WO2004026978A1 - Radiation curable inkjet inks compositions - Google Patents
Radiation curable inkjet inks compositions Download PDFInfo
- Publication number
- WO2004026978A1 WO2004026978A1 PCT/GB2003/003836 GB0303836W WO2004026978A1 WO 2004026978 A1 WO2004026978 A1 WO 2004026978A1 GB 0303836 W GB0303836 W GB 0303836W WO 2004026978 A1 WO2004026978 A1 WO 2004026978A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- ink
- compounds
- mono
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 230000005855 radiation Effects 0.000 title claims abstract description 13
- 239000000976 ink Substances 0.000 title description 76
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 165
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003086 colorant Substances 0.000 claims abstract description 18
- 239000000049 pigment Substances 0.000 claims description 85
- -1 phenoxy ethyl Chemical group 0.000 claims description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000007641 inkjet printing Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- 229940059574 pentaerithrityl Drugs 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 claims description 3
- AXZCJGWLPJEZHS-UHFFFAOYSA-N 1-methoxy-2,2-dimethylpropane-1,3-diol Chemical compound COC(O)C(C)(C)CO AXZCJGWLPJEZHS-UHFFFAOYSA-N 0.000 claims description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 3
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- NPRMIIDMJWVVPM-UHFFFAOYSA-N 3-ethoxy-2-nonylphenol Chemical compound CCCCCCCCCC1=C(O)C=CC=C1OCC NPRMIIDMJWVVPM-UHFFFAOYSA-N 0.000 claims description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 229940097275 indigo Drugs 0.000 claims description 3
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229940068917 polyethylene glycols Drugs 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIXZBXRQFZHIT-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol Chemical compound COCC(O)COC(C)COC(C)CO XUIXZBXRQFZHIT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012958 Amine synergist Substances 0.000 claims description 2
- 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 claims description 2
- 239000012949 free radical photoinitiator Substances 0.000 claims description 2
- 239000001056 green pigment Substances 0.000 claims description 2
- 239000001053 orange pigment Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000001054 red pigment Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229940048053 acrylate Drugs 0.000 description 105
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229940110337 pigment blue 1 Drugs 0.000 description 2
- 229940099800 pigment red 48 Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- UCEOKYLZELCHSG-UHFFFAOYSA-N 1-diazoxanthene Chemical compound C1=CC=C2C=C3C(=[N+]=[N-])C=CC=C3OC2=C1 UCEOKYLZELCHSG-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- XVVGBFGMWMOBLB-UHFFFAOYSA-N 2-(4-chlorophenyl)-2-oxoacetaldehyde Chemical compound ClC1=CC=C(C(=O)C=O)C=C1 XVVGBFGMWMOBLB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- RXDYOLRABMJTEF-UHFFFAOYSA-N 2-chloro-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Cl)C(=O)C1=CC=CC=C1 RXDYOLRABMJTEF-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- QPCZLWABNCOSEF-UHFFFAOYSA-N 2-diazopyranthren-1-one Chemical class [N+](=[N-])=C1C(C=2C=C3C=CC4=CC5=C6C=CC=CC6=CC6=CC=C7C=C(C2C=C1)C3=C4C7=C65)=O QPCZLWABNCOSEF-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- XQGDNRFLRLSUFQ-UHFFFAOYSA-N 2H-pyranthren-1-one Chemical class C1=C(C2=C3C4=C56)C=CC3=CC5=C3C=CC=CC3=CC6=CC=C4C=C2C2=C1C(=O)CC=C2 XQGDNRFLRLSUFQ-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- DDLXBFDBKPCGQK-UHFFFAOYSA-N 3-hydroxy-2-methoxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(CO)(OC)C(=O)C1=CC=CC=C1 DDLXBFDBKPCGQK-UHFFFAOYSA-N 0.000 description 1
- SOFRHZUTPGJWAM-UHFFFAOYSA-N 3-hydroxy-4-[(2-methoxy-5-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound COc1ccc(cc1N=Nc1c(O)c(cc2ccccc12)C(=O)Nc1cccc(c1)[N+]([O-])=O)[N+]([O-])=O SOFRHZUTPGJWAM-UHFFFAOYSA-N 0.000 description 1
- WFFZGYRTVIPBFN-UHFFFAOYSA-N 3h-indene-1,2-dione Chemical compound C1=CC=C2C(=O)C(=O)CC2=C1 WFFZGYRTVIPBFN-UHFFFAOYSA-N 0.000 description 1
- ULVDMKRXBIKOMK-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2,3-dihydroisoindol-1-one Chemical class ClC1=C(Cl)C(Cl)=C2CNC(=O)C2=C1Cl ULVDMKRXBIKOMK-UHFFFAOYSA-N 0.000 description 1
- FWTBRYBHCBCJEQ-UHFFFAOYSA-N 4-[(4-phenyldiazenylnaphthalen-1-yl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 FWTBRYBHCBCJEQ-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 150000005125 dioxazines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical class C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- BASGHVRDJXCOQO-UHFFFAOYSA-N phenyl-[4-(trichloromethyl)phenyl]methanone Chemical compound C1=CC(C(Cl)(Cl)Cl)=CC=C1C(=O)C1=CC=CC=C1 BASGHVRDJXCOQO-UHFFFAOYSA-N 0.000 description 1
- 229940067265 pigment yellow 138 Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 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
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- 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
Definitions
- Ink jet printing is a non-contact method by which droplets of ink are ejected through a fine nozzle onto a substrate.
- ink jet printing There are many demanding performance requirements for inks used in ink jet printing. For example they should provide sharp, non-feathered images having good water, solvent- light- and ozone fastness, attractive colour and high optical density.
- Further desirable properties for ink jet printing inks include a fast dry time (to facilitate high-speed printing), a low viscosity to enable the inks to be used in a wide range of ink jet printers, excellent mechanical resistance (to avoid the prints being rubbed off), low curl and good adhesion to a range of substrates.
- organic solvents are included in ink jet printing inks to lower their viscosity.
- US 4,303,924 discloses radiation curable ink jet printing inks containing organic solvent and large proportions of trifunctional monomers.
- WO 02/38688 discloses low viscosity radiation curable compositions which are free from solvent and have low proportions of difunctional and tri- or higher functional monomers.
- a non- aqueous, substantially solvent-free, radiation curable ink having a viscosity less than 30m Pa.s at 60°C, comprising: (i) a colorant (ii) a photo-initiator; and (iii) a mixture of (meth)acrylate compounds; wherein:
- the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more
- the value of Formula (1) is from 40 to 60, more preferably from 42.6 to 57, especially from 49 to 55.8.
- the amount of colorant in the ink is preferably from 0.1 to 14%, more preferably from 1 to 10% and especially from 1.1 to 8% by weight, relative to the total weight of the ink.
- the colorant is not white.
- Preferred colorants are yellow, magenta, cyan, black, blue, indigo, violet, green, orange, red and mixtures comprising two or more thereof.
- the ink is free from titanium dioxide.
- the colorant is preferably a dye, a pigment or a mixture thereof. More preferably the colorant is a pigment.
- Preferred dyes and pigments are free from ionic groups, for example disperse dyes and water-insoluble pigments are especially preferred colorants.
- Preferred pigments are organic or inorganic.
- the pigment is preferably in the form particles which are small enough to pass through the very fine nozzles used in the phntheads of ink jet printers. Typically these nozzles are half the diameter of a human hair.
- the average particle size of the pigment is preferably from 0.003 to 15 ⁇ m, more preferably from 0.004 to 5 ⁇ m and especially from 0.005 to 1 ⁇ m.
