WO2009074833A1 - A printing ink - Google Patents
A printing ink Download PDFInfo
- Publication number
- WO2009074833A1 WO2009074833A1 PCT/GB2008/051179 GB2008051179W WO2009074833A1 WO 2009074833 A1 WO2009074833 A1 WO 2009074833A1 GB 2008051179 W GB2008051179 W GB 2008051179W WO 2009074833 A1 WO2009074833 A1 WO 2009074833A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- cyclic group
- acrylate
- bridged cyclic
- total weight
- Prior art date
Links
- 238000007639 printing Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 29
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical group C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical group C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 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 claims description 4
- 239000012958 Amine synergist Substances 0.000 claims description 4
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- QSJFDOVQWZVUQG-XLPZGREQSA-N 3',5'-cyclic dTMP Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@@H]2COP(O)(=O)O[C@H]2C1 QSJFDOVQWZVUQG-XLPZGREQSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000976 ink Substances 0.000 description 90
- 239000000975 dye Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000012949 free radical photoinitiator Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 206010073306 Exposure to radiation Diseases 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- -1 methacrylates) Chemical compound 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 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 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical group C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- XYRRJTMWSSGQGR-UHFFFAOYSA-N 2,2-bis(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.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO XYRRJTMWSSGQGR-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
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- UXMQORVHJMUQFD-UHFFFAOYSA-N Heptanophenone Chemical compound CCCCCCC(=O)C1=CC=CC=C1 UXMQORVHJMUQFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- BDGDYAHBIXFCIS-UHFFFAOYSA-N [(2,6-dimethylbenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethylphenyl)methanone Chemical compound CC=1C=CC=C(C)C=1C(=O)P(=O)(CC(CC(C)(C)C)C)C(=O)C1=C(C)C=CC=C1C BDGDYAHBIXFCIS-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000003139 biocide Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001789 chalcones Chemical class 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 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
- 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
Definitions
- This invention relates to a printing ink and in particular to a photochromic ink which is cured by irradiation.
- ink-jet printing minute droplets of black, white or coloured ink are ejected in a controlled manner from one or more reservoirs or printing heads through narrow nozzles on to a substrate which is moving relative to the reservoirs.
- the ejected ink forms an image on the substrate.
- the inks must flow rapidly from the printing heads, and, to ensure that this happens, they must have in use a low viscosity, typically below 200 mPas at 25 0 C although in most applications the viscosity should be below 100 mPas or 50 mPas, and often below 25 mPas.
- the ink when ejected through the nozzles, the ink has a viscosity of less than 25 mPas, preferably 5-15 mPas and ideally 10.5 mPas at the jetting temperature which is often elevated to about 4O 0 C (the ink might have a much higher viscosity at ambient temperature).
- the inks must also be resistant to drying or crusting in the reservoirs or nozzles.
- ink-jet inks for application at or near ambient temperatures are commonly formulated to contain a large proportion of a mobile liquid vehicle or solvent. In one common type of ink-jet ink this liquid is water - see for example the paper by Henry R. Kang in the Journal of Imaging Science, 35(3), pp.
- ink-jet inks that include a large proportion of water or solvent cannot be handled after printing until the inks have dried, either by evaporation of the solvent or its absorption into the substrate. This drying process is often slow and in many cases (for example, when printing on to a heat-sensitive substrate such as paper) cannot be accelerated.
- ink-jet ink contains unsaturated organic compounds, termed monomers, which polymerise by irradiation, commonly with ultraviolet light, in the presence of a photoinitiator.
- This type of ink has the advantage that it is not necessary to evaporate the liquid phase to dry the print; instead the print is exposed to radiation to cure or harden it, a process which is more rapid than evaporation of solvent at moderate temperatures.
- Photochromic dyes are dyes that undergo a reversible colour change upon exposure to radiation, for example UV light. The colour change may be from colourless to coloured, or from one colour to another colour. The change in colour is due to structural changes in the dye molecule caused by the radiation.
