OA17344A - Polymer-bonded perylene dyes and compositions containing same. - Google Patents
Polymer-bonded perylene dyes and compositions containing same. Download PDFInfo
- Publication number
- OA17344A OA17344A OA1201200492 OA17344A OA 17344 A OA17344 A OA 17344A OA 1201200492 OA1201200492 OA 1201200492 OA 17344 A OA17344 A OA 17344A
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- OA
- OAPI
- Prior art keywords
- groups
- polymer
- perylene dye
- represent
- different
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- 229920000642 polymer Polymers 0.000 title claims abstract description 131
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 title claims description 59
- 239000000975 dye Substances 0.000 title description 108
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 230000001965 increased Effects 0.000 claims abstract description 6
- -1 cycloaliphatic Chemical group 0.000 claims description 132
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 87
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 238000007639 printing Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000001072 heteroaryl group Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 229910006069 SO3H Inorganic materials 0.000 claims description 18
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 18
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 201000002674 obstructive nephropathy Diseases 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims 1
- 239000000976 ink Substances 0.000 description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 25
- 239000000049 pigment Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000007641 inkjet printing Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 125000000547 substituted alkyl group Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 125000002877 alkyl aryl group Chemical group 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000001400 nonyl 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])[H] 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 125000003107 substituted aryl group Chemical group 0.000 description 6
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical group C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M Lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 125000004423 acyloxy group Chemical group 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 4
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000005333 aroyloxy group Chemical group 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 4
- 125000005842 heteroatoms Chemical group 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001225 Polyester resin Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000005418 aryl aryl group Chemical group 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 210000004080 Milk Anatomy 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000269 nucleophilic Effects 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000002417 nutraceutical Substances 0.000 description 2
- 230000003287 optical Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000004642 transportation engineering Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- IBPHXKCFBXEFQP-UHFFFAOYSA-N 1,1,1,2,2-pentafluoroethane Chemical group F[C](F)C(F)(F)F IBPHXKCFBXEFQP-UHFFFAOYSA-N 0.000 description 1
- KGCJCDXZSPVGGX-UHFFFAOYSA-N 1-bromoperylene Chemical group C1=CC(C=2C(Br)=CC=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 KGCJCDXZSPVGGX-UHFFFAOYSA-N 0.000 description 1
- WOPGSMVMUKLOCF-UHFFFAOYSA-N 1-chloroperylene Chemical group C1=CC(C=2C(Cl)=CC=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 WOPGSMVMUKLOCF-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004539 5-benzimidazolyl group Chemical group N1=CNC2=C1C=CC(=C2)* 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 210000003666 Nerve Fibers, Myelinated Anatomy 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical class [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N Perylene Chemical compound C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M Potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- BKBKEFQIOUYLBC-UHFFFAOYSA-N Tetrabutylammonium hexafluorophosphate Chemical compound F[P-](F)(F)(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC BKBKEFQIOUYLBC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 230000003115 biocidal Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000006384 methylpyridyl group Chemical group 0.000 description 1
- 125000004312 morpholin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])OC([H])(*)C1([H])[H] 0.000 description 1
- 125000004572 morpholin-3-yl group Chemical group N1C(COCC1)* 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000004483 piperidin-3-yl group Chemical group N1CC(CCC1)* 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000005344 pyridylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 125000004943 pyrimidin-6-yl group Chemical group N1=CN=CC=C1* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- QHOKENWFMZXSEU-UHFFFAOYSA-N tetrabutylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC QHOKENWFMZXSEU-UHFFFAOYSA-N 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000005301 thienylmethyl group Chemical group [H]C1=C([H])C([H])=C(S1)C([H])([H])* 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
A method of increasing the solubility and/or dispersibility of a perylene dye in a liquid medium. The method comprises binding the perylene dye to a polymer which is soluble in the liquid medium.
Description
POLYMER-BONDED PERYLENE DYES AND COMPOSITIONS CONTAINING SAME
BACKGROUND OF THE INVENTION
1. Field of the Invention [0001] The présent invention relates to polymer-bonded perylene dyes and compositions such as, e.g., printing inks which comprise polymer-bonded perylene dyes as colorants.
2. Discussion of Background Information [0002] Counterfeiting and market diversion of mass produced goods are facilitated if the products are handled on a lot base rather than on an îndividual item base. In such case counterfeit or diverted products are easily introduced into the supply chain. Producers and retailers would like to be in a position to distinguish their original products from such counterfeit or diverted (parallel imported or smuggled) products at the level of the îndividual unit that is sold.
[0003] Further, secure documents such as currency, passports, or identity cards are increasingly counterfeit around the world. This situation is a very critical issue for governments and society in general. For example criminal organizations may use fake passports or identity cards for human beings traffic. As reprographie technologies become more and more sophisticated, it becomes even more difficult to make a clear distinction between a fake document and the original. Document security has therefore a considérable impact on the economy of the countries and also on the victims of illicit traffic involving counterfeit documents.
[0004] In an attempt to prevent counterfeiting marking is currently used extensively for the récognition, identification and authentication of îndividual items. The marking may be applied, for example, in the form of indicia such as 1-dimensional barcodes, stacked 1-dimensional barcodes, 2-dimensional barcodes, 3-dimensional barcodes, a data matrix, and the like. The application of markings is frequently carried out by a printing process which uses a printing ink with spécifie optical properties that are imparted to the ink by one or more substances contained therein such as, e.g., luminescent dyes and pigments and cholesteric liquid crystal compounds.
[0005] A class of compounds which is suitable for use in, e.g., printing inks for marking purposes are perylene dyes. The parent compound perylene displays fluorescence and there are many dérivatives of perylene which are known and may theoretically be employed as colorants in compositions for marking such as printing inks and the like. However, a drawback of perylene dyes is their often unsatisfactorily low solubility or dispersibility in liquid media such as those which are useful in printing inks. This low solubility/dispersibility limits the suitability of perylene dyes as colorants for liquid compositions in general. It would thus, be advantageous to be able to increase the solubility and/or dispersibility of perylene dyes in liquid media and in particular, liquid media for use in printing inks.