- Pigment particle sizes outside these ranges may be used where printheads have particularly large nozzle diameters.
- Very fine dispersions of pigments and methods for their preparation are disclosed in, for example, EP 0 776 952, US 5,538,548, US 5,443,628, EP 0 259 130, US 5,285,064, EP 0 429 828 and EP 0 526 198.
- inorganic pigments include carbon black, titania, iron oxide, zinc oxide and mixtures thereof.
- organic pigments include phthalocyanines, anthraquinones, perylenes, carbazole, monoazo and disazobenzimidazolones, isoindolinones, monoazonaphthols, diarylidepyrazolones, rhodamines, indigoids, quinacridones, diazopyranthrones, dinitranilines, pyrazolones, dianisidines, pyranthrones, tetrachloroisoindolinones, dioxazines, monoazo acrylides, anthrapyrimidines and mixtures thereof.
- carbon black pigments examples include Regal 400R, MogulTM L, ElftexTM 320 from Cabot Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550, PrintexTM 25, PrintexTM 35, PrintexTM 55 and PrintexTM 150T from Degussa Co., and Pigment Black 7. Further examples of pigments include CI. Pigment Yellow 17, CI. Pigment Blue 27. CI. Pigment Red 49:2, CI. Pigment Red 81 :1 , CI. Pigment Red 81 :3, CI. Pigment Red 81 :x, CI. Pigment Yellow 83, CI. Pigment Red 57: 1 , CI. Pigment Red 49:1 , CI. Pigment Violet 23, CI.
- Pigment Black 1 1 CI. Pigment Metal 1 , CI. Pigment Metal 2, CI. Pigment Yellow 128, CI. Pigment Yellow 93, CI. Pigment Yellow 74, CI. Pigment Yellow 138, CI. Pigment Yellow 139, CI. Pigment Yellow 154, CI. Pigment Yellow 185, CI. Pigment Yellow 180, CI. Pigment Red 122, CI. Pigment Red 184, and bridged aluminium phthalocyanine pigments.
- the especially preferred pigments are Pigment Yellow 128, 93, 17, 74, 138, 139, 154, 185, 180; Pigment Red 122, 57:1 , 184; Pigment Blue 15:3, 15:4 and carbon black.
- Preferred dyes include azo, diazo, xanthene, anthraquinone, triaryl methane, azine, thiazine, phthalocyanine and nigrosine types.
- Dyes may be used singly or in combination with other dyes and/or pigments. Dyes are preferably disperse or solvent soluble, examples of which may be selected from The Colour Index especially the 3 rd edition, 1982, pages 147-263. Dyes can be metalised or non-metalised.
- the ink optionally further contains a dispersant.
- a dispersant is often not necessary because the dye may be soluble in the formulation.
- the pigment is self-dispersible (e.g. the pigment carries dispersing groups or is surface modified to be self-dispersible) no further dispersant is needed.
- a dispersant is preferably included in the ink to assist storage stability.
- Suitable dispersants include, for example, polyester, polyurethane and polyacrylate dispersants, especially those in the form of high molecular weight block copolymer.
- dispersants examples include DisperbykTM (ex BYK Chemie) and SolsperseTM (ex Avecia) dispersants.
- DisperbykTM Ex BYK Chemie
- SolsperseTM Ex Avecia
- a detailed list of non-polymeric as well as some polymeric dispersants appears in, for example, McCutcheon's Functional Materials, North American Edition, Manufacturing Confectioner Publishing Co., Glen Rock, N.J., pp.110- 129 (1990), the entire disclosure of which is incorporated herein by reference.
- Dispersants suitable for use with pigments are also disclosed in DE 19636382, US 5,720,802, US 5,713,993, PCT/GB95/02501 , US 5,085,689 and GB 2303376. When the ink contains a dispersant this is preferably present in an amount of 50 to 150% by weight relative to the weight of colorant.
- self-dispersing pigments include surface treated carbon blacks carrying carboxy, sulphonate and/or ethylene oxide groups.
- the pigment and dispersant are preferably added to the ink as a mixture.
- a mixture of a pigment and a dispersant may be made by milling pigment in a small amount of the (meth)acrylate components c), d) and e) with a milling media, e.g. glass beads.
- the pigment dispersion is then typically screened and "let down" by slowly adding the remaining ink components.
- the amount of photo-initiator in the ink is preferably 0.1 to 15%, more preferably 3 to 12% by weight, relative to the total weight of the ink.
- Preferred photo-initiators include alpha diketones, monoketals of alpha-diketones or ketoaldehydes, acyloins and their corresponding ethers, chromophore-substituted halo-s-triazines, and chromophore- substituted halomethyl-oxadiozoles.
- photo-initiators include acetophenone, propiophenone, 2-phenyl-acetophenone, 2-chloro-2-phenyl-acetophenone, 2-2-dichloro-2-phenyl-acetophenone, 2-butoxy-2-phenyl acetophenone, 2,2-dimethoxy-2- phenyl-acetophenone, 2,2-diethoxy-acetophenone, 2-methylol-2-methoxy-2-phenyl- acetophenone, benzophenone, 4-trichloromethyl benzophenone, indenone, 1-3- indanedione, fluorenone, xanthone, thioxanthone, 2-chlorothioxanthone, anthraquinone, 2-ethylanthraquinone, biacetyl, glyoxal, 1 ,2-indanedione, p-chlorophenyl-glyoxal, benzil, campho
- photo-initiators particularly suitable for use in the present invention include SpeedcureTM ITX, and IrgacureTM 369.
- the ink optionally further contains one or more co-initiators or amine synergists in order to improve cure rate. Examples include isopropylthioxanthone, ethyl-4-(dimethylamine) benzoate, 2-ethyl hexyl dimethylaminobenzoate and dimethylaminoethyl methacrylate.
- the photo-initiator is other than a cationic photo-initiator.
- the photo-initiator is a free radical photo-initiator.
- the photo-initiator is soluble in the ink.
- a single photo-initiator may be used although it is preferable that the photo-initiator is a mixture of two or more photo-initiators because this can lead to a broader spectral response, improved depth of cure and improved cure rate with opacifying pigments such as carbon black.
- the ink further comprises a stabiliser to improve the storage stability of the ink and prevent premature curing.
- the stabiliser is preferably an antioxidant, a radical trap, a radical quencher or the like, e.g. a phenol, thiol, quinone, hydroquinone, amine, xanthate or an N-alkyl or N-aryl aniline. Too much stabiliser will prevent cure entirely.
- preferred amounts of stabiliser are from 0 to 10%, more preferably from 0.01 to 5%, and especially from 0.1 to 3% by weight relative to the total weight of the ink. Mixtures of stabilisers are preferable for the best ink storage lifetime.
- the ink is curable by actinic radiation or particle beam, especially by UV or electron beam radiation.
- Mono (meth)acrylate compounds have one (and only one) acrylate or methacrylate group. This group is, as is known in the art, is polymerisable when irradiated in the presence of a photo-initiator.
- (Meth)acrylate groups are represented by the formula:
- R is H or methyl
- the mono (meth)acrylate compound is preferably a monomer.
- mono (meth)acrylate monomers include cyclic trimethylolpropane formal (meth)acrylate, ethoxylated tetra hydrofurfuryl (meth)acrylate, phenoxy ethyl (meth)acrylate, trimethylol propane formal (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, monomethoxy neopentyl glycol propoxylate mono (meth)acrylate, monomethoxy tripropylene glycol mono (meth)acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, iso- decyl (meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, tridecyl (meth)acrylate, iso-bomyl (meth)acrylate, eth
- Preferred mono (meth)acrylate monomers include lauryl (meth)acrylate, tetrahydro furfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, iso-octyl (meth)acrylate, iso-decyl (meth)acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, isobomyl (meth)acrylate, cyclic trimethylol propane formal (meth)acrylate.