- Photochromic dyes are currently used in Transitions® spectacle lenses, in special effect toys and in inks for use in speciality clothing and security purposes.
- identification marks can be applied to a document using a colourless photochromic ink. Upon exposure to radiation, the identification mark becomes visible, allowing authentication of the document.
- the present invention provides an ink comprising at least one acrylate monomer that comprises a non-bridged cyclic group, at least one photoinitiator and at least one photochromic dye.
- the "acrylate monomer that comprises a non-bridged cyclic group” is a compound of the following formula
- Non-bridged cyclic group means a cyclic group that does not include a bridge.
- the IUPAC Compendium of Chemical Technology defines a bridge as "a valence bond or an atom or an unbranched chain of atoms connecting two different parts of a molecule".
- non-bridged cyclic group therefore means a cyclic group that includes no valence bond or atom or unbranched chain of atoms connecting two different parts of the cyclic group.
- the non-bridged cyclic group is therefore monocyclic.
- An example of a cyclic group that does include a bridge is the isobornyl group.
- non-bridged cyclic groups include saturated or partially saturated carbocyclic rings having, for example, 3 to 8 carbon atoms and which may optionally include one or more heteroatoms selected from N, O and S; monocyclic aryl groups wherein aryl means a carbocyclic aromatic ring, and monocylic heterocyclic aromatic rings containing one or more heteroatoms selected from N, O and S.
- the non-bridged cyclic group is preferably a C3-C7 cycloalkyl group, a phenyl group or a 3- to 5-membered heterocycle.
- C3-C7 cycloalkyl is meant a saturated monocyclic ring structure containing 3 to 7 carbon atoms.
- 5- to 7-membered heterocycle is meant a 5- to 7- membered monocyclic heterocyclic ring which is either saturated or aromatic.
- Each heterocycle consists of 3 or more carbon atoms and 1 to 3 heteroatoms independently selected from O, N and S. Saturated rings comprising one or more oxygen heteroatoms are preferred.
- the non-bridged cyclic group may be attached to the ester moiety of the acrylate by a chemical bond, or by a hydrocarbyl linking group wherein one or more carbon atoms may be replaced with a heteroatom, for example a straight or branched chain Ci-C 6 alkylene group, or a C 2 -C 6 alkylene group in which one of the carbon atoms is replaced with -O- .
- Preferred acrylate monomers that comprise a non-bridged cyclic group include phenoxyethyl acrylate (PEA), tetrahydrofurfuryl acrylate (THFA) and cyclic TMP formal acrylate (CTFA). These monomers are well known in the art and have the structures shown below:
- the ink of the invention may comprise one acrylate monomer that comprises a non- bridged cyclic group or a mixture of two or more acrylate monomers that comprise a non-bridged cyclic group.
- the ink of the invention comprises one acrylate monomer that comprises a non-bridged cyclic group.
- the ink of the present invention may optionally comprise one or more mono functional monomers in addition to the acrylate monomer that comprises a non-bridged cyclic group.
- mono functional monomers include mono functional (meth)acrylate monomers, N-vinyl amides and N-acryloyl amines.
- Suitable monofunctional (meth)acrylate monomers are well known in the art and are preferably the esters of acrylic acid. Preferred examples include:
- IBOA Isobornyl acrylate
- Isodecyl acrylate (IDA) Lauryl acrylate mol wt 212 g/mol mol wt 240 g/mol
- N- Vinyl amides have a vinyl group attached to the nitrogen atom of an amide which may be further substituted in an analogous manner to the (meth)acrylate monomers.
- Examples include N-vinyl caprolactam (NVC) and N-vinyl pyrrolidone (NVP):
- N-Acryloyl amines also have a vinyl group attached to an amide but via the carbonyl carbon atom and again may be further substituted in an analogous manner to the (meth)acrylate monomers.
- acryloyl incorporates a carbonyl group
- the amide is actually named as an amine.
- An example is N-acryloylmorpholine (ACMO):
- the ink of the invention comprises one or more additional mono functional monomers selected from N-vinyl amides and N-acryloyl amines, preferably NVC.
