbers such that the sum of x, y, z, and p may range from about 3 to 20; and x, p, and y are each equal to or greater than 1 , and z may be 0; and B is AOCOCR 5 CH 2 wherein A is a linear or branched divalent alkylene of from about 1 to 20 carbon atoms, or an oxyalkylated derivative thereof as described for R 6
- aromatic partial esters of anhydride containing copolymers are those sold by Sartomer, Inc. under the Sarbox tradename, such as SB-400, SB-500, and SB-600.
- aromatic acid methacrylate half ester in ethoxylated trimethylolpropane triacrylate which is sold by Sartomer, Inc. under the tradename Sarbox 5B500E50.
- carboxylic acid functional monomers include acrylic acid, bisacrylaniidoacetic acid, 4,4-bis(4-hydroxphenyl)pentanoic acid, 3-butene-l ,2,3- tricarboxylic acid, 2-carboxyethyl acrylate, itaconic acid, methacrylic acid, 4- vinylbenzoic acid, and mixtures of these materials.
- Examples of monomers containing sulfonic acid groups include 2-acrylamido-2- methyl- 1-propanesulfonic acid; 2-methyl-2-propene-l-sulfonic acid. 2-propene-l-sulfonic acid. 4- styrenesulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyldimethyl-3- methacrylamidopropyl ammonium inner salt, 3-sulfopropyl methacrylate, vinysulfonic acid, and so on.
- Examples of monomers containing phosphoric acid functional groups include bis(2- methacryloxyethy ⁇ )phosphate, monoacryloxy ethyl phosphate, and so on.
- the ink compositions may contain about 5-95 % , preferably about 10-
- Suitable monomers include epoxides, cycloaliphatic epoxides, vinyl chloride, styrene, ethyl acrylate, vinyl acetate, difunctional acrylic monomers such as hydroxy alkyl acrylates, or hydroxy alkyl methacrylates, vinyl butyrate, vinyl methyl ether, methyl methacrylate, isobornyl acrylate, acrylonitrile, or mixtures thereof.
- Suitable polymers include oligomers, homo- or copolymers, terpolymers, graft copolymers of the above monomers provided they have a molecular weight of less than about 50,000, otherwise it is too difficult to effect polymerization, i.e. curing.
- Preferred are acrylate homopolymers or acrylate or methacrylate copolymers, preferably aery late or methacrylate copolymers.
- examples of such acrylate or methacrylate copolymers include epoxy acrylates, copolymers of propylene glycol and a dicarboxylic acid, urethane acrylates, and the like.
- the compositions contain one or more polymerizable reactants selected from the group consisting of urethane acrylate copolymers, tripropylene glycol acrylate, epoxy acrylate, and mixtures thereof.
- the radiation curable compositions of the invention contain about 5-
- compositions used in the invention preferably contain 5-95 % , preferably 5-
- pigments are suitable including organic and inorganic pigments. Examples of such pigments are set forth in U.S. patent no. 5, 178,952, which is hereby incorporated by reference.
- Inorganic pigments include extender pigments such are baryites, barium sulfate, calcium carbonate, talc, clay, alumina, titanium dioxide, white carbon, Chinese white, zinc sulfide, lithopone, ultramarine, Prussian blue, cobalt, chrome oxide, viridian chrome green yellows, oranges, and reds, cadmium, chromium, iron oxides, carbon black, metallic pigments, aluminum powder, bronze powder, zinc chromate, strontium chromate, zinc dust, copper, and so on.
- suitable organic pigments include azo pigments, indolinones, isoindolinones, vat pigments, the Lakes, pthalocyanine pigments and so on.
- the preferred pigment to impart white color to the ink composition is titanium dioxide.
- Preferred red and yellow pigments are isoindolinones and pyrrolopyrrols as disclosed in U.S. patent nos. 4,415,685; 4,579,949; 4,791,204; 4,666,455; 5,074,918; 4,783,540; 4,914,211; 4,585,878; as well as U.S. patent no. No. 5,571,359 of Kamen, et. al. , all of which are hereby incorporated by reference. These pyrrolopyrrols are generally of the formula:
- R t and R 2 are each independently alkyl, arylalkyl, aryl, substituted or unsubstituted isocyclic or heterocyclic aromatic radicals;
- R 3 and R 4 are each independently H, substituted or unsubstituted alkyl, alkoxycarbonyl, aroyl (e.g. benzoyl), arylalkyl (e.g. benzyl), aryl (e.g. phenyl), alkanoyl, C 5 . 6 cycloalkyl, alkenyl, alkynyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, or alkoxycarbonyl; and
- X is O or S.