- the one or more monomer (meth)acrylate compounds is or comprises isobomyl acrylate.
- Di (meth)acrylate compounds have two (and only two) groups selected from acrylate and methacrylate.
- Preferred di (meth)acrylate compounds are di (meth)acrylate monomers, for example di(meth)acrylates of 1 ,4 butane diol, 1-6 hexane diol, neopentyl glycol, mono, di, tri and poly ethylene glycols, mono, di, tri and poly propylene glycols, mono methoxy ethoxylated trimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1 ,2 butylene glycol and ethoxylated hexane diol.
- the one or more di(meth)acrylate compounds is or comprises 1 ,6 hexane diol diacrylate.
- the compound(s) having three or more (meth) acrylate groups have three or more groups selected from acrylate and methacrylate.
- the compound having three or more (meth)acrylate groups is preferably a monomer, oligomer or polymer, preferred examples of which include trimethylol propane tri(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate, propoxylated trimethylol propane tri(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated di-pentaerylthritol tetra (meth)acrylate, tetra methylol methane t
- the one or more compounds comprising three or more (meth)acrylate groups is or comprises trimethylol propane triacrylate and/or ethoxylated trimethylol propane triacrylate.
- Inks which contain acrylates polymerise more quickly than those containing methacrylates when exposed to actinic or particle beam radiation. Consequently, the amount of methacrylate is preferably not greater than 20%, more preferably not greater than 10% and especially not greater than 5% of component (iii). It is particularly preferred that component (iii) contains no methacrylate.
- the ink further comprises a polymer or oligomer containing no (meth)acrylate groups.
- a polymer or oligomer containing no (meth)acrylate groups is present in the ink at from 0 to15%, more preferably from 0 to 10% and most preferably from 0 to 5% by weight relative to the total weight of the ink.
- Inks of the present invention are substantially solvent free. That is to say no solvent or water is present in the ink except for trace amounts which may be present as impurities in any of the ink components. Preferably any such residues are less than 2%, more preferably less than 0.5% and especially less than 0.01 % by weight relative to the total weight of ink. As hereinbefore described inks of the present invention are particularly suitable for use in ink jet printing. A preferred ink jet type for inks of the present invention is piezo ink jet printing.
- the viscosity of the inks of the present invention are preferably 1 to 30 mPa.s, more preferably from 2 to 25 mPa.s at 60°C
- the ink composition may optionally have a higher viscosity at room temperature provided that the final ink meets the above viscosity requirements at the above temperature.
- the surface tension of the ink of the present invention is preferably below 40 dynes/cm.
- Inks of the present invention are preferably free from particulate impurities that would tend to block an ink jet nozzle.
- the ink is preferably filtered through a filter with a pore size of less than 10um, more preferably less than 34m and especially less than 14 .
- a particularly preferred ink according to the invention is a non-aqueous, substantially solvent-free, radiation curable ink having a viscosity of 1 to 30m Pa.s at 60°C comprising:
- the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth )acry late compounds, di (meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1 ) is from 40 to 60:
- the photo-initiator is present in the ink in an amount of 3 to 12% by weight relative to the total weight of ink;
- the one or more mono (meth)acrylate compounds are selected from the group consisting of cyclic trimethylolpropane formal (meth)acrylate, ethoxylated tetra hydrofurfuryl (meth)acrylate, phenoxy ethyl (meth)acrylate, trimethylol propane formal (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, monomethoxy neopentyl glycol propoxylate mono (meth)acrylate, monomethoxy t propylene glycol mono (meth)acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, iso-decyl (meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, tridecyl (meth)acrylate, iso-bomyl (meth)acrylate, ethoxyl nonyl
- the one or more di (meth)acrylate compounds are selected from the group consisting of di(meth)acrylates of 1 ,4 butane diol, 1-6 hexane diol, neopentyl glycol, mono, di, tri and poly ethylene glycols, mono, di, tri and poly propylene glycols, mono methoxy ethoxylated trimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1 ,2 butylene glycol and ethoxylated hexane diol and mixtures thereof; and
- the one or more compounds having three or more (meth)acrylate groups are selected from the group consisting of trimethylol propane tri(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate, propoxylated trimethylol propane tri(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated di- pentaerylthritol tetra (meth)acrylate, tetra methylol methane tetra
- the mixture of (meth)acrylate compounds is preferably present in the ink in an amount of from 70 to 95.9%, more preferably from 75 to 95.9%, and especially from 78 to 95.9% by weight relative to the total weight of ink. Any difference between the weight of components (i), (ii) and (iii) and 100% is made up by other customary ink additives, e.g. flow control agents, dispersants, biocides, rheology modifiers and so on other than water or organic solvent.
- customary ink additives e.g. flow control agents, dispersants, biocides, rheology modifiers and so on other than water or organic solvent.
- Inks of the present invention may contain further components in addition to components (i) to (iii) specified above, for example preservatives, biocides, rheology modifiers, surfactants, levelling agents, antifoaming agents, anti-kogation agents and combinations thereof.
- a process for printing an image onto a substrate comprising applying thereto an ink according to the first aspect of the present invention by means of an ink jet printer and curing the ink, preferably using an electron beam or more preferably using ultra violet light.
- Printed substrates obtained by this process form a further feature of the present invention.
- Preferred substrates are metal, plastic, ceramic, glass, wood, printed circuit boards and plain and coated papers.
- Preferred applications include printing for home/office use, packaging, labelling and barcodes, particularly wide format graphics, printed circuit board manufacture, signage, wall coverings and decorative laminates.
- an ink jet printer cartridge comprising a chamber and an ink wherein the ink is present in the chamber and is as defined in the first aspect of the invention.
- a radiation curable ink was prepared containing the following components:
- a millbase was prepared by bead milling RegalTM 250R pigment with a small amount of SartomerTM 256 and SartomerTM 238 together with SolsperseTM 32000 and 5000 dispersants until a fine particle dispersion was formed. The remaining components were then added in the dark and the mixture was homogenised and then filtered through a 1 micron WhatmanTM syringe filter.
- a radiation curable ink was prepared (in an analogous manner to Example 1 ) containing the following components:
- the percentages of mono acrylate , di acrylate and tri acrylate compounds by weight relative to the total weight of such compounds are such that the value of Formula (1 ) was 84.79.
- Example 1 and Comparative Example 1 were each coated onto sheen cards using an 8 ⁇ m K-bar coater.
- the coatings were cured using Fusion Systems apparatus fitted with a "D" 300W/inch bulb using cure energy in the range UV A 0.37 - 0.74, UV B 0.172 - 0.99 and UV C 0.07 - 0.11 at belt/cure speeds of 25M/min or 15M/min.
- the Reflectance Optical Density (ROD) of the cured coated sheen cards was measured using an XRite 938 Spectrodensitometer using density status T, illuminant D50 and 2° observer.
- the Chemical Resistance (% loss) was determined by performing 5 x MEK (methyl ethyl ketone) double rubs on the coated cured sheen cards and then measuring the ROD in the rubbed region. The Chemical Resistance (% loss) value was then expressed via
- the surface tension of the inks were determined at 25°C using a Kruss Surface Tension Balance.
- the hardness of the print was assessed in the conventional manner using pencils of different hardness, where the hardness is determined as the lowest hardness value that forms a scratch in the print.