- the at least one acrylate monomer that comprises a non-bridged cyclic group is preferably present in an amount of 40 to 95 wt%, and one or more additional mono functional monomers are present in an amount of 0 to 40 wt%, based on the total weight of the ink.
- the ink of the invention comprises at least 50 wt% of at least one acrylate monomer that comprises a non-bridged cyclic group, more preferably at least 70 wt%, more preferably at least 80 wt% and most preferably at least 85 wt%, based on the total weight of the ink.
- the mono functional monomer component of the ink consists essentially of at least one acrylate monomer that comprises a non-bridged cyclic group.
- inks of this invention comprise 40 to 70 wt% of at least one acrylate monomer that comprises a non-bridged cyclic group and 20 to 40 wt% of one or more additional mono functional monomers, based on the total weight of the ink.
- the ink of the present invention comprises PEA and NVC.
- Preferred inks of this embodiment comprise 40 to 70 wt% PEA and 20 to 40 wt% NVC, based on the total weight of the ink.
- the ink of the present invention dries primarily by curing, i.e. by the polymerisation of the monomers present, as discussed hereinabove, and hence is a curable ink.
- the ink does not therefore require the presence of water or a volatile organic solvent to effect drying of the ink, although the presence of such components may be tolerated.
- the ink of the present invention is substantially free of water and volatile organic solvents.
- Examples of the multifunctional acrylate monomers which may be included in the ink formulation include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethyleneglycol diacrylate, for example, tetraethyleneglycol diacrylate, dipropyleneglycol diacrylate, tri(propylene glycol) triacrylate, neopentylglycol diacrylate, bis(pentaerythritol) hexa-acrylate, and the acrylate esters of ethoxylated or propoxylated glycols and polyols, for example, propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, and mixtures thereof.
- Particularly preferred are difunctional acrylates with a molecular weight greater than 200.
- suitable multifunctional acrylate monomers include esters of methacrylic acid (i.e. methacrylates), such as hexanediol dimethacrylate, trimethylolpropane trimacrylate, triethyleneglycol dimethacrylate, diethyleneglycol dimethacylate, ethyleneglycol dimethacrylate, 1,4-butanediol dimethacrylate.
- methacrylates esters of methacrylic acid (i.e. methacrylates), such as hexanediol dimethacrylate, trimethylolpropane trimacrylate, triethyleneglycol dimethacrylate, diethyleneglycol dimethacylate, ethyleneglycol dimethacrylate, 1,4-butanediol dimethacrylate.
- the ink is substantially free of multifunctional monomer, meaning that only trace amounts will be present, for example as impurities in the mono functional material or as a component in a commercially available pigment dispersion.
- the multifunctional monomer is present in an amount of no more than 15 wt%, preferably no more than 10 wt%, more preferably no more than 7 wt%, more preferably no more than 5 wt% and most preferably no more than 2 wt% based on the total weight of the ink.
- the multifunctional monomer which is limited in amount may be any multifunctional monomer which could be involved in the curing reaction, such as a multifunctional (meth)acrylate monomer or a multifunctional vinyl ether.
- the ink is substantially free of oligomeric and polymeric material meaning that only trace amounts will be present.
- the oligomeric and polymeric material is present in an amount of no more than 20 wt%, more preferably no more than 10 wt%, most preferably no more than 5 wt% based on the total weight of the ink.
- Oligomeric and polymeric materials e.g. acrylate oligomers and inert thermoplastic resins, respectively
- the upper limit is less relevant, but is preferably less than 10,000, more preferably less than 5,000.
- the ink of the invention includes a photoinitiator, which, under irradiation by, for example, ultraviolet light, initiates the polymerisation of the monomers.
- a photoinitiator which, under irradiation by, for example, ultraviolet light, initiates the polymerisation of the monomers.
- photoinitiators which produce free radicals on irradiation (free radical photoinitiators) such as, for example, benzophenone,
- the photoinitiator is present from 1 to 20% by weight, preferably from 4 to 10% by weight, of the ink.