SUMMARY OF THE INVENTION [0006] The présent invention provides a method of increasing the solubility and/or dispersibility of a perylene dye in a liquid medium such as, e.g., a liquid medium comprised in a printing ink composition. The method comprises binding the perylene dye to a polymer which is soluble in the liquid medium.
[0007] In one aspect of the method, the liquid medium may be a polar liquid medium.
[0008] In another aspect, the perylene dye may be covalently bonded to the polymer. For example, the polymer may comprise at least one (recurring) monomer unit that comprises at least one polar group which may, for example, be selected from hydroxy, carboxy and amino groups. Accordingly, the polymer may, for example, comprise a phenolic resin such as, e.g., a phenolic resin of formula
(IV) wherein the groups R4 may be the same or different and are selected from alkyl groups having from l to about 10 carbon atoms and the average number of m is from about l to about 30, for example, from about l to about 25, from about 1 to about 15, from about 1 to about 10, from about 1 to about 5, from about 1 to about 3, from about 5 to about 15, from about 5 to about 10, from about 10 to about 20, or from about 20 to about 30. The groups R4 may be the same or different (preferably the same) and may, for example, be selected from tert-butyl, tert-octyl and branched nonyl. Further, a group R4 may be in the meta- or para-position with respect to the OH group (in formula (IV) only the para position is shown), and there may be more than one group R4 (e.g., 2 or 3 groups R4) présent on a phenyl ring. For example, if two groups R4 are présent on a phenyl ring (the same or different, preferably the same groups R4) they may be présent in any of the available positions on the phenyl ring, such as, e.g., meta/para or meta/meta.
[0009] In another aspect of the method of the présent invention, the perylene dye may be bonded to the polymer by reacting a group comprised in the perylene dye with the at least one (preferably) polar group of the polymer. The at least one polar group may, for example, be a hydroxy group and/or the group comprised in the perylene dye may be a halogen such as, e.g., Br or Cl.
[0010] In a still further aspect of the method compound of formula (A) or formula (B):
of the présent invention, the perylene dye may be a
(B) (A) wherein:
the groups Z, the same or different from each other, represent O, S or N-R, provided that in the above formulae the unit -CO-Z-CO- (in the case of formula (B) one or both units of formula -CO-Z-CO-) may be replaced by a unit -CS-Z-CO-, or a unit -CS-Z-CS-, or by [-COOH HOOC-] (i.e., the dicarboxylic acid instead ofthe cyclic anhydride) and further provided that for Z = N-R the unit -CO-Z-CO- may be replaced by a unit of formula -C(=NR’)-NR-CO-;
R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms; and R and R’ may also be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
the groups X may be the same or different and represent halogen, COOH, and isocyanate (NCO);
the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different
X and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms and, where two groups R” are présent, may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
n and p each represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7 or 8), provided that (n+p) is not higher than 8 and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent.
[0011] In one aspect of the compounds of the above formulae, the (only) group Z or at least one of the groups Z represents N-R wherein R may be selected, for example, from optionally substituted alkyl having from 1 to about 6 carbon atoms, optionally substituted alkylaryl or arylalkyl having from 7 to about 12 carbon atoms, optionally substituted aryl having from about 6 to about 20 carbon atoms, and optionally substituted heteroaryl having from about 3 to about 20 carbon atoms such as, e.g., from optionally substituted alkyl having from 1 to about 4 carbon atoms, optionally substituted phenyl, or optionally substituted benzyl. By way of non-limiting example, R may represent phenyl substituted with from 1 to about 3 groups selected from halogen and alkyl having from 1 to about 6 carbon atoms such as, e.g., a phenyl group substituted by at least two alkyl groups which comprise a secondary or tertiary carbon atom, examples of which include isopropyl and tert.-butyl groups.
[0012] In another aspect of the compounds of the above formulae, the perylene dye may be a compound of formula (A). Alternatively, the perylene dye may be a compound of formula (B) such as, e.g., a compound of formula (B) wherein the groups Z may be the same or different and represent O or N-R (including compounds wherein both groups Z are O, compounds wherein both groups Z are N-R (with the groups R being the same or different), and compounds wherein one group Z is O and the other group Z is N-R).
[0013] The présent invention also provides a perylene dye whose solubility and/or dispersibility in a polar liquid medium has been increased by having been bonded to a polymer, as well as a polymer-bonded perylene dye of formula (A) or formula (B):
λ
(B) wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that the unit -CO-Z-CO- (in the case of formula (B) one unit or both units) may be replaced by -CS-Z-CO- or a unit -CS-Z-CS-, or may be replaced by [-COOH HOOC-] (i.e., the dicarboxylic acid instead of the anhydride) and further provided that for Z = N-R the unit -CO-Z-CO- may be replaced by a unit of formula -C(=NR’)-NR-CO-;
R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyi or heteroarylalkyl group having from l to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
the groups X may be the same or different and represent halogen, isocyanate and COOH, with the proviso that at least one group X (which may be the only group X) represents a group of formula -L-P wherein L represents a covalent (direct) bond or a bridging group and P represents a polymer molécule;
the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyi or heteroarylalkyl group having from 1 to about 20 carbon atoms and, where two groups R” are présent, may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
n and ρ each represent 0 or an integer of from l to 8 (i.e., I, 2, 3, 4, 5, 6, 7 or 8), provided that (n+p) is not higher than 8 and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent.
[0014] In one aspect of the polymer-bonded perylene dye of the présent invention, the (only) group Z or at least one of the groups Z (in the case of formula (B)) represents N-R wherein R may be selected, for example, from optionally substituted alkyl having from 1 to about 6 carbon atoms, optionally substituted alkylaryl or arylalkyl having from 7 to about 12 carbon atoms, optionally substituted aryl having from about 6 to about 20 carbon atoms, and optionally substituted heteroaryl having from about 3 to about 20 carbon atoms such as, e.g., from optionally substituted alkyl having from 1 to about 4 carbon atoms, optionally substituted phenyl, or optionally substituted benzyl. By way of non-limiting example, R may represent phenyl substituted with from 1 to about 3 groups selected from halogen and alkyl having from 1 to about 6 carbon atoms such as, e.g., a phenyl group substituted by at least two alkyl groups which comprise a secondary or tertiary carbon atom, non-limiting examples of which include isopropyl and tert.-butyl groups.