- Example 1 has better chemical resistance and a faster cure speed than Comparative Example 1 whilst still retaining a low viscosity suitable for ink jet printing. Furthermore, Example 1 has better pencil hardness and a higher ROD than Comparative Example 1.
- the ink described in Example 1 was readily jetted through a Spectra Galaxy printhead. Further inks of the present invention were prepared (in an analogous manner to
- Example 1 containing:
- Such inks showed excellent printing performance through a Spectra Galaxy printhead and had very good chemical resistance.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A non-aqueous, substantially solvent-free, radiation curable ink having a viscosity less than 30m Pa.s at 60°C, comprising: (iv) a colorant (v) a photo-initiator; and (vi) a mixture of (meth)acrylate compounds; wherein: (a) the colorant is present in the ink in an amount of 0.1 to 14.9% by weight relative to the total weight of ink; and (b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth)acrylate compounds, di (meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1) is less than or equal to 60:
Description
COMPOSITIONS
This invention relates to radiation curable inks and to their use in ink jet printing. Ink jet printing is a non-contact method by which droplets of ink are ejected through a fine nozzle onto a substrate. There are many demanding performance requirements for inks used in ink jet printing. For example they should provide sharp, non-feathered images having good water, solvent- light- and ozone fastness, attractive colour and high optical density. Further desirable properties for ink jet printing inks include a fast dry time (to facilitate high-speed printing), a low viscosity to enable the inks to be used in a wide range of ink jet printers, excellent mechanical resistance (to avoid the prints being rubbed off), low curl and good adhesion to a range of substrates. Often organic solvents are included in ink jet printing inks to lower their viscosity.
However such solvents can give rise to undesirable odours, particularly in the home and small, poorly ventilated offices. Inclusion of low boiling point organic solvents should be avoided in order to minimise the release of volatile organic solvents into the atmosphere. Inclusion of high boiling point solvents can increase ink dry times significantly. US 5,270,368 discloses radiation-curable etch-resistant compositions for ink jet printing containing large proportions of monofunctional and difunctional monomers in combination with large amounts of organic solvents such as methanol to achieve a sufficiently low viscosity for jetting.
US 4,303,924 discloses radiation curable ink jet printing inks containing organic solvent and large proportions of trifunctional monomers.
WO 02/38688 discloses low viscosity radiation curable compositions which are free from solvent and have low proportions of difunctional and tri- or higher functional monomers.
According to the first aspect of the present invention there is provided a non- aqueous, substantially solvent-free, radiation curable ink having a viscosity less than 30m Pa.s at 60°C, comprising: (i) a colorant (ii) a photo-initiator; and (iii) a mixture of (meth)acrylate compounds; wherein:
(a) the colorant is present in the ink in an amount of 0.1 to 14.9% by weight relative to the total weight of ink; and
(b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more
(meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth)acrylate compounds, di (meth)acrylate compounds and compounds having three or more
(meth)acrylate groups and are such that the value of Formula (1 ) is less than or equal to 60:
c% + 0.628 d% + e% \ V sin 60 tan 607
Formula (1).
Preferably the value of Formula (1) is from 40 to 60, more preferably from 42.6 to 57, especially from 49 to 55.8. The amount of colorant in the ink is preferably from 0.1 to 14%, more preferably from 1 to 10% and especially from 1.1 to 8% by weight, relative to the total weight of the ink. Preferably the colorant is not white. Preferred colorants are yellow, magenta, cyan, black, blue, indigo, violet, green, orange, red and mixtures comprising two or more thereof. Preferably the ink is free from titanium dioxide. The colorant is preferably a dye, a pigment or a mixture thereof. More preferably the colorant is a pigment. Preferred dyes and pigments are free from ionic groups, for example disperse dyes and water-insoluble pigments are especially preferred colorants. Preferred pigments are organic or inorganic. The pigment is preferably in the form particles which are small enough to pass through the very fine nozzles used in the phntheads of ink jet printers. Typically these nozzles are half the diameter of a human hair. Thus the average particle size of the pigment is preferably from 0.003 to 15 μm, more preferably from 0.004 to 5 μm and especially from 0.005 to 1 μm. By choosing particles of this size advantages can be achieved in terms of storage stability for the ink and high optical density for the resultant prints. Pigment particle sizes outside these ranges may be used where printheads have particularly large nozzle diameters. Very fine dispersions of pigments and methods for their preparation are disclosed in, for example, EP 0 776 952, US 5,538,548, US 5,443,628, EP 0 259 130, US 5,285,064, EP 0 429 828 and EP 0 526 198.
Examples of inorganic pigments include carbon black, titania, iron oxide, zinc oxide and mixtures thereof. Examples of organic pigments include phthalocyanines, anthraquinones, perylenes, carbazole, monoazo and disazobenzimidazolones, isoindolinones, monoazonaphthols, diarylidepyrazolones, rhodamines, indigoids, quinacridones, diazopyranthrones, dinitranilines, pyrazolones, dianisidines, pyranthrones, tetrachloroisoindolinones, dioxazines, monoazo acrylides, anthrapyrimidines and mixtures thereof.
Examples of carbon black pigments include Regal 400R, Mogul™ L, Elftex™ 320 from Cabot Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550, Printex™ 25, Printex™ 35, Printex™ 55 and Printex™ 150T from Degussa Co., and Pigment Black 7.
Further examples of pigments include CI. Pigment Yellow 17, CI. Pigment Blue 27. CI. Pigment Red 49:2, CI. Pigment Red 81 :1 , CI. Pigment Red 81 :3, CI. Pigment Red 81 :x, CI. Pigment Yellow 83, CI. Pigment Red 57: 1 , CI. Pigment Red 49:1 , CI. Pigment Violet 23, CI. Pigment Green 7, CI. Pigment Blue 61 , CI. Pigment Red 48:1 , CI. Pigment Red 52:1 , CI. Pigment Violet 1 , CI. Pigment White 6, CI. Pigment Blue 15, CI. Pigment Yellow 12, CI. Pigment Blue 56, CI. Pigment Orange 5, CI. Pigment Black 7, CI. Pigment Yellow 14, CI. Pigment Red 48:2, C.I. Pigment Blue 15:3, CI. Pigment Yellow 1 , CI. Pigment Yellow 3, CI. Pigment Yellow 13, CI. Pigment Orange 16, CI. Pigment Yellow 55, CI. Pigment Red 41 , CI. Pigment Orange 34, CI. Pigment Blue 62, CI. Pigment Red 22, CI. Pigment Red 170, CI. Pigment Red 88, CI. Pigment Yellow 151 , CI. Pigment Red 184, CI. Pigment Blue 1 :2, CI. Pigment Red 3, CI. Pigment Blue 15:1 , CI. Pigment Blue 15:3, CI. Pigment Blue 15:4, CI. Pigment Red 23, CI. Pigment Red 1 12, CI. Pigment Yellow 126, CI. Pigment Red 169, CI. Pigment Orange 13, CI. Pigment Red 1-10, 12, CI. Pigment Blue 1 :X, CI. Pigment Yellow 42, C.I. Pigment Red 101 , CI. Pigment Brown 6, CI. Pigment Brown 7, CI. Pigment Brown 7:X, CI. Pigment Black 1 1 , CI. Pigment Metal 1 , CI. Pigment Metal 2, CI. Pigment Yellow 128, CI. Pigment Yellow 93, CI. Pigment Yellow 74, CI. Pigment Yellow 138, CI. Pigment Yellow 139, CI. Pigment Yellow 154, CI. Pigment Yellow 185, CI. Pigment Yellow 180, CI. Pigment Red 122, CI. Pigment Red 184, and bridged aluminium phthalocyanine pigments.