- the ink of the present invention comprises at least one ⁇ - amino ketone photoinitiator.
- ⁇ -amino ketone photoinitiator is meant a radical photoinitiator that comprises the following moiety, where the dashed lines represent bonds to other atoms or chemical groups:
- the ⁇ -amino ketone photoinitiator is an ⁇ -amino phenyl ketone.
- Preferred examples of ⁇ -amino ketone photoinitiators include 2-benzyl-2-(dimethylamino)-l-[4- (4-morpholinyl)phenyl]-l-butanone, and 2-methyl-l-[4-(methyl thio)phenyl]- 2-(4-morpholinyl)-l-propanone.
- photoinitiators are known and commercially available under the trade names Irgacure 369 and Irgacure 907 (from Ciba).
- the photoinitiator component of the ink of the invention consists essentially of at least one ⁇ -amino ketone photoinitiator. It has surprisingly been found that the use of an ⁇ -amino ketone photoinitiator in the inks of the invention is particularly advantageous.
- inks according to this preferred embodiment of the invention show a more pronounced photochromic effect than inks comprising other commonly-used free radical photoinitiators.
- the inks according the preferred embodiment can be printed in relatively thin films, while still providing a useful photochromic effect.
- the inks of this preferred embodiment can be printed in thicknesses of 5 to 10 microns. This is advantageous because films having the required photochromic effect can be printed in a single pass, which means that film production is efficient. For inks comprising less preferred photoinitiators, films having the required photochromic effect can be produced by increasing the printed film thickness.
- the photoinitiator may optionally be used together with an amine synergist.
- Amine synergists are well known in the art and include methyldiethanolamine (MDA) and ethyl 4-dimethylaminobenzoate (EPD).
- MDA methyldiethanolamine
- EPD ethyl 4-dimethylaminobenzoate
- an amine synergist is present, it is preferably used in an amount of 1 to 10 % by weight, based on the total weight of the ink.
- the ink of the present invention also comprises at least one photochromic dye.
- Photochromic dyes are materials that undergo a reversible colour change when exposed to radiation, preferably UV radiation. Suitable photochromic dyes are known and include spiropyrans, azobenzenes, stilbenes, naphthopyrans, spiro-oxazines, chalcones, diarylethenes and fulgides.
- the ink of the present invention is preferably capable of reversibly changing colour many times. If the radiation used to cure the ink of the present invention is of the same wavelength as the radiation that causes the colour change in the photochromic dye, exposure to radiation in the cure step may cause degradation of the photochromic dye.
- the photochromic dye used in the ink of the invention is therefore preferably fatigue-resistant.
- fatigue-resistant is meant that the photochromic dye does not degrade significantly upon exposure to radiation, particularly UV radiation.
- Preferred fatigue-resistant photochromic dyes are spiro- naphthoxazines and naphthopyrans.
- Spiro-naphthoxazines and naphthopyrans are known and are commercially available for example under the name Reversacol from James Robinson Ltd. Examples include Palatinate Purple, Sea Green, Aqua Green and Plum Red.
- the at least one photochromic dye is preferably present in an amount of 0.01 wt% to 20 wt% based on the total weight of the ink, preferably 0.1 to 10 wt%, most preferably 0.5 to 5 wt%.
- the inks of the invention may contain a silicone surface additive in an amount of 0.05 to 3 wt %, based on the total weight of the ink.
- the present invention also provides a method of printing using the above-described ink and a substrate having the cured ink thereon.
- Suitable substrates include styrene, PolyCarb (a polycarbonate), BannerPVC (a PVC) and VIVAK (a polyethylene terephthalate glycol modified).
- the inks of the invention can be printed on optical media such as DVDs and high density (HD)-DVDs, which are made from polycarbonate, and CDs and Blu-ray Discs (BDs), which are also made from polycarbonate but which have a coating on the outer layer.
- the ink of the present invention is preferably cured by ultraviolet irradiation.