- Rj and R 2 are each independently phenyl or naphthyl, R 3 and R 4 are hydrogen, and X is O.
- a red pigment is pyrrolo 3,4-C pyrrol- 1,4-dione, 2,5-dihydro-3,6-di-4-chlorophenyl which has a CAS number 84632-65-5 and is known by the common name C.I. pigment red 254.
- This pigment is commercially available from Ciba-Geigy Pigments Division, Newport, DE, under the tradename Irgazin DPP Red 80.
- Other Ciba-Geigy red pigments sold under the tradename Irgazin are also suitable.
- Suitable isoindolinones are as set forth in U.S. patent nos. 3,884,955, 3,867,404,
- isoindolinones are tetrachlorocyanobenzoic acid alkyl esters, particularly benzoic acid, 2,3,4,5-tetrachloro-6-cyano-methyl ester which is reacted with 2-methyl-l ,3-benzenediamine and sodium methoxide.
- This pigment composition has the common name C.I. Pigment Yellow 109 and is available commercially from Ciba-Geigy Pigments Division, Newport DE under the tradename Irgazin yellow 2GLTE.
- Other pigments in the Irgazin Yellow series as manufactured by Ciba-Geigy are also suitable.
- blue pigments marketed by Ciba-Geigy under the tradename Irgazin Blue X-3367, or by Whittaker, Clark, & Daniels under the tradename Ultramarine Blue 5009.
- the ink compositions used in the invention also preferably contain about 0.01- 10% of a defoaming agent, preferably a polyether-containing defoaming agent, which will cause the ink to apply smoothly on the glass substrate without bubbles or unevenness.
- a defoaming agent preferably a polyether-containing defoaming agent
- a wide variety of defoamers are suitable, but preferred are defoamers sold by BYK Chemie under the BYK tradename. Examples of such defoaming agents are alkylvinyl ether polymers set forth in U.S. Patent No. 5, 187,201 , which is hereby incorporated by reference. Examples of other defoamers include poly ethers such as BYK-052, BYK-053, and BYK-033.
- BYK-052 and -053 are polyethers such as polyethylene or polypropylene glycol ethers, and in particular, poly vinyl ethers. Also suitable is BYK-354 which is a polyacrylate solution, and BYK-022 which is a mixture of hydrophobic solids and foam destroying polysiloxanes in poly glycol.
- the poly ether defoaming agent is an alkoxylated alkyl phenol, more particularly a mixtures of petroleum distillates and an ethoxylated alkyl phenol, such as that sold by BYK- Chemie under the tradename BYK-033. Adhesion Promoter
- the ink compositions used in the invention also preferably contain about 0.0 1-
- silane adhesion promoter which will enhance adhesion of the cured resin to the glass surface.
- silanes are silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, amino silanes, or isocyanoto silanes.
- Suitable silanes include organo functional silanes of the formula:
- X is each independently CH 3 , Cl, OCOCH 3 , OC 2 H 4 OCH 3 , (0C 2 H 4 ) 2 OCH 3 . or
- R is a C,_ 20 straight or branched chain alkyl, preferably methyl or ethyl.
- Silanes having this formula are commercially available under the Dynasylan trademark from Huls, America, Inc. , Piscataway, New Jersey or Osi Specialities Inc.
- Other organofunctional silanes such as those disclosed in U.S. patent no. 5,221,560, which is hereby incorporated by reference, are also suitable.
- Such organosilanes are acryloxyfunctional silanes including 3-methacryloxypropyltrimethoxysilane, 3- acryloxypropyltrimethoxysilane, 2-methacryloxyethyltrimethyoxysilane, 2- acryloxyethyltrimethyoxy silane, 3 -methacryloxypropyltriethoxy silane, 3- acryloxypropyltrimethyoxysilane, 3-acryloxypropyltriethoxysilane, 2- methacryloxyethyltriethoxysilane, 2-methacryloxyethyltriethoxysilane, 2- acryloxyethyltriethoxysilane, etc.