Further pigments are listed in The Colour Index and updates thereof, especially the 3rd edition, 1982, pages 6-146.
The especially preferred pigments are Pigment Yellow 128, 93, 17, 74, 138, 139, 154, 185, 180; Pigment Red 122, 57:1 , 184; Pigment Blue 15:3, 15:4 and carbon black. Preferred dyes include azo, diazo, xanthene, anthraquinone, triaryl methane, azine, thiazine, phthalocyanine and nigrosine types. Dyes may be used singly or in combination with other dyes and/or pigments. Dyes are preferably disperse or solvent soluble, examples of which may be selected from The Colour Index especially the 3rd edition, 1982, pages 147-263. Dyes can be metalised or non-metalised. The ink optionally further contains a dispersant. When the colorant is a disperse dye a dispersant is often not necessary because the dye may be soluble in the formulation. Similarly when the pigment is self-dispersible (e.g. the pigment carries dispersing groups or is surface modified to be self-dispersible) no further dispersant is needed. However when the colorant is insoluble in the mixture of (meth)acrylate compounds (component (iii)) a dispersant is preferably included in the ink to assist storage stability. Suitable dispersants include, for example, polyester, polyurethane and polyacrylate dispersants, especially those in the form of high molecular weight block copolymer. Examples of dispersants include Disperbyk™ (ex BYK Chemie) and Solsperse™ (ex Avecia) dispersants. A detailed list of non-polymeric as well as some polymeric dispersants appears in, for example, McCutcheon's Functional Materials, North
American Edition, Manufacturing Confectioner Publishing Co., Glen Rock, N.J., pp.110- 129 (1990), the entire disclosure of which is incorporated herein by reference. Dispersants suitable for use with pigments are also disclosed in DE 19636382, US 5,720,802, US 5,713,993, PCT/GB95/02501 , US 5,085,689 and GB 2303376. When the ink contains a dispersant this is preferably present in an amount of 50 to 150% by weight relative to the weight of colorant.
Examples of self-dispersing pigments include surface treated carbon blacks carrying carboxy, sulphonate and/or ethylene oxide groups.
The pigment and dispersant are preferably added to the ink as a mixture. For example, a mixture of a pigment and a dispersant may be made by milling pigment in a small amount of the (meth)acrylate components c), d) and e) with a milling media, e.g. glass beads. The pigment dispersion is then typically screened and "let down" by slowly adding the remaining ink components.
The amount of photo-initiator in the ink is preferably 0.1 to 15%, more preferably 3 to 12% by weight, relative to the total weight of the ink. Preferred photo-initiators include alpha diketones, monoketals of alpha-diketones or ketoaldehydes, acyloins and their corresponding ethers, chromophore-substituted halo-s-triazines, and chromophore- substituted halomethyl-oxadiozoles. Specific examples of photo-initiators include acetophenone, propiophenone, 2-phenyl-acetophenone, 2-chloro-2-phenyl-acetophenone, 2-2-dichloro-2-phenyl-acetophenone, 2-butoxy-2-phenyl acetophenone, 2,2-dimethoxy-2- phenyl-acetophenone, 2,2-diethoxy-acetophenone, 2-methylol-2-methoxy-2-phenyl- acetophenone, benzophenone, 4-trichloromethyl benzophenone, indenone, 1-3- indanedione, fluorenone, xanthone, thioxanthone, 2-chlorothioxanthone, anthraquinone, 2-ethylanthraquinone, biacetyl, glyoxal, 1 ,2-indanedione, p-chlorophenyl-glyoxal, benzil, camphoquinone, and benzoin methyl and ethyl esters. Commercial photo-initiators particularly suitable for use in the present invention include Speedcure™ ITX, and Irgacure™ 369. The ink optionally further contains one or more co-initiators or amine synergists in order to improve cure rate. Examples include isopropylthioxanthone, ethyl-4-(dimethylamine) benzoate, 2-ethyl hexyl dimethylaminobenzoate and dimethylaminoethyl methacrylate.
Preferably the photo-initiator is other than a cationic photo-initiator. Preferably the photo-initiator is a free radical photo-initiator.
Preferably the photo-initiator is soluble in the ink.
A single photo-initiator may be used although it is preferable that the photo-initiator is a mixture of two or more photo-initiators because this can lead to a broader spectral response, improved depth of cure and improved cure rate with opacifying pigments such as carbon black.
Preferably the ink further comprises a stabiliser to improve the storage stability of the ink and prevent premature curing. The stabiliser is preferably an antioxidant, a radical trap, a radical quencher or the like, e.g. a phenol, thiol, quinone, hydroquinone, amine,
xanthate or an N-alkyl or N-aryl aniline. Too much stabiliser will prevent cure entirely. Hence preferred amounts of stabiliser are from 0 to 10%, more preferably from 0.01 to 5%, and especially from 0.1 to 3% by weight relative to the total weight of the ink. Mixtures of stabilisers are preferable for the best ink storage lifetime.
Preferably the ink is curable by actinic radiation or particle beam, especially by UV or electron beam radiation.
Mono (meth)acrylate compounds have one (and only one) acrylate or methacrylate group. This group is, as is known in the art, is polymerisable when irradiated in the presence of a photo-initiator. (Meth)acrylate groups are represented by the formula:
CH2 ==< c =o
wherein R is H or methyl
The mono (meth)acrylate compound is preferably a monomer. Examples mono (meth)acrylate monomers include cyclic trimethylolpropane formal (meth)acrylate, ethoxylated tetra hydrofurfuryl (meth)acrylate, phenoxy ethyl (meth)acrylate, trimethylol propane formal (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, monomethoxy neopentyl glycol propoxylate mono (meth)acrylate, monomethoxy tripropylene glycol mono (meth)acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, iso- decyl (meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, tridecyl (meth)acrylate, iso-bomyl (meth)acrylate, ethoxyl nonyl phenol (meth)acrylate, ethoxylated phenol (meth)acrylate, 2-hydroxyl ethyl (meth) acrylate, 4-hydroxyl butyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cetyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl hexyl (meth)acrylate, 2-dimethyl amino ethyl (meth) acrylate, trifluoro ethyl (meth)acrylate, 3- methoxy butyl (meth)acrylate, dicyclopentenyl (meth)acrylate, polyethylene glycol mono (meth)acrylate and poly propylene glycol mono (meth)acrylate. Preferred mono (meth)acrylate monomers include lauryl (meth)acrylate, tetrahydro furfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, iso-octyl (meth)acrylate, iso-decyl (meth)acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, isobomyl (meth)acrylate, cyclic trimethylol propane formal (meth)acrylate.
It is especially preferred that the one or more monomer (meth)acrylate compounds is or comprises isobomyl acrylate.
Di (meth)acrylate compounds have two (and only two) groups selected from acrylate and methacrylate. Preferred di (meth)acrylate compounds are di (meth)acrylate monomers, for example di(meth)acrylates of 1 ,4 butane diol, 1-6 hexane diol, neopentyl glycol, mono, di, tri and poly ethylene glycols, mono, di, tri and poly propylene glycols, mono methoxy
ethoxylated trimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1 ,2 butylene glycol and ethoxylated hexane diol.
It is especially preferred that the one or more di(meth)acrylate compounds is or comprises 1 ,6 hexane diol diacrylate. The compound(s) having three or more (meth) acrylate groups have three or more groups selected from acrylate and methacrylate. The compound having three or more (meth)acrylate groups is preferably a monomer, oligomer or polymer, preferred examples of which include trimethylol propane tri(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate, propoxylated trimethylol propane tri(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated di-pentaerylthritol tetra (meth)acrylate, tetra methylol methane tetra (meth)acrylate, multifunctional (meth)acrylate-urethanes, (meth)acrylate-polyesters and (meth)acrylate acrylics.