[0015] In another aspect of the polymer-bonded perylene dye of the présent invention, the perylene dye may be a compound of formula (A). Alternatively, the polymer-bonded perylene dye may be a compound of formula (B) such as, e.g., a compound of formula (B) wherein the groups Z may be the same or different and represent O or N-R (including compounds wherein both groups Z are O, compounds wherein both groups Z are N-R (the groups R being the same or different) and compounds wherein one group Z is O and the other group Z is N-R).
[0016] In yet another aspect of the polymer-bonded perylene dye of the présent invention, L may be selected from O, C(=O)O, OC(=O), C(=O)NH, NHC(=O)O, NHC(=O)NH and C(=O)OC(=O). For example, L may represent O.
[0017] In a still further aspect of the polymer-bonded perylene dye of the présent invention, P may represent a polymer molécule that comprises at least one (recurring) monomer unit that comprises at least one polar group such as, e.g., at least one polar group selected from hydroxy, carboxy and amino groups. By way of non-limiting example, the polymer may comprise a phenolic resin such as, e.g., a phenolic resin of formula
OH
OH
OH
(IV) wherein the groups R4 may be the same or different and are selected from alkyl groups having from l to about 10 carbon atoms and the average number of m is from about l to about 30, for example, from about l to about 25, from about l to about 15, from about 1 to about 10, from about 1 to about 5, from about 1 to about 3, from about 5 to about 15, from about 5 to about 10, from about 10 to about 20, or from about 20 to about 30. The groups R4 may be the same or different (preferably the same) and may, for example, be selected from tert-butyl, tert-octyl and branched nonyl. Further, a group R4 may be in the meta- or para-position with respect to the OH group (in formula (IV) only the para position is shown), and there may be more than one group
R4 (e.g., 2 or 3 groups R4) présent on a phenyl ring. For example, if two groups R4 are présent on a phenyl ring (the same or different, preferably the same groups R4) they may be présent in any of the available positions on the phenyl ring, such as, e.g., meta/para or meta/meta.
[0018] In another aspect of the polymer-bonded perylene dye of the présent invention, P may 15 hâve one or more than one perylene dye molécule bonded thereto.
[0019] The présent invention also provides a process for making a polymer-bonded perylene dye as set forth above (including the various aspects thereof). The process comprises contacting a perylene dye of formula (A) or formula (B):
O .O
O.
O z
O (A) (B)
I wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that the unit -CO-Z-CO- (in the case of formula (B) one or both units) may be replaced by -CS-Z-CO- or a unit -CS-Z-CS-, or may be replaced by [-COOH HOOC-] (i.e., the dicarboxylic acid instead of the anhydride) and that for Z = N-R the unit -CO-Z-CO- may be replaced by a unit of formula -C(=NR’)-NR-CO-;
R and R’ in the above formulae (A) and (B) independently represent an optionally substîtuted aliphatîc, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms; and R and R’ may also be combined to form, together with the N atoms to which they are attached, an optionally substîtuted and/or fused 5- to 7-membered ring;
the groups X may be the same or different and represent halogen, isocyanate and COOH;
the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substîtuted aliphatîc, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms and may also be combined to form, together with the N atom to which they are attached, an optionally substîtuted and/or fiised 5- to 7-membered ring;
n and p each represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7 or 8), provided that (n+p) is not higher than 8, and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent;
with a polymer P under conditions which cause a reaction of a (at least one) group X of the perylene dye with a functional group of the polymer to covalently bind the polymer to the perylene dye.
[0020] In one aspect of the process, a group X of the perylene dye that represents halogen may be caused to react with an OH group of the polymer P to replace X by a group -O-P. For example, the OH group of the polymer may be a phenolic OH group.
[0021] In another aspect of the process of the présent invention, the process may be carried out in the presence of a base.
[0022] The présent invention also provides a polymer-bonded perylene dye of one of formulae (I)to(III):
wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that in the case of formula (III) one or both units -CO-Z-CO- may be replaced by -CS-Z-CO- or a unit -CS-Z-CS-, or may be replaced by [-COOH HOOC-] (i.e., the dicarboxylic acid instead of the anhydride) and that for Z = N-R the unit -CO-Z-CO- may be replaced by a unit of formula -C(=NR’)-NR-CO-;
R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
Ri, R2 and R3 are independently selected from hydrogen, optionally substituted Ci-C4 alkyl, optionally substituted CrC4 alkyl-COOH, optionally substituted C]-C4 alkyl-SChH, optionally substituted Ci-C4 alkoxy, optionally substituted mono(Ci-C4)alkylamino, optionally substituted di(Ci-C4)alkylamino, optionally substituted CrC4 aminoalkyl, halogen, cyano, nitro, and SO3H;
the groups X may be the same or different and represent halogen, isocyanate and COOH;
the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic,
alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms and, where two groups R” are présent, may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;
in the case of formula (II), n and p each represent 0 or an integer of from l to 8 (i.e., I, 2, 3, 4, 5, 6, 7 or 8), provided that (n+p) is not higher than 8; and in the case of formulae (I) and (III), n and p each represent 0 or an integer of from 1 to 7 (i.e., 1, 2, 3, 4, 5, 6 or 7), provided that (n+p) is not higher than 7 (and preferably not higher than 4); and
P represents a polymer molécule.
[0023] In one aspect of the above polymer-bonded perylene dye, P may represent a polymer molécule that comprises at least one monomer unit that comprises at least one polar group such as, e.g., a group selected from hydroxy, carboxy and amino groups. By way of non-limiting example, the polymer may comprise a phenolic resin such as, e.g., a resin of formula
OH
OH
OH (IV) wherein the groups Ri may be the same or different and are selected from alkyl groups having from 1 to about 10 carbon atoms and the average number of m is from about 1 to about 30, for example, from about 1 to about 25, from about 1 to about 15, from about 1 to about 10, from about 1 to about 5, from about 1 to about 3, from about 5 to about 15, from about 5 to about 10, from about 10 to about 20, or from about 20 to about 30. The groups R4 may be the same or different (preferably the same) and may, for example, be selected from tert-butyl, tert-octyl and branched nonyl. Further, a group R4 may be in the meta- or para-position with respect to the OH group (in formula (IV) only the para position is shown), and there may be more than one group R4 (e.g., 2 or 3 groups R4) présent on a phenyl ring. For example, if two groups R4 are présent on a phenyl ring (the same or different, preferably the same groups R4) they may be présent in any of the available positions on the phenyl ring, such as, e.g., meta/para or meta/meta.