- Suitable glycidoxy silanes include 3 - glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2-glycidoxyethyltriethoxysilane, 3- glycidoxypropyltrimethyl silane, and so on.
- Preferred for use in the compositions of the invention are acryloxy- functional silanes, isocyanato silanes, and amino silanes.
- the preferred acryloxy- functional silane is 3- methacryloxypropyl trimethoxy silane, which is sold by Huls America, Inc. under the tradename DYNASYLAN MEMO.
- the preferred amino silane is sold by Huls America, Inc. under the tradename
- the preferred isocyanoto silane is sold by Osi Specialities Inc. , under the tradename A- 1310.
- a mixture of the three silanes is preferred, generally 0.01-2% by weight of each.
- the ink compositions also preferably contain 0.01-20% , preferably 0.5-10%, more preferably 1-5 % by weight of a fluorinated surfactant.
- fluorinated surfactant means a fluorine containing compound having at least one lipophilic group or portion and at least one hydrophilic group or portion.
- fluorocarbon or fluorosilicone surfactants are most desirable. Suitable surfactants include those set forth in U.S. patent no. 4,961,976 which is hereby incorporated by reference. Preferred are fluorocarbon surfactants, such as those marketed under the Fluorad trademark by 3M Company.
- fluorochemical surfactants include fluorinated alkyl esters, fluorinated alkyl polyoxyethylene ethanols, and the like. Particularly preferred are nonionic fluorinated alkyl alkoxylates e.g. those marketed by 3M under the trademark FC-171.
- fluorinated C_.. 30 alkyl ethoxylates and propoxylates are preferred.
- the ink compositions preferably contain a photoinitiator which catalyzes the polymerization of the monomers upon exposure to the radiation by which the monomers are curable.
- a photoinitiator which catalyzes the polymerization of the monomers upon exposure to the radiation by which the monomers are curable.
- photo initiators free radical and cationic.
- Free radical initiators are more commonly used with ethylenically unsaturated monomers and oligomers, while cationic photo initiators are used with epoxy or vinyl ether functional resins.
- the compositions used in the invention contain free radical photoinitiators.
- Suitable free radical-type photoinitiators include carbonyl compounds such as ketones, acetophenones, benzophenones, and derivatives thereof.
- Such materials include, for example, methyl ethyl ketone; benzophenone; benzyl dimethyl ketal; 1-hydroxycyclohexylphenylketone; diethyoxyacetophenone; 2-methyl-l- (methylethiophenyl)-2-(4-morpholinyl)-l-propanone; 2-benzyl-2-N,N-dimethylamino- l ,4(4-morpholinophenyl)-l-butanone; 2,2-dimethoxy-2-phenyl acetophenone; 2-methyl-l- [4-(methylthio)phenyl]-2-morpholino propan-1-one; 2-hydroxy-2-methyl-l-phenyl- propan-1-one; 4-(2-hydroxyethoxy)phenyl-2(2-hyrroxy-2-methylpropyl)letone; and a mixture of bis(2,6-dimethyoxybenzoyl)-2-4-4-trimethylPentyl phosphine
- Preferred is a mixture of 25% bis(2,6- dimethyoxybenzoyl)-2-4-4-trimethylpentyl phosphine oxide and 75% 2-hydroxy-2- methyl-1-phenyl-propan-l-one, which is sold under the tradename Irgacure 1700 by Ciba-Geigy.
- cationically curable monomers or oligomers may be used in the compositions of the invention, for example less than about 10% , preferably less than about 5% by weight of the ink composition.
- cationically cured compositions generally exhibit a high bond strength to glass, such that if they are used in substantial amounts in the compositions of the invention, the ink will not be stripped from the glass upon exposure to alkali. If cationically curable monomers or oligomers are used in the compositions of the invention, it is desirable to use cationic photoinitiators.
- cationic photoinitiator means a molecule or ingredient which, upon excitation, undergoes a photochemical transformation which efficiently generates a species capable of initiating cationic polymerization. If the ink composition of the invention is cured by UV or actinic radiation rather than electron beam it is desirable to add a cationic photoinitiator which catalyzes cross-linking of the resin upon exposure to the radiation to which the resin is sensitive. On the other hand, if the ink compositions of the invention are cured with electron beam it may be possible to dispense with the cationic photoinitiator. Various types of cationic photoinitiators are suitable.