It is especially preferred that the one or more compounds comprising three or more (meth)acrylate groups is or comprises trimethylol propane triacrylate and/or ethoxylated trimethylol propane triacrylate.
Inks which contain acrylates polymerise more quickly than those containing methacrylates when exposed to actinic or particle beam radiation. Consequently, the amount of methacrylate is preferably not greater than 20%, more preferably not greater than 10% and especially not greater than 5% of component (iii). It is particularly preferred that component (iii) contains no methacrylate.
Optionally the ink further comprises a polymer or oligomer containing no (meth)acrylate groups. Preferably the polymer and oligomer containing no (meth)acrylate groups is present in the ink at from 0 to15%, more preferably from 0 to 10% and most preferably from 0 to 5% by weight relative to the total weight of the ink.
Inks of the present invention are substantially solvent free. That is to say no solvent or water is present in the ink except for trace amounts which may be present as impurities in any of the ink components. Preferably any such residues are less than 2%, more preferably less than 0.5% and especially less than 0.01 % by weight relative to the total weight of ink. As hereinbefore described inks of the present invention are particularly suitable for use in ink jet printing. A preferred ink jet type for inks of the present invention is piezo ink jet printing. The viscosity of the inks of the present invention are preferably 1 to 30 mPa.s, more preferably from 2 to 25 mPa.s at 60°C The ink composition may optionally have a higher viscosity at room temperature provided that the final ink meets the above viscosity requirements at the above temperature.
The surface tension of the ink of the present invention is preferably below 40 dynes/cm.
Inks of the present invention are preferably free from particulate impurities that would tend to block an ink jet nozzle. To achieve this the ink is preferably filtered through a filter with a pore size of less than 10um, more preferably less than 34m and especially less than 14 .
A particularly preferred ink according to the invention is a non-aqueous, substantially solvent-free, radiation curable ink having a viscosity of 1 to 30m Pa.s at 60°C comprising:
(i) a yellow, magenta, cyan, black, blue, indigo, violet, green, orange or red pigment or a mixture comprising two or more thereof;
(ϋ) a photo-initiator; and (iii) a mixture of (meth)acrylate compounds; wherein: (a) the pigment is present in the ink an amount of from 1.1 to 8% by weight relative to the total weight of ink;
(b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth )acry late compounds, di (meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1 ) is from 40 to 60:
C% + 0.628 d% + e%
' sin 60 t taann 60/
Formula (1 )
(c) the photo-initiator is present in the ink in an amount of 3 to 12% by weight relative to the total weight of ink;
(d) the one or more mono (meth)acrylate compounds are selected from the group consisting of cyclic trimethylolpropane formal (meth)acrylate, ethoxylated tetra hydrofurfuryl (meth)acrylate, phenoxy ethyl (meth)acrylate, trimethylol propane formal (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, monomethoxy neopentyl glycol propoxylate mono (meth)acrylate, monomethoxy t propylene glycol mono (meth)acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, iso-decyl
(meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, tridecyl (meth)acrylate, iso-bomyl (meth)acrylate, ethoxyl nonyl phenol (meth)acrylate, ethoxylated phenol (meth)acrylate, 2-hydroxyl ethyl (meth) acrylate, 4-hydroxyl butyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cetyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl hexyl (meth)acrylate, 2-dimethyl amino ethyl (meth) acrylate, trifluoro ethyl (meth)acrylate, 3-methoxy butyl (meth)acrylate, dicyclopentenyl (meth)acrylate, polyethylene glycol mono (meth)acrylate and poly propylene glycol mono (meth)acrylate and mixtures thereof;
(e) the one or more di (meth)acrylate compounds are selected from the group consisting of di(meth)acrylates of 1 ,4 butane diol, 1-6 hexane diol, neopentyl glycol, mono, di, tri and poly ethylene glycols, mono, di, tri and poly propylene glycols, mono methoxy ethoxylated trimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1 ,2 butylene glycol and ethoxylated hexane diol and mixtures thereof; and
(f) the one or more compounds having three or more (meth)acrylate groups are selected from the group consisting of trimethylol propane tri(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate, propoxylated trimethylol propane tri(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated di- pentaerylthritol tetra (meth)acrylate, tetra methylol methane tetra
(meth)acrylate, multifunctional (meth)acrylate-urethanes, (meth)acrylate- polyesters and (meth)acrylate acrylics and mixtures thereof. In this preferred ink the mixture of (meth)acrylate compounds is preferably present in the ink in an amount of from 70 to 95.9%, more preferably from 75 to 95.9%, and especially from 78 to 95.9% by weight relative to the total weight of ink. Any difference between the weight of components (i), (ii) and (iii) and 100% is made up by other customary ink additives, e.g. flow control agents, dispersants, biocides, rheology modifiers and so on other than water or organic solvent.
Inks of the present invention may contain further components in addition to components (i) to (iii) specified above, for example preservatives, biocides, rheology modifiers, surfactants, levelling agents, antifoaming agents, anti-kogation agents and combinations thereof.
According to a second aspect of the present invention there is provided a process for printing an image onto a substrate comprising applying thereto an ink according to the first aspect of the present invention by means of an ink jet printer and curing the ink, preferably using an electron beam or more preferably using ultra violet light. Printed substrates obtained by this process form a further feature of the present invention.
Preferred substrates are metal, plastic, ceramic, glass, wood, printed circuit boards and plain and coated papers. Preferred applications include printing for home/office use, packaging, labelling and barcodes, particularly wide format graphics, printed circuit board manufacture, signage, wall coverings and decorative laminates.
According to a third aspect of the present invention there is provided an ink jet printer cartridge comprising a chamber and an ink wherein the ink is present in the chamber and is as defined in the first aspect of the invention.
The invention in further illustrated by the following examples in which all parts and percentages are by weight unless otherwise stated.
Example 1
A radiation curable ink was prepared containing the following components:
The procedure for preparation of the above ink was as follows:
A millbase was prepared by bead milling Regal™ 250R pigment with a small amount of Sartomer™ 256 and Sartomer™ 238 together with Solsperse™ 32000 and 5000 dispersants until a fine particle dispersion was formed. The remaining components were then added in the dark and the mixture was homogenised and then filtered through a 1 micron Whatman™ syringe filter.
The percentages of mono acrylate (16.7%), di acrylate (16.7%) and tri acrylate (66.6%) compounds by weight relative to the total weight of such compounds (100%) are such that the value of Formula (1) was (16.7 + 0.628 X (16.7/sin 60 + 66.6/tan60) = 52.93.
Comparative Example 1
A radiation curable ink was prepared (in an analogous manner to Example 1 ) containing the following components:
The percentages of mono acrylate , di acrylate and tri acrylate compounds by weight relative to the total weight of such compounds are such that the value of Formula (1 ) was 84.79.
Results
The inks describe in Example 1 and Comparative Example 1 were each coated onto sheen cards using an 8μm K-bar coater. The coatings were cured using Fusion Systems apparatus fitted with a "D" 300W/inch bulb using cure energy in the range UVA 0.37 - 0.74, UVB 0.172 - 0.99 and UVC 0.07 - 0.11 at belt/cure speeds of 25M/min or 15M/min.
The Reflectance Optical Density (ROD) of the cured coated sheen cards was measured using an XRite 938 Spectrodensitometer using density status T, illuminant D50 and 2° observer.