[0024] In another aspect of the above polymer-bonded perylene dye, P may hâve one or more than one perylene dye molécule (e.g., 1, 2, 3, 4, 5, 6, or more perylene dye molécules) bonded thereto. Conversely, a perylene dye molécule may hâve one or more than one polymer molécule
P (e.g., I, 2, 3, 4 or more polymer molécules P) bonded thereto. Even further, a polymer molécule P may hâve at least two perylene dye molécules bonded thereto, at least one of these perylene dye molécules being bonded to at least one additional polymer molécule P (which in turn may or may not be bonded to one or more additional perylene dye molécules).
[0025] In yet another aspect, in the above polymer-bonded perylene dye Ri, R2, and R3 may independently be selected from hydrogen, Ci-C4 alkyl, C1-C4 alkoxy, halogen, and SO3H and/or the perylene dye may be a compound of formula (I) or (III) wherein (n+p) is 1, 2 or 3 and X represents Cl or Br, or wherein (n+p) is 0 and/or R| and R2 are selected from C1-C4 alkyl groups. Even further, the perylene dye may be a compound of formula (I) where R3 represents hydrogen, or a compound of formula (I) wherein R] represents SO3H and R2 and R3 represent hydrogen.
[0026] The présent invention also provides a process for making a polymer-bonded perylene dye of any one of formulae (I) to (III) set forth above. The process comprises contacting a compound of formula (I’) to (III’)
wherein Rb R2, R3, X and Y are as defined above for formulae (I) to (III) and n is at least 1 and (n+p) is 1, 2, 3 or 4, with a polymer P, i.e., a polymer molécule which comprises a group that is capable of reacting with X to replace X by a group of formula OP.
[0027] In one aspect, the process may be carried out in a polar aprotic organic solvent in which the polymer P is soluble. For example, the polar solvent may comprise at least one of Nmethylpyrrolidone, dimethyl formamide, dimethyl acetamide, and dimethylsulfoxide.
[0028] In another aspect, the process may be carried out in the presence of an inorganic base and/or a strong organic non-nucleophilic base and/or in the presence of at least one anti-foam agent such as a polyethylene glycol and/or a dérivative thereof.
[0029] In yet another aspect of the process, from about 0.2 g to about 10 g of perylene dye may be employed per 100 g of polymer P, for example at least about 0.4 g, at least about 0.5 g, at least about 0.6 g, at least about 0.8 g, at least about 1 g, at least about 2 g, at least about 5 g, or at least about 8 g of perylene dye per 100 g of polymer P.
[0030] The présent invention also provides a printing ink composition which comprises a polar liquid medium that has at least one polymer-bonded perylene dye of the présent invention as set forth above (including the various aspects thereof) dissolved or dispersed therein.
[0031] In one aspect, the printing ink composition may comprise from about 0.01 % to about 40 % by weight of the at least one polymer-bonded perylene dye based on the total weight of the composition. In another aspect, the printing ink composition may further comprise at least one conductivity imparting substance (e.g., a sait).
[0032] The présent invention also provides a marking or security feature which is made with the printing ink composition of the présent invention as set forth above (including the various aspects thereof).
[0033] In one aspect, the marking or security feature may comprise at least one polymer-bonded perylene dye according to the présent invention, e.g. a polymer-bonded perylene dye of formula (A) or formula (B) and/or of any one of formulae (I) to (III) as set forth above (including the various aspects thereof). In another aspect, the marking or security feature may comprise at least one of a thread, a label, a barcode, a 2D code, a pattern, indicia, and a data matrix.
[0034] The présent invention also provides an article which comprises the marking or security feature of the présent invention as set forth above (including the various aspects thereof).
[0035] In one aspect of the article, the marking or security feature may be présent on the article in the form a layer. In another aspect, the article may be at least one of a label such as, e.g., a tax label, packaging, a can, a métal, an aluminum foil, a cartridge, a closed cartridge (e.g., a capsule) that contains, e.g., a pharmaceutical, a nutraceutical, a foodstuff or a beverage (such as, e.g., coffee, tea, milk, chocolaté, etc.), an article made of glass, an article made of ceramic, a banknote, a stamp, a security document, an identity card, a passport, a driver’s license, a crédit card, an access card, a ticket such as, e.g., a transportation ticket or an event ticket, a voucher, a value document, an ink-transfer film, a reflective film, a thread, and a commercial good.
[0036] The présent invention further provides a method of authenticating an article. The method comprises providing the article with the marking or security feature of the présent invention as set forth above and/or the application onto the article of the printing ink composition of the présent invention as set forth above.
[0037] In one aspect of the method, the article may be at least one of a a tax label, packaging, a can, a métal, an aluminum foil, a cartridge, a closed cartridge (e.g., a capsule) that contains, e.g., a pharmaceutical, a nutraceutical, a foodstuff or a beverage (such as, e.g., coffee, tea, milk, chocolaté, etc.), an article made of glass, an article made of ceramic, a banknote, a stamp, a security document, an identity card, a passport, a driver’s license, a crédit card, an access card, a ticket such as, e.g., a transportation ticket or an event ticket, a voucher, a value document, an ink-transfer film, a reflective film, a thread, and a commercial good.
[0038] The présent invention also provides a dye-doped polymer which is obtainable by a method according to the présent invention as set forth above (including the various aspects thereof). In this polymer at least about 0.1 % to 10% of ail polymer molécules hâve bonded thereto a perylene dye.