- ionic cationic photoinitiators such as onium salts or organometallic salts are suitable as well as nonionic cationic photoinitiators such as organosilanes, latent sulphonic acids and the like.
- Preferred are photosensitive onium salts, in particular, onium salts such as those disclosed in U.S. patent nos. 4,058,401, 4, 138,255, 4,161,478, 4, 175,972, all of which are hereby incorporated by reference.
- Triaryl sulphonium salts are most preferred, in particular triaryl sulphonium salts such as those sold by Union Carbide under the tradename Cyracure UVI 6990 and 6974.
- ferrocenium salts such as those sold under the Irgacure tradename by Ciba-Geigy, in particular Irgacure 261.
- Sulphonyloxy ketones and silyl benzyl ethers are also good cationic photoinitiators.
- a detailed analysis of the mechanism of cationic curing is disclosed in "Photosensitized Epoxides as a Basis for Light-Curable Coatings" by William R. Watt, American Chemical Society Symposium, Ser.
- Photosensitive onium salts are used as photoinitiators in cationic curing, in particular, onium salts such as those disclosed in U.S. patent nos. 4,058,401, 4,138,255, 4, 161,478, 4,175,972, all of which are hereby incorporated by reference.
- Triaryl sulphonium salts are most preferred, in particular triaryl sulphonium salts such as those sold by Union Carbide under the tradename Cyracure UVI 6990 and 6974.
- the photoinitiator is generally present at about 0.1-15%, preferably about 0.5- 12% , more preferably about 0.5-10% by weight of the total composition.
- the preferred ink compositions used in the invention comprise: 5-95 % of an ethylenically unsaturated monomer or oligomer containing at least one free acid group, 5-95% pigment, and
- the ink composition comprises, in addition, an ingredient selected from the group consisting of about 0.1-25% of a silane adhesion promoter, about 0.01-10% of a poly ether defoaming agent, about 0.01-20% of a fluorinated surfactant, and about 0.1-1 % of a photoinitiator.
- ceramic or “vitreous article” when used in accordance with the invention shall mean glass, ceramic, tile, and similar vitreous materials.
- the articles which may be decorated or printed according to the method of the invention may be in any shape or form, such as a container, sheet, tile, figurine, or the like.
- the article is made of glass or ceramic and is a container, such as a cosmetic or beverage container.
- the ink composition is applied to the article to be decorated in a predetermined design using a variety of printing methods including screen printing, offset printing, gravure, hand painting and the like. After the ink is applied the substrate or article is irradiated with UV or actinic radiation using a conventional UV light source.
- UV means ultraviolet light which generally has a wavelength of 4 to 400, preferably 325 to 400 nanometers.
- actinic means radiation having a wavelength of 200 to 600 nanometers.
- Electron beam may be used instead of a UV light source. If a UV conveyer is used, it is set up so that the substrate passes through the beam of radiation for an amount of time appropriate to completely cure the ink composition and cause it to adhere to the substrate. If desired, the substrate may be moved through the conveyer in one or more passes to achieve the required curing. The appropriate time varies depending on the ink formula, but generally curing is complete in a period of time ranging from fractions of a second to 30 minutes.
- the ink is completely cured and fused to the substrate surface.
- the decorated substrate is subjected to post-UV cure heating at a temperature of 90 to 2000 C , preferably 100-
- ink compositions are well suited for use in automated systems such as the multiple color printing apparatus disclosed in copending application serial no. 432,485, filed May 1 , 1995 by Kamen, et al. , entitled “Apparatus and Method For Screen Printing Radiation Curable Compositions", or with the methods disclosed in U.S. patent no. 5,562,951, both of which are hereby incorporated by reference.
- the ink composition of the invention without the pigment and print it on the glass substrate in predetermined design according to the methods described above.
- a substrate such as a container may be decorated in a pre-determined design by silk screening the unpigmented ink composition on the substrate and curing with the appropriate radiation.
- a layer of hot stamping foil is then compressed against the substrate with a press which is heated to a temperature sufficient to cause the hot stamping foil to adhere to the printed ink design but not to the ink-free areas of the glass.