- the ink of the invention can be used for flexographic printing, the ink of the present invention is preferably an ink-jet ink and is suitable for application by ink-jet printing.
- the inks of the present invention can be used for security purposes in the optical media market.
- a small logo could be printed on a DVD using colourless photochromic ink when the DVD is produced.
- the DVD can be irradiated with UV light which would cause the ink to become visible, allowing the user to verify that the DVD is genuine.
- the ink exhibits a desirable low viscosity (less than 200 mPas, preferably less than 100 mPas, more preferably 50 mPas and most preferably less than 25 mPas at 25 0 C). Viscosity may be measured using a digital Brookfield viscometer fitted with a thermostatically controlled cup and spindle arrangement, such as model LDV 1+ with the ULA spindle and cup arrangement and a spindle speed of 20 rpm.
- (Meth)acrylate is intended herein to have its standard meaning, i.e. acrylate and/or methacrylate.
- Mono and multifunctional are also intended to have their standard meanings, i.e. one and two or more groups, respectively, which take part in the polymerisation reaction on curing.
- the inks of the invention may be prepared by known methods such as, for example, stirring with a high-speed water-cooled stirrer, milling on a horizontal bead-mill or ultrasonification. Throughout the text amounts are provided in weight percentages unless stated otherwise.
- the inks of the examples comprise the following materials:
- Irgacure 907 2-methyl-l-[4-(methylthio)phenyl]-2-(4-morpholinyl)-l-propanone.
- Irgacure 369 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-l-one.
- Irgacure 184 1-hydroxycyclohexyl phenyl ketone.
- TPO diphenyl (2,4,6-trimethylbenzoyl) phospine oxide.
- Darocur 1173 2-hydroxy-2-methyl-l -phenyl- 1-propanone.
- ITX isopropylthioxanthone.
- BAPO bis acyl phosphine oxide.
- MDA methyl diethanol amine.
- EPD - ethyl 4 - dimethyl amino benzoate.
- TPO-XL - TPO photoinitiator available from BASF.
- Byk 307 - silicone surface additive available from BYK-Chemie (provided as a 1 wt% solution in PEA).
- Inks were prepared as 5 g samples in 30 ml glass jars. Raw materials were weighed on a 3 decimal place balance. Each sample was ultrasonicated for approximately 5 minutes.
- Drawdowns of the inks of Examples 1 to 11 were produced on self-adhesive backed PVC using a Maya bar 10 and a RK Print-Coat Instruments Ltd. drawdown machine operating at speed 4. The resulting drawdown thickness was 8 microns. Each drawdown was cured at 30 m/min with 2 lamps on full power until a reasonable cure was achieved (one to three passes). The inks of Examples 1, 2 and 4 produced drawdowns having a slight red tint. The remaining inks produced light green/yellow drawdowns.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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GB1011571.5A GB2468104B (en) | 2007-12-13 | 2008-12-12 | A printing ink |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GBGB0724350.4A GB0724350D0 (en) | 2007-12-13 | 2007-12-13 | A printing link |
GB0724350.4 | 2007-12-13 |
Publications (1)
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WO2009074833A1 true WO2009074833A1 (en) | 2009-06-18 |
Family
ID=39048081
Family Applications (1)
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PCT/GB2008/051179 WO2009074833A1 (en) | 2007-12-13 | 2008-12-12 | A printing ink |
Country Status (2)
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GB (2) | GB0724350D0 (en) |
WO (1) | WO2009074833A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011027162A1 (en) | 2009-09-03 | 2011-03-10 | Sericol Limited | Printing ink |
EP2412768A2 (en) | 2010-07-27 | 2012-02-01 | Fujifilm Corporation | Inkjet ink composition, inkjet recording method, and printed material |