[0039] In one aspect, the polymer may comprise a phenolic resin such as, e.g., a phenolic resin of formula
(IV) wherein the groups R4 may be the same or different and are selected from alkyl groups having from l to about 10 carbon atoms and the average number of m is from about l to about 30, for example, from about l to about 25, from about l to about 15, from about l to about 10, from about l to about 5, from about l to about 3, from about 5 to about 15, from about 5 to about 10, from about 10 to about 20, or from about 20 to about 30.. The groups R4 may be the same or different (preferably the same) and may, for example, be selected from tert-butyl, tert-octyl and branched nonyl. Further, a group R4 may be in the meta- or para-position with respect to the OH group (in formula (IV) only the para position is shown), and there may be more than one group R4 (e.g., 2 or 3 groups R4) présent on a phenyl ring. For example, if two groups R4 are présent on a phenyl ring (the same or different, preferably the same groups R4) they may be présent in any ofthe available positions on the phenyl ring, such as, e.g., meta/para or meta/meta.
DETAILED DESCRIPTION OF THE PRESENT INVENTION [0040] The particulars shown herein are by way of example and for purposes of illustrative discussion of the embodiments of the présent invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the présent invention. In this regard, no attempt is made to show structural details of the présent invention in more detail than is necessary for the fundamental understanding of the présent invention, the description making apparent to those skilled in the art how the several forms of the présent invention may be embodied in practice.
[0041] As set forth above, the perylene dyes which in accordance with the présent invention are to be bonded to a polymer may be of formulae (A) or (B):
[0042] In the above formulae (A) and (B) the groups Z may represent O, S or N-R. Additionally, the unit or units -CO-Z-CO- may independently be replaced by a unit -CS-Z-CO-, or a unit -CS-Z-CS-, or by the corresponding dicarboxylic acid. Further, for Z = N-R the unit -CO-Z-COmay further be replaced by a unit of formula -C(=NR’)-NR-CO-. In the case of formula (B) the two units -CO-Z-CO-may be the same or different. If these units are different, one of the units may, for example, be -CO-O-CO- and the other one may be -CO-NR-CO-, or one may be -CO-NR-CO- and the other one may be -C(=NR’)-NR-CO, or may be -CS-O-CS-, or one unit may be -CO-NR-CO- and the other one may be -CO-NR*-CO-, with R and R* being different from each other, etc. (R* having the same meanings as R).
[0043] The groups R and R’ in the above formulae independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyi or heteroarylalkyl group having from 1 to about 20 carbon atoms. Additionally, R and
R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring.
[0044] Regarding the meanings of the groups R, R’, R”, R], R2, R3 and R4 mentioned herein, the following applies throughout the présent spécification and the appended daims (it being understood that throughout the présent spécification and the appended daims the indicated number of carbon atoms invariably refers to the respective unsubstituted group):
[0045] An “optionally substituted alkyl” group includes linear and branched alkyl groups which preferably hâve from 1 to about 12 carbon atoms, e.g., from 1 to about 8 carbon atoms, from 1 to about 6 carbon atoms, or from 1 to about 4 carbon atoms. Spécifie non-limiting examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, secbutyl, linear or branched pentyl (e.g., 2-methylbutyl, 2-ethylpropyl and 2,2-dimethylpropyl), linear or branched hexyl (e.g., 2-ethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2,3-dimethylbutyl), linear or branched heptyl, linear or branched octyl (e.g., 2-ethylhexyl), and linear or branched nonyl. The alkyl groups may be substituted with one or more substituents (e.g., one, two, three, four, etc.). Non -limiting examples of these substituents include O H, halogen such as, e.g., F, Cl, Br, and I (as in, e.g., trifluoromethyl, trichloromethyl, pentafluorethyl and 2,2,2-trifluoroethyl), alkoxy having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as, e.g., methoxy, ethoxy, propoxy and butoxy, acyloxy having from 1 to about 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxy having from about 6 to about 10 carbon atoms such as, e.g., (optionally substituted) phenoxy, aroyloxy having from about 6 to about 10 carbon atoms such as, e.g., benzoyloxy, -COOH (including partially or completely salified forms thereof), alkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyl groups such as, e.g., methoxycarbonyl and ethoxycarbonyl, -SO3H, alkylsulfonyl, arylsulfonyl, alkylsulfonylamino, nitro, cyano, amino, monoalkylamino and dialkylamino wherein the alkyl groups hâve from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino, diethylamino, propylamino and dipropylamino. The alkyl groups may also be substituted by one or more optionally substituted cycloalkyl groups (preferably having from 3 to about 8 ring carbon atoms) as further set forth below. Preferred substituents for the alkyl groups include F, Cl, Br, OH, methoxy, ethoxy, -COOH, -SO3H, amino, methylamino, ethylamino, dimethylamino and diethylamino. If more than one substituent is présent, the substituents may be the same or different. Also, one or more (e.g., one or two) of the C atoms of the alkyl group may be replaced by a heteroatom such as, e.g., O, S and NR’” (with R’” representing, for example, H or alkyl having from 1 to about 4 carbon atoms). Further, the alkyl group may hâve one or more carbonyl groups (C=O) incorporated therein and/or may comprise one or more carbon-carbon double and/or triple bonds (such as in, e.g., vinyl, allyl and propargyl).
[0046] An “optionally substituted cycloalkyl” group preferably comprises from about 3 to about 12 ring carbon atoms, more preferably from about 5 to about 8 ring carbon atoms such as, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkyl groups may be substituted with one or more substituents (e.g., one, two, three, four, etc). Non-limiting examples of these substituents include OH, halogen such as, e.g., F, Cl, Br, and I, alkoxy having from l to about 6 carbon atoms, e.g., from l to about 4 carbon atoms, such as, e.g., methoxy, ethoxy, propoxy and butoxy, acyloxy having from l to about 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxy having from about 6 to about 10 carbon atoms such as, e.g., (optionally substituted) phenoxy, aroyloxy having from about 6 to about 10 carbon atoms such as, e.g., benzoyloxy, -COOH (including partially or completely salified forms thereof), alkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyi groups such as, e.g., methoxycarbonyl and ethoxycarbonyl, -SO3H, alkylsulfonyl, arylsulfonyl, alkylsulfonylamino, nitro, cyano, amino, monoalkylamino and dialkylamino wherein the alkyi groups hâve from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino, diethylamino, propylamino and dipropylamino. The cycloalkyl groups may also be substituted by one or more optionally substituted alkyi groups (preferably having from 1 to about 4 carbon atoms) as set forth above. Preferred substituents for the alkyi groups include F, Cl, Br, OH, methoxy, ethoxy, -COOH, -SO3H, amino, methylamino, ethylamino, dimethylamino and diethylamino. If more than one substituent is présent, the substituents may be the same or different. Further, the cycloalkyl group may hâve one or more carbonyl groups (C=O) incorporated therein and/or may comprise one or more carbon-carbon double bonds (such as in, e.g., cyclopentenyl and cyclohexenyl).