- Hot stamping foil is generally a laminate comprised of a carrier material (often polyester or a similar material capable of release), a release film between the carrier and a subsequent decorative coat which is usually color or a metallized coat, most often aluminum or colored aluminum.
- the foil may contain other optional layers such as one or more protective layers, hot melt adhesive layers, etc. between the metallized layer or layers and the carrier material.
- hot stamping foil can be defined as a multilayer web comprised of a backing film carrier, a release coating, one or more protective top coatings, one or more color coatings, and a hot melt adhesive in that order. The hot stamping foil is then compressed against the container with the hot melt adhesive layer being compressed against the substrate.
- the compress which may be a standard hot stamping press or a hand held press, is heated to a temperature sufficient to cause the hot melt adhesive layer of the hot stamping foil to adhere to the ink decorated portion of the substrate. Generally this temperature ranges from about 250 to 4000 F. Temperatures higher than this may cause deterioration of the hot stamping foil.
- the application of heat causes the adhesive side of the hot stamping foil to become adhesively adhered to the ink design but not to the ink- free areas of the substrate. When the compress is removed, a portion of the foil laminate adheres to the ink decoration but not to the ink free areas of the glass.
- the hot melt adhesive layer adhered to the ink design on the substrate is the hot melt adhesive layer, the color coatings, and the protective top coatings, in that order, of the hot stamping foil.
- Portions of the release coating may or may not be adhered to the protective top coating because the release coating is designed to melt upon application of heat and cause the polyester carrier backing layer to release from the protective top coat layer and some remnants may remain.
- the resulting hot stamped substrate exhibits a metallic gold, silver, or colored appearance depending on the color of the hot stamping foil.
- a decorated substrate which has a two tone effect where all or a portion of the colored ink on the substrate is hot stamped.
- a pigmented ink composition is applied to the substrate in a predetermined design and cured by exposing it to the radiation by which it is curable for a time sufficient to effect complete cure.
- Hot stamping foil is applied as described above to either the entire ink design or to only a part (i.e. complete or partial registration). If the hot stamping foil is applied in partial registration, or applied to a portion of the pigmented ink design, a pleasant two tone effect is achieved. Many times it is more economical to print the entire design on the substrate using colored ink and then hot stamp over the desired portion of the design, rather than applying clear ink and hot stamping, and then printing colored ink in the desired design in a second application.
- the ink compositions of the invention provide sufficient adhesion to glass as well as exhibiting sufficient resistance to scuffing and scratching to make the decorated articles suitable for use on commercial beverage and cosmetic bottles.
- the ink compositions of the invention can be removed from glass upon exposure of the glass to alkali.
- the free acid groups found in the polymerized ink composition are capable of reacting with the hydroxyl groups of the base to form a salt which is easily stripped or removed from the glass.
- the aqueous alkaline solution comprises about 1-20% , preferably about 2-15 % , more preferably about 2-12% by weight alkali.
- Suitable alkali materials include metal hydroxides (e.g. alkali metal and alkaline earth metal hydroxides) such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like.
- the cured ink compositions should be removed from the glass upon exposure to the aqueous alkali after a period of about 1 to 120, preferably about 1-60, more preferably about 1-30 minutes.
- the glass substrate is generally immersed in the aqueous alkali solution for the appropriate time period, after which the ink compositions are removed from the glass surface.
- the glass container is subjected to the aqueous alkaline solution at a temperature of 60 to 1000 C , more preferably 70 to 950 C , most preferably 72 to 900 C.
- the ink composition is removed from the glass containers after exposure of the glass to a 4 % (approximately) aqueous solution of sodium hydroxide at a temperature of 70 to 1000 C, after 1-15 minutes.
- the decorating method and compositions of the invention are excellent for use on glass containers used in the returnable beverage market.
- the decorative indicia applied according to the invention remains on the glass for the useful commercial life of the container, yet can be easily removed upon exposure to an aqueous alkali solution. This eliminates the need for paper labels and decals, which results in a significant cost savings.
- the indicia are much more aesthetically pleasing, similar to the aesthetics achieved with ACL.
- beverage and cosmetic manufacturers are able to offer glass containers that provide aesthetics similar to ACL, with indicia that can be easily removed upon exposure to alkali solutions when the glass container is returned to the filler.