The Chemical Resistance (% loss) was determined by performing 5 x MEK (methyl ethyl ketone) double rubs on the coated cured sheen cards and then measuring the ROD in the rubbed region. The Chemical Resistance (% loss) value was then expressed via
Chemical Resistance (% loss) = 100 (ROD Initial - ROD after 5 x MEK rubs)
ROD Initial
Hence small values of Chemical Resistance (% loss) represent higher solvent resistance.
The viscosity was measured by using a Brookfield viscometer at 50°C operating at 100 revolutions per minute and using a UL spindle
The surface tension of the inks were determined at 25°C using a Kruss Surface Tension Balance.
The hardness of the print was assessed in the conventional manner using pencils of different hardness, where the hardness is determined as the lowest hardness value that forms a scratch in the print.
The above table shows that the ink of Example 1 has better chemical resistance and a faster cure speed than Comparative Example 1 whilst still retaining a low viscosity suitable for ink jet printing. Furthermore, Example 1 has better pencil hardness and a higher ROD than Comparative Example 1. The ink described in Example 1 was readily jetted through a Spectra Galaxy printhead. Further inks of the present invention were prepared (in an analogous manner to
Example 1 ) containing:
Such inks showed excellent printing performance through a Spectra Galaxy printhead and had very good chemical resistance.
Claims
1. A non-aqueous, substantially solvent-free, radiation curable ink having a viscosity less than 30m Pa.s at 60°C, comprising: (i) a colorant
(ii) a photo-initiator; and
(iii) a mixture of (meth)acrylate compounds; wherein:
(a) the colorant is present in the ink in an amount of 0.1 to 14.9% by weight relative to the total weight of ink; and
(b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth)acrylate compounds, di
(meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1) is less than or equal to 60:
c% + 0.628 ( d% + e% \ ' sin 60 tan 60/
Formula (1).
2. An ink according to claim 1 wherein the colorant is a pigment.
3. An ink according to any one of the preceding claims wherein the mono (meth)acrylate compounds and di (meth)acrylate compounds are monomers.
4. An ink according to any one of the preceding claims wherein the value of Formula (1) is from 49 to 55.8.
5. An ink according to any one of the preceding claims wherein the photo-initiator is a free radical photo-initiator.
6. An ink according to any one of the preceding claims wherein the one or more mono (meth)acrylate compounds is or comprises isobomyl acrylate.
7. An ink according to any one of the preceding claims wherein the one or more di (meth)acrylate compounds is or comprises 1 ,6 hexanediol diacrylate.
8. An ink according to any one of the preceding claims wherein the one or more compound comprising three or more (meth)acrylate groups is or comprises trimethylolpropane triacrylate and/or ethoxylated trimethylolpropane triacrylate.
9. An ink according to any one of the preceding claims which further comprises a dispersant and/or an amine synergist.
10. An ink according to any one of the preceding claims wherein the colorant is present in an amount of 1.1 to 8% by weight, relative to the total weight of the ink.
11. An ink according to any one of the preceding claims wherein the colorant is not white.
12. An ink according to any one of the preceding claims which is free from titanium dioxide.
13. An ink according to any one of the preceding claims wherein the photo-initiator is present in an amount of 3 to 12 % by weight, relative to the total weight of the ink.
14. An ink according to claim 1 comprising:
(i) a yellow, magenta, cyan, black, blue, indigo, violet, green, orange or red pigment or a mixture comprising two or more thereof;
(ii) a photo-initiator; and
(iii) a mixture of (meth)acrylate compounds; wherein:
(a) the pigment is present in the ink an amount of from 1.1 to 8% by weight relative to the total weight of ink;
(b) the mixture of (meth)acrylate compounds comprises c% of one or more mono (meth)acrylate compounds, d% of one or more di (meth)acrylate compounds and e% of one or more compounds having three or more (meth)acrylate groups, wherein the values of c%, d% and e% are by weight relative to the total weight of the mono (meth)acrylate compounds, di (meth)acrylate compounds and compounds having three or more (meth)acrylate groups and are such that the value of Formula (1 ) is from 40 to 60:
c% + 0.628 d + e% sin 60 tan 60/
Formula (1 ) (c) the photo-initiator is present in the ink in an amount of 3 to 12% by weight relative to the total weight of ink;
(d) the one or more mono (meth)acrylate compounds are selected from the group consisting of cyclic trimethylolpropane formal (meth)acrylate, ethoxylated tetra hydrofurfuryl (meth)acrylate, phenoxy ethyl (meth)acrylate, trimethylol propane formal (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, monomethoxy neopentyl glycol propoxylate mono (meth)acrylate, monomethoxy tripropylene glycol mono (meth)acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, iso-decyl (meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, tridecyl
(meth)acrylate, iso-bomyl (meth)acrylate, ethoxyl nonyl phenol (meth)acrylate, ethoxylated phenol (meth)acrylate, 2-hydroxyl ethyl (meth) acrylate, 4-hydroxyl butyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cetyl (meth)acrylate, cyclohexyl (meth)acrylate, ethyl hexyl (meth)acrylate, 2-dimethyl amino ethyl (meth) acrylate, trifluoro ethyl
(meth)acrylate, 3-methoxy butyl (meth)acrylate, dicyclopentenyl (meth)acrylate, polyethylene glycol mono (meth)acrylate and poly propylene glycol mono (meth)acrylate and mixtures thereof;
(e) the one or more di (meth)acrylate compounds are selected from the group consisting of di(meth)acrylates of 1 ,4 butane diol, 1-6 hexane diol, neopentyl glycol, mono, di, tri and poly ethylene glycols, mono, di, tri and poly propylene glycols, mono methoxy ethoxylated trimethylolpropane, propoxylated neopentyl glycol, ethoxylated neopentyl glycol, 1 ,2 butylene glycol and ethoxylated hexane diol and mixtures thereof; and
(f) the one or more compounds having three or more (meth)acrylate groups are selected from the group consisting of trimethylol propane tri(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate, propoxylated trimethylol propane tri(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2- hydroxyethyl) isocyanurate triacrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated di-pentaerylthhtol tetra (meth)acrylate, tetra methylol methane tetra (meth)acrylate, multifunctional (meth)acrylate-urethanes, (meth)acrylate-polyesters and (meth)acrylate acrylics and mixtures thereof.
15. An ink according to any one of the preceding claims which has been filtered through a filter having a mean pore size of less than 10urn.
16. An ink according to any one of the preceding claims for use in ink jet printing.
17. A process for printing an image onto a substrate comprising printing an image onto a substrate using an ink according to any one of the preceding claims by means of an ink jet printer and curing the ink.
18. A process according to claim 17 wherein the curing is performed using an electron beam or ultra violet light.
19. A printed substrate obtained by the process of claim 17 or 18.
20. An ink jet printer cartridge comprising a chamber and an ink wherein the ink is present in the chamber and is as defined in one of claims 1 to 16.