US10543577B2 (en) | 2018-01-23 | 2020-01-28 | Clear and Dark Ltd. | Systems, methods, and apparatus for forming optical articles, and optical articles formed by the same |
WO2021095372A1 (en) * | 2019-11-13 | 2021-05-20 | 富士フイルム株式会社 | Ink composition for ink-jet recording and method for recording image |
Citations (6)
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JP2503016B2 (en) * | 1987-06-09 | 1996-06-05 | 東レ株式会社 | Water-soluble photochromic polymer |
WO2006102524A2 (en) * | 2005-03-23 | 2006-09-28 | Imtech, Inc. | Curable thermally ejectable printing fluid |
WO2007045580A1 (en) * | 2005-10-21 | 2007-04-26 | Agfa Graphics Nv | Set of curable liquids and methods for inkjet printing |
EP1803784A2 (en) * | 2005-12-28 | 2007-07-04 | Fujifilm Corporation | Ink composition, inkjet recording method, printed material, method for producing planographic printing plate, and planographic printing plate |
US20070211110A1 (en) * | 2006-03-09 | 2007-09-13 | Xerox Corporation | Radiation curable photochromic inks |
WO2007125273A1 (en) * | 2006-04-27 | 2007-11-08 | Sericol Limited | A printing ink |
-
2007
- 2007-12-13 GB GBGB0724350.4A patent/GB0724350D0/en not_active Ceased
-
2008
- 2008-12-12 WO PCT/GB2008/051179 patent/WO2009074833A1/en active Application Filing
- 2008-12-12 GB GB1011571.5A patent/GB2468104B/en not_active Expired - Fee Related
Patent Citations (6)
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JP2503016B2 (en) * | 1987-06-09 | 1996-06-05 | 東レ株式会社 | Water-soluble photochromic polymer |
WO2006102524A2 (en) * | 2005-03-23 | 2006-09-28 | Imtech, Inc. | Curable thermally ejectable printing fluid |
WO2007045580A1 (en) * | 2005-10-21 | 2007-04-26 | Agfa Graphics Nv | Set of curable liquids and methods for inkjet printing |
EP1803784A2 (en) * | 2005-12-28 | 2007-07-04 | Fujifilm Corporation | Ink composition, inkjet recording method, printed material, method for producing planographic printing plate, and planographic printing plate |
US20070211110A1 (en) * | 2006-03-09 | 2007-09-13 | Xerox Corporation | Radiation curable photochromic inks |
WO2007125273A1 (en) * | 2006-04-27 | 2007-11-08 | Sericol Limited | A printing ink |
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DATABASE WPI Week 199627, Derwent World Patents Index; AN 1989-035329, XP002517916 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011027162A1 (en) | 2009-09-03 | 2011-03-10 | Sericol Limited | Printing ink |
US9447302B2 (en) | 2009-09-03 | 2016-09-20 | Sericol Limited | Printing ink |
EP2467438B2 (en) † | 2009-09-03 | 2020-01-29 | Sericol Limited | Printing ink |
EP2412768A2 (en) | 2010-07-27 | 2012-02-01 | Fujifilm Corporation | Inkjet ink composition, inkjet recording method, and printed material |
US8752950B2 (en) | 2010-07-27 | 2014-06-17 | Fujifilm Corporation | Inkjet ink composition, inkjet recording method, and printed material |
US10543577B2 (en) | 2018-01-23 | 2020-01-28 | Clear and Dark Ltd. | Systems, methods, and apparatus for forming optical articles, and optical articles formed by the same |
WO2021095372A1 (en) * | 2019-11-13 | 2021-05-20 | 富士フイルム株式会社 | Ink composition for ink-jet recording and method for recording image |
JPWO2021095372A1 (en) * | 2019-11-13 | 2021-05-20 | ||
CN114729218A (en) * | 2019-11-13 | 2022-07-08 | 富士胶片株式会社 | Ink composition for inkjet recording and image recording method |
JP7309895B2 (en) | 2019-11-13 | 2023-07-18 | 富士フイルム株式会社 | Ink composition for inkjet recording and image recording method |
Also Published As
Publication number | Publication date |
---|---|
GB201011571D0 (en) | 2010-08-25 |
GB0724350D0 (en) | 2008-01-30 |
GB2468104A (en) | 2010-08-25 |
GB2468104B (en) | 2012-05-23 |
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