[0047] An “optionally substituted aryl” group and an “optionally substituted heteroaryl” group dénoté optionally fused aryl and heteroaryl groups which preferably comprise from about 5 to about 15 ring members, e.g., from about 6 to about 10 ring members. The heteroaryl groups will usually comprise from 1 to about 3 ring members selected from O, S and N and may be partially or fully hydrogenated. Spécifie examples of these aryl and heteroaryl groups include phenyl, naphthyl, anthranyl, phenanthryl, 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, 1,2,3-triazol1-, -4- or -5-yl, 1,2,4-triazol-l-, -3- or -5-yl, 1 - or 5-tetrazolyl, l,2,3-oxadiazol-4- or -5-yl, l,2,4-oxadiazol-3- or -5-yl, l,3,4-thiadiazol-2- or -5-yl, l,2,4-thiadiazol-3- or -5-yl, 1,2,316
X thiadiazol-4- or -5-yl, 3- or 4-pyridazinyl, pyrazinyl, l-, 2-, 3-, 4-, 5-, 6- or 7-indolyl, indazolyl,
4- or 5-isoindolyl, l-, 2-, 4- or 5-benzimidazolyl, l-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzothiazolyl, 2-, 4-,
5- , 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,l,3-oxadiazolyl, 2-, 3, 4-, 5-, 6-, 7- or 8quinolyl, l-, 3-, 4-, 5-, 6-, 7- or 8-isoquinoIyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl, 5- or 6-quinoxalinyl, 2-, 3-, 5-, 6-, 7- or 8-2H- benzo-l,4-oxazinyl, 1,3benzodioxol-5-yl, l,4-benzo-dioxane-6-yl, 2,l,3-benzothiadiazol-4- or -5-yl or 2,1,3benzoxadiazol-5-yl, 2,3-dihydro-2-, -3-, -4- or -5-furyl, 2,5-dihydro-2-, -3-, -4- or -5-furyl, tetrahydro-2- or -3-furyl, l,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-l-, -2-, -3-, 4- or -5-pyrrolyl, 2,5-dihydro-l-, -2-, -3-, -4- or -5-pyrrolyl, 1-, 2- or 3-pyrrolidinyl, tetrahydro1-, -2- or -4-imidazolyl, 2,3-dihydro-l-, -2-, -3-, -4- or -5-pyrazolyl, tetrahydro-1-, -3- or -4pyrazolyl, 1,4-dihydro-l-, -2-, -3- or -4-pyridyl, 1,2,3,4-tetrahydro-l-, -2-, -3-, -4-, -5- or -6pyridyl, 1-, 2-, 3- or 4-piperidinyl, 2-, 3- or 4-morpholinyl, tetrahydro-2-, -3- or -4-pyranyl, 1 ,4dioxaneyl, l,3-dioxane-2-, -4- or -5-yl, hexahydro-1-, -3- or -4-pyridazinyl, hexahydro-1-, -2-, -4- or -5-pyrimidinyl, 1 -, 2- or 3-piperazinyl, 1 ,2,3,4-tetrahydro-l -, -2-, -3-, -4-, -5-, -6-, -Ί- or -8-quinolyl, 1,2,3,4-tetrahydro-l-, -2-, -3-, -4-, -5-, -6-, -7- or -8-isoquinolyl, 2-, 3-, 5-, 6-, 7- or 8-3,4-dihydro-2H-benzo-l,4-oxazinyl, 2,3-methylenedioxyphenyl, 3,4-methylenedioxyphenyl, 2,3-ethylenedioxyphenyl, 3,4-ethylenedioxyphenyl, 3,4-(difluoromethylenedioxy)phenyl, 2,3dihydrobenzofuran-5- or -6-yl, 2,3-(2-oxomethylenedioxy)phenyl, 3,4-dihydro-2H-l,5benzodioxepin-6- or -7-yl, 2,3-dihydrobenzofuranyl, 2,3-dihydro-2-oxofuranyl. The aryl a nd heteroaryl groups may be substituted with one or more (e.g., one, two, three, four, etc.) substituents which are preferably selected from halogen such as, e.g., F, Cl, Br, and I, OH, -COOH (including partially or completely salified forms thereof), -SO3H, nitro, cyano, alkoxy having from 1 to about 4 carbon atoms such as, e.g., methoxy and ethoxy, acyloxy having from 1 to about 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxy having from about 6 to about 10 carbon atoms such as, e.g., phenoxy, aroyloxy having from about 6 to about 10 carbon atoms such as, e.g., benzoyloxy, amino, monoalkylamino and dialkylamino wherein the alkyl groups hâve from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino, diethylamino, propylamino and dipropylamino, acylamino having from 1 to about 8 carbon atoms such as, e.g., acetylamino and propionylamino, aminocarbonyl, monoalkylaminocarbonyl, diaminocarbonyl and alkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyl groups such as, e.g., methoxycarbonyl and ethoxycarbonyl, optionally substituted acyl having from 2 to about 8 carbon atoms such as acetyl and propionyl, alkylsulfonyl, arylsulfonyl and alkylsulfonylamino. If more than one substituent is présent, the substituents may be the same or different. Also, the aryl and heteroaryl groups may be substituted by aryl groups and/or alkylaryl groups. Spécifie and non-limiting examples of substituted aryl groups include chlorophenyl, dichlorophenyl, fluorophenyl, bromophenyl, phenoxyphenyl, hydroxyphenyl, dihydroxyphenyl, methoxyphenyl, aminophenyl, dimethylaminophenyl and biphenylyl.