- a white ink composition was made as follows: grams wt% Dipentaerythritol pentaacrylate 1 25.0 24.8
- Beta carboxyethyl acrylate 4 10.0 9.9
- Aromatic urethane acrylate with polyacrylated polyol diluent 5 10.0 9.9
- a blue ink composition was made as follows: grams wt% Dipentaerythritol pentaacrylate 1 25.0 23.9
- Beta carboxyethyl acrylate 4 10.0 9.6
- Aromatic urethane acrylate with polyacrylated polyol diluent 5 10.0 9.6
- a white ink composition was made as follows:
- Monofunctional acrylate resin 3 15.0 14.7 Epoxy acrylate + tripropylene glycol acrylate 4 5.0 4.9
- Titanium dioxide 15.0 14.7
- Ciba-Geigy Corp Mixture of 25 % by weight bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl phosphine oxide and 75% by weight 2-hydroxy-2-methyl-l- pheny lpropan- 1 -one .
- photoinitiator 6 BYK-Chemie, A mixture of 92% by weight petroleum distillates and 5% by weight ethoxylated alkyl phenol (defoaming agent)
- An ultramarine blue composition was made as follows:
- Beta carboxyethyl acrylate 2 30.0 29.1
- a white ink composition was made as follows:
- Epoxy acrylate + tripropylene glycol acrylate 2 10.0 9.1
- Beta-carboxyethyl acrylate 3 30.0 27.3
- Aromatic oligomer containing pendant carboxy functional groups Henkel Corporation (polymerizable reactant with free acid group)
- composition was made by combining the ingredients and mixing the ingredients well.
- a blue ink composition was made according to the following formula:
- Ciba-Geigy Co ⁇ Mixture of 25 % by weight bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl phosphine oxide and 75% by weight 2-hydroxy-2-methyl-l- phenyl-propan-1-one. (photoinitiating agent) 5 9 BYK-Chemie, A mixture of 92% by weight petroleum distillates and 5% by weight ethoxylated alkyl phenol (defoaming agent)
- the white ink composition of Example 2 was applied to alcoholic beverage 5 bottles by screen printing with a 230 mesh screen using an autoroU M-25 semiautomatic screen printing machine.
- the ink on the bottle was screened by exposure to UV light from a P600 power supply having a 9mm. D bulb. The curing speed was less than one second per bottle.
- the blue ink of Example 2 was screened onto the bottle in partial registration with the cured white ink.
- the ink was cured upon exposure to the UV light source.
- the bottle was then subjected to post heat curing at a temperature of 100° C. for 30 minutes.
- the indicia adhered well to the bottle and exhibited bright, true coloration.
- Example 7 The finished bottles decorated in accordance with Example 7 were immersed in a water bath containing 4% sodium hydroxide at a temperature of 72° C. The cured inks were completely removed from the bottles after 4 minutes.
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Surface Treatment Of Glass (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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US868409 | 1992-04-14 | ||
US86230497A | 1997-05-23 | 1997-05-23 | |
US862304 | 1997-05-23 | ||
US08/868,409 US6093455A (en) | 1997-05-23 | 1997-06-03 | Method and compositions for decorating glass |
PCT/US1998/010624 WO1998052700A1 (en) | 1997-05-23 | 1998-05-22 | Method and compositions for decorating glass |
Publications (2)
Publication Number | Publication Date |
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EP1003613A1 true EP1003613A1 (en) | 2000-05-31 |
EP1003613A4 EP1003613A4 (en) | 2002-07-17 |
Family
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Family Applications (1)
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EP98923736A Withdrawn EP1003613A4 (en) | 1997-05-23 | 1998-05-22 | Method and compositions for decorating glass |
Country Status (12)
Country | Link |
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EP (1) | EP1003613A4 (en) |
JP (1) | JP2002511805A (en) |