21. A substrate printed with an image using an ink according to any one of the claims 1 to 16.
22. A substrate printed with an image by a process according to claim 17 or 18.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0503494A GB2406858B (en) | 2002-09-20 | 2003-09-04 | Radiation curable inkjet inks compositions |
| AU2003263312A AU2003263312A1 (en) | 2002-09-20 | 2003-09-04 | Radiation curable inkjet inks compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0221894.9 | 2002-09-20 | ||
| GB0221894A GB0221894D0 (en) | 2002-09-20 | 2002-09-20 | Compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004026978A1 true WO2004026978A1 (en) | 2004-04-01 |
Family
ID=9944480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2003/003836 WO2004026978A1 (en) | 2002-09-20 | 2003-09-04 | Radiation curable inkjet inks compositions |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU2003263312A1 (en) |
| GB (2) | GB0221894D0 (en) |
| TW (1) | TW200418938A (en) |
| WO (1) | WO2004026978A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2396621A (en) * | 2002-11-27 | 2004-06-30 | Konica Minolta Holdings Inc | Actinic ray curable ink jet solventless ink, image forming method using the same, and ink jet recording apparatus |
| WO2005047405A1 (en) * | 2003-11-12 | 2005-05-26 | Vutek, Incorporated | Radiation curable ink compositions and applications thereof |
| EP1593718A1 (en) * | 2004-05-06 | 2005-11-09 | Agfa-Gevaert | Radiation-curable ink-jet printing. |
| WO2007000566A1 (en) * | 2005-06-25 | 2007-01-04 | Fujifilm Imaging Colorants Limited | Process |
| US7700263B2 (en) | 2003-12-20 | 2010-04-20 | Fujifilm Imaging Colorants Limited | Substantially solvent-free and photoinitiator-free curable ink |
| US8083338B2 (en) | 2004-05-06 | 2011-12-27 | Agfa Graphics N.V. | Radiation-curable ink-jet printing |
| US20120171434A1 (en) * | 2009-09-08 | 2012-07-05 | Sun Chemical B.V. | Photoinitiator composition |
| US8585814B2 (en) * | 2005-04-14 | 2013-11-19 | Konica Minolta Medical & Graphic, Inc. | Active ray curable ink-jet ink, image forming method and ink-jet recording apparatus using the same |
| EP3092268A4 (en) * | 2014-01-08 | 2017-08-23 | Sun Chemical Corporation | Energy curable inks with improved adhesion a method for formulating |
| US10190018B2 (en) | 2015-08-31 | 2019-01-29 | Kateeva, Inc. | Di- and mono(meth)acrylate based organic thin film ink compositions |
| WO2018195066A3 (en) * | 2017-04-21 | 2020-03-26 | Kateeva, Inc. | Compositions and techniques for forming organic thin films |
| WO2024118440A1 (en) * | 2022-12-01 | 2024-06-06 | Sun Chemical Corporation | Uv coatings for monoweb films and labels |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0608466D0 (en) | 2006-04-27 | 2006-06-07 | Sericol Ltd | A printing ink |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275646A (en) * | 1990-06-27 | 1994-01-04 | Domino Printing Sciences Plc | Ink composition |
| WO1999029788A1 (en) * | 1997-12-05 | 1999-06-17 | Xaar Technology Limited | Radiation curable ink jet ink compositions |
| WO1999029787A2 (en) * | 1997-12-05 | 1999-06-17 | Xaar Technology Limited | Radiation curable ink jet ink compositions |
| US6114406A (en) * | 1996-02-21 | 2000-09-05 | Coates Brothers Plc | Radiation curable ink composition |
| EP1323795A1 (en) * | 2001-12-20 | 2003-07-02 | Ucb S.A. | Radiation curable compositions for pigmented liquid inks |
-
2002
- 2002-09-20 GB GB0221894A patent/GB0221894D0/en not_active Ceased
-
2003
- 2003-09-04 GB GB0503494A patent/GB2406858B/en not_active Expired - Fee Related
- 2003-09-04 WO PCT/GB2003/003836 patent/WO2004026978A1/en not_active Application Discontinuation
- 2003-09-04 AU AU2003263312A patent/AU2003263312A1/en not_active Abandoned
- 2003-09-19 TW TW92125909A patent/TW200418938A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275646A (en) * | 1990-06-27 | 1994-01-04 | Domino Printing Sciences Plc | Ink composition |
| US6114406A (en) * | 1996-02-21 | 2000-09-05 | Coates Brothers Plc | Radiation curable ink composition |
| WO1999029788A1 (en) * | 1997-12-05 | 1999-06-17 | Xaar Technology Limited | Radiation curable ink jet ink compositions |
| WO1999029787A2 (en) * | 1997-12-05 | 1999-06-17 | Xaar Technology Limited | Radiation curable ink jet ink compositions |
| EP1323795A1 (en) * | 2001-12-20 | 2003-07-02 | Ucb S.A. | Radiation curable compositions for pigmented liquid inks |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7104642B2 (en) | 2002-11-27 | 2006-09-12 | Konica Minolta Holdings, Inc. | Active ray curable ink jet solventless ink, image forming method using the same, and ink jet recording apparatus |
| GB2396621A (en) * | 2002-11-27 | 2004-06-30 | Konica Minolta Holdings Inc | Actinic ray curable ink jet solventless ink, image forming method using the same, and ink jet recording apparatus |
| GB2396621B (en) * | 2002-11-27 | 2007-03-14 | Konica Minolta Holdings Inc | Active ray curable ink jet solventless ink,image forming method using the same, and ink jet recording apparatus |
| WO2005047405A1 (en) * | 2003-11-12 | 2005-05-26 | Vutek, Incorporated | Radiation curable ink compositions and applications thereof |
| US7365105B2 (en) | 2003-11-12 | 2008-04-29 | Electronics For Imaging, Inc. | Radiation curable ink compositions and applications thereof |
| US7579388B2 (en) | 2003-11-12 | 2009-08-25 | Electronics For Imaging, Inc. | Radiation curable ink compositions and applications thereof |
| US7700263B2 (en) | 2003-12-20 | 2010-04-20 | Fujifilm Imaging Colorants Limited | Substantially solvent-free and photoinitiator-free curable ink |
| EP1593718A1 (en) * | 2004-05-06 | 2005-11-09 | Agfa-Gevaert | Radiation-curable ink-jet printing. |
| US8083338B2 (en) | 2004-05-06 | 2011-12-27 | Agfa Graphics N.V. | Radiation-curable ink-jet printing |
| US8585814B2 (en) * | 2005-04-14 | 2013-11-19 | Konica Minolta Medical & Graphic, Inc. | Active ray curable ink-jet ink, image forming method and ink-jet recording apparatus using the same |
| WO2007000566A1 (en) * | 2005-06-25 | 2007-01-04 | Fujifilm Imaging Colorants Limited | Process |
| US20120171434A1 (en) * | 2009-09-08 | 2012-07-05 | Sun Chemical B.V. | Photoinitiator composition |
| US9321853B2 (en) * | 2009-09-08 | 2016-04-26 | Sun Chemical Corporation | Photoinitiator composition |
| EP3092268A4 (en) * | 2014-01-08 | 2017-08-23 | Sun Chemical Corporation | Energy curable inks with improved adhesion a method for formulating |
| US10190018B2 (en) | 2015-08-31 | 2019-01-29 | Kateeva, Inc. | Di- and mono(meth)acrylate based organic thin film ink compositions |
| WO2018195066A3 (en) * | 2017-04-21 | 2020-03-26 | Kateeva, Inc. | Compositions and techniques for forming organic thin films |
| US11844234B2 (en) | 2017-04-21 | 2023-12-12 | Kateeva, Inc. | Compositions and techniques for forming organic thin films |
| WO2024118440A1 (en) * | 2022-12-01 | 2024-06-06 | Sun Chemical Corporation | Uv coatings for monoweb films and labels |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0503494D0 (en) | 2005-03-30 |
| TW200418938A (en) | 2004-10-01 |
| GB2406858A (en) | 2005-04-13 |
| AU2003263312A1 (en) | 2004-04-08 |
| GB2406858B (en) | 2006-04-05 |
| GB0221894D0 (en) | 2002-10-30 |
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