[0048] An “optionally substituted alkylaryl” group and an “optionally substituted alkylheteroaryl” group dénoté optionally substituted aryl groups and optionally substituted heteroaryl groups as set forth above which are (further) substituted by at least one optionally substituted alkyl group (preferably comprising from l to about 6, e.g., from l to about 4 carbon atoms) as set forth above. Spécifie examples thereof include tolyl, xylyl, mesityl, ethylphenyl, cumyl, trifluormethylphenyl, hydroxytolyl, chlorotolyl, methylpyridyl, methylfuryl, methylthienyl, diisopropylphenyl, di(tert-butyl)phenyl, and methylnaphthyl.
[0049] An “optionally substituted arylalkyl” group and an “optionally substituted heteroarylalkyl” group dénoté optionally substituted alkyl groups (preferably comprising from l to about 6, e.g., from l to about 4 carbon atoms) as set forth above which are (further) substituted by at least one optionally substituted aryl group and/or optionally substituted heteroaryl group as further set forth above. Spécifie examples thereof include benzyl, methylbenzyl, chlorobenzyl, dichlorbenzyl, hydroxybenzyl, l-phenylethyl, 2-phenylethyl, pyridylmethyl, thienylmethyl, furylmethyl, and naphthylmethyl.
[0050] An “optionally substituted and/or fused 5- to 7-membered ring” dénotés a saturated, partially unsaturated or aromatic N-heterocyclic ring which in addition to the one or two N atoms already présent therein may comprise one or two additional heteroatoms which are selected from O, N and S. The ring will usually hâve five or six ring members. Also, the ring will often comprise no additional heteroatom. Further, the ring may hâve one or two aromatic and/or heteroaromatic rings (e.g., benzene rings) fused to it and/or may be substituted with one or more (e.g., one, two, three, four, etc.) substituents which are preferably selected from F, Cl, Br, and I, OH, -COOH (including partially or completely salified forms thereof), -SO3H, cyano, nitro, alkoxy having from l to about 4 carbon atoms such as, e.g., methoxy and ethoxy, acyloxy having from l to about 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxy having from about 6 to about 10 carbon atoms such as, e.g., phenoxy, aroyloxy having from about 6 to about 10 carbon atoms such as, e.g., benzoyloxy, amino, monoalkylamino and dialkylamino wherein the alkyl groups hâve from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino, diethylamino, propylamino and dipropylamino, acylamino having from 1 to about 8 carbon atoms such as, e.g., acetylamino and propionylamino, aminocarbonyl, monoalkylaminocarbonyl, diaminocarbonyl and alkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyl groups such as, e.g., methoxycarbonyl and ethoxycarbonyl, optionally substîtuted acyl having from 2 to about 8 carbon atoms such as acetyl and propionyl, alkylsulfonyl, arylsulfonyl and alkylsulfonylamino, optionally substîtuted alkyl having from 1 to about 6 carbon atoms such as, e.g., methyl, ethyl, hydroxymethyl and hydroxyethyl, optionally substîtuted (hetero)aryl such as, e.g., phenyl, tolyl, xylyl, hydroxyphenyl, pyridinyl and pyrrolyl, and optionally substîtuted alkylaryl such as, e.g., benzyl. If more than one substituent is présent, the substituents may be the same or different. Non-limiting examples of unsubstituted N-containing 5- to 7- membered rings include pyrrolyl, pyrrolidinyl, pyridinyl, pyrimidinyl, piperidinyl, morpholinyl, piperazinyl, thienyl, pyrazolyl, pyrazolidinyl, oxazolyl and oxazolidinyl.
[0051] Preferred halogens as meaning for X in the above formulae (A) and (B) are Cl and Br, although F and I are suitable as well.
[0052] Regarding the values for n and p in the above formulae (A) and (B) it is to be noted that the value of (n+p) will often be not higher than 5, not higher than 4, e.g., not higher than 3, or not higher than 2, with n and p each preferably having a value of 0, 1, 2, 3 or 4. Further, the value of p will often be 0. If n equals 0, at least one of R, R’ and R” comprises at least one group X as substituent. In the latter case often only one group X will be présent in R, R’ or R”, although it is entirely possible for two, three or more groups X to be présent in R and/or R’ and/or R”.
[0053] If two or more groups X are présent in compounds of formulae (A) and (B) they may be the same or different (and preferably are the same) and may be présent as substituents on the perylene skeleton and/or be a part of one or more of R, R’ and R”. However, if two or more groups X are présent they will preferably be présent either as substituents on the perylene skeleton or as a part of R and/or R’.
[0053a] By way of non-limiting example and also as a preferred embodiment, compounds of general formula (I) set forth above include compounds wherein n = p = 0, Ri = H, R2 = R3 = Cm alkyl (e.g., C3 alkyl such as isopropyl), and P represents a group derived from a phenolic resin of general formula (IV) wherein m = 1 to 4 and the groups R4 are preferably identical and represent Ci-10 alkyl groups (e.g., C4 alkyl such as tert.-butyl); compounds of general formula (II) set forth above include compounds wherein n = p = 0, Ri = R2 = CM alkyl (e.g., C3 alkyl such as isopropyl or C4 alkyl such as tert.-butyl), and P represents a group derived from a phenolic resin of general formula (IV) wherein m = 1 and the groups R4 are preferably identical and represent C|.l0 alkyl groups (e.g., C4 alkyl such as tert.-butyl); and compounds of general formula (III) set forth above include compounds wherein n = 0 or 3, p = 0, for n = 3, X = halogen (such as Cl or
Br), the groups Z are identical and represent N-R, with R being an alkylaryl group, e.g., a dialkylphenyl group wherein the two alkyl groups are preferably identical and represent Ci.4 alkyl groups (e.g., C3 alkyl such as isopropyl), and P represents a group derived from a phenolic resin of general formula (IV) wherein m = l and the groups R4 are preferably identical and represent Cmo alkyl groups (e.g., C4 alkyl such as tert-butyl).
[0054] According to the method of the présent invention the solubility and/or the dispersibility of a perylene dye in a liquid medium is increased by (preferably covalently) binding the perylene dye to a (at least one) polymer that is soluble in the liquid medium. The term “soluble in the liquid medium” means that the polymer shows a more than a negligible solubility in the liquid medium, such as, e.g., a solubility of at least about 0.2 g of polymer per 100 g of liquid medium, for example, at least about 0.4 g, at least about 0.5 g, at least about 0.6 g, at least about 0.8 g, at least about l g, at least about 2 g, at least about 5 g, at least about 8 g, or at least about 10 g of polymer per 100 g of liquid medium. If the liquid medium is a polar liquid medium (as it is ofiten encountered in printing inks) the polymer may comprise at least one (recurring) monomer unit that comprises at least one polar group which may, for example, be selected from hydroxy, carboxy and amino groups. Accordingly, the polymer may, for example, comprise a phenolic resin such as, e.g., a novolac resin or any other kind of phénol formaldéhyde condensation product. For example, the phenolic resin may be or include a phenolic resin of formula
wherein the groups R4 may be the same or different and are selected from (optionally substituted) alkyl groups having fforn 1 to about 10 carbon atoms and the average number of m is from about 1 to about 30, for example, from about 1 to about 25, from about 1 to about 15, from about 1 to about 10, from about 1 to about 5, from about 1 to about 3, from about 5 to about 15, from about 5 to about 10, from about 10 to about 20, or from about 20 to about 30. The groups R4 may be the same or different (preferably the same) and may, for example, be selected from tert-butyl, tert-octyl and branched nonyl. Further, a group R4 may be in the meta- or paraposition with respect to the OH group (in formula (IV) only the para position is shown), and there may be more than one group R4 (e.g., 2 or 3 groups R4) présent on a phenyl ring. For example, if two groups R4 are présent on a phenyl ring (the same or different, preferably the same groups R4) they may be présent in any of the available positions on the phenyl ring, such as, e.g., meta/para or meta/meta with respect to the OH group.
[0055] Regarding formula (IV) it is to be appreciated that each of the phenyl rings comprised therein may comprise 1 or 2 additional substituents. These substituents may, for example, be additional optionally substituted alkyl groups (preferably having from 1 to about 10 carbon atoms), halogen such as, e.g., F, Cl and Br, OH, COOH, and amino. If additional substituents are présent they may be the same or different.
[0056] The average value of m in the above formula (IV) will often be at least about 1, at least about 2, e.g., at least about 3, or at least about 4, and will also often be not higher than about 20, e.g., not higher than about 15, or not higher than about 10.
[0057] The weight ratio of perylene dye to polymer(s) that is employed in the method of the présent invention dépends on several factors such as, e.g., the molecular weights of the perylene dye and the polymer(s), the average number of perylene dye molécules that are to be bonded to a single polymer molécule or the average number of polymer molécules that are to be bonded to a single perylene dye molécule. In particular, in a polymer-bonded perylene dye of the présent invention a single polymer molécule P may hâve one or more than one perylene dye molécule (e.g., an average of 1, 2, 3, 4, 5, 6, or more perylene dye molécules) bonded thereto. Conversely, a perylene dye molécule may hâve one or more than one polymer molécule P (e.g., an average of 1, 2, 3, 4, or more polymer molécules P) bonded thereto. Even further, a polymer molécule P may hâve at least two perylene dye molécules bonded thereto, at least one of these perylene dye molécules being bonded to at least one additional polymer molécule P (which in turn may or may not be bonded to one or more additional perylene dye molécules).
[0058] It further is possible (and sometimes preferred) to employ a relatively large stoichiometric excess of polymer(s) with respect to perylene dye. This will resuit in a polymer wherein only a small fraction (e.g., not more than about 0.1%, not more than about 0.5 %, not more than about 1 %, or not more than about 2 %, not more than about 4%, not more than about 6%, not more than about 8%, not more than about 10%) of the polymer molécules hâve at least one perylene dye molécule bonded thereto, thereby affording a perylene dye-doped polymer of the présent invention. The perylene dye-doped polymer can be used for the same purposes for which the polymer-bonded perylene dye of the présent invention is employable such as, e.g., as a component of a printing ink composition.
[0059] By way of non-limiting example, in the process for making the polymer-bonded perylene dyes of formulae (Γ) to (III’) set forth above it is preferred to use about 0.2 g to about 10 g of perylene dye per 100 g of polymer such as, e.g., phenolic resin. In particular, it will often be advantageous to employ at least about 0.5 g, e.g., at least about 0.8 g, or at least about l g, but not more than about 5 g, e.g., not more than about 3 g, or not more than about 2 g of perylene dye per 100 g of polymer.
[0060] It is, of course, possible to react one perylene dye with more than one or more than one type of polymer. By way of non-limiting example, a perylene dye of the above formula (A) or (B) may be reacted with a mixture of polymers of the above formula (IV). Conversely, two or more different perylene dyes may be reacted with (bonded to) a single (type of) polymer. Finally, two or more different perylene dyes may be reacted with two or more different (types of) polymers, although this will usually resuit in difficult to control reaction mixtures.
[0061] The reaction conditions which are required or advantageous, respectively for the reaction between a perylene dye and a polymer to which the former is to be bonded dépend on many factors such as, e.g., the groups that are to participate in the reaction and any other (reactive) groups that may be présent in the perylene dye and/or the polymer. Reaction conditions which are suitable for a spécifie pair of reactive groups in the perylene dye and in the polymer are well known to those of skill in the art. For example, especially in cases where a nucleophilic substitution is involved it will often be bénéficiai to carry out the reaction in an aprotic polar organic solvent such as, e.g., N-methylpyrrolidone (NMP), dimethyl formamide, dimethyl acetamide, and dimethylsulfoxide or a mixture of two or more thereof, and in the presence of an inorganic or strong non-nucleophilic organic base. Examples of inorganic and organic bases suitable for catalyzing nucleophilic substitution reactions are well known to those of skill in the art. An example of a suitable inorganic base is K2CO3. Reaction températures will often range from about 50° C to about 140° C, also depending on the boiling point of the solvent used. It further will often be désirable to employ an anti-foam agent such as, e.g., a polyethylene glycol or dérivative thereof. The reaction product (polymer-bonded perylene dye) can usually be isolated from the résultant reaction mixture and optionally purified by conventional means such as, e.g., filtration, centrifugation, extraction, chromatographie methods, etc.
[0062] Typical (non-limiting) reactions between a perylene dye and a polymer (phenolic resin) in accordance with the processes of the présent invention are represented below:