AU (1) | AU751447B2 (en) |
BR (1) | BR9809156A (en) |
CA (1) | CA2290430C (en) |
DE (1) | DE1003613T1 (en) |
ES (1) | ES2161662T1 (en) |
IL (1) | IL133047A0 (en) |
NO (1) | NO995719L (en) |
TR (1) | TR199902877T2 (en) |
TW (1) | TW589353B (en) |
WO (1) | WO1998052700A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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ES2285868T3 (en) * | 1998-12-22 | 2007-11-16 | Vitro Europa, Ltd. | COMPOSITION OF CURABLE PAINTING BY ULTRAVIOLET RADIATION AND PROCESS FOR APPLICATION IN GLASS SUBSTRATES. |
US6413618B1 (en) | 1999-05-11 | 2002-07-02 | Congoleum Corporation | Laminated glass floor tile and flooring made therefrom and method for making same |
JP2006328227A (en) * | 2005-05-26 | 2006-12-07 | Fujifilm Holdings Corp | Ink composition, image-forming method and recorded article |
WO2009101401A1 (en) * | 2008-02-11 | 2009-08-20 | Sun Chemical B.V. | Inkjet inks and printing |
GB0805495D0 (en) * | 2008-03-26 | 2008-04-30 | Sun Chemical Bv | An ink jet-printable composition and a masking process |
AT506074B1 (en) | 2008-06-12 | 2009-06-15 | Durst Phototech Digital Tech | ADHESION ADDITIVE ADDITION TO AN INK FOR PRINTING GLASS |
CA2738808A1 (en) * | 2008-10-20 | 2010-04-29 | Plastipak Packaging, Inc. | Digital printing plastic containers with improved adhesion and recyclability |
KR101175056B1 (en) | 2012-05-14 | 2012-08-23 | 강양석 | Method for manufacturing of reinforced frame and the reinforced frame manufactured same method |
DE102013207799A1 (en) * | 2013-04-29 | 2014-10-30 | Krones Ag | Direct printing method for printing on plastic containers with cover layer |
DE102013207809A1 (en) * | 2013-04-29 | 2014-10-30 | Heidelberger Druckmaschinen Ag | Direct printing with underlayer |
JP6606393B2 (en) * | 2015-09-30 | 2019-11-13 | 大日本塗料株式会社 | Active energy ray-curable ink composition for decorating inorganic substrates |
KR102210938B1 (en) * | 2017-11-28 | 2021-02-01 | 주식회사 엘지화학 | A composition for shielding a waveguide edge with excellent adhesion |
CN110577367B (en) * | 2018-08-13 | 2022-03-22 | 蓝思科技(长沙)有限公司 | Glass protection processing technology, glass and equipment |
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US3872044A (en) * | 1972-09-25 | 1975-03-18 | Ferro Corp | Thermoplastic screen process inks |
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-
1998
- 1998-05-22 EP EP98923736A patent/EP1003613A4/en not_active Withdrawn
- 1998-05-22 TR TR1999/02877T patent/TR199902877T2/en unknown
- 1998-05-22 ES ES98923736T patent/ES2161662T1/en active Pending
- 1998-05-22 DE DE1003613T patent/DE1003613T1/en active Pending
- 1998-05-22 CA CA002290430A patent/CA2290430C/en not_active Expired - Fee Related
- 1998-05-22 BR BR9809156-5A patent/BR9809156A/en unknown
- 1998-05-22 JP JP55073098A patent/JP2002511805A/en not_active Ceased
- 1998-05-22 AU AU75955/98A patent/AU751447B2/en not_active Ceased
- 1998-05-22 IL IL13304798A patent/IL133047A0/en unknown
- 1998-05-22 WO PCT/US1998/010624 patent/WO1998052700A1/en active IP Right Grant
- 1998-05-28 TW TW087107974A patent/TW589353B/en not_active IP Right Cessation
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1999
- 1999-11-22 NO NO995719A patent/NO995719L/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
AU7595598A (en) | 1998-12-11 |
NO995719L (en) | 2000-01-24 |
WO1998052700A1 (en) | 1998-11-26 |
CA2290430C (en) | 2004-08-17 |
NO995719D0 (en) | 1999-11-22 |
EP1003613A4 (en) | 2002-07-17 |
JP2002511805A (en) | 2002-04-16 |
DE1003613T1 (en) | 2001-09-20 |
AU751447B2 (en) | 2002-08-15 |
BR9809156A (en) | 2000-08-01 |
CA2290430A1 (en) | 1998-11-26 |
ES2161662T1 (en) | 2001-12-16 |
TR199902877T2 (en) | 2000-06-21 |
TW589353B (en) | 2004-06-01 |
IL133047A0 (en) | 2001-03-19 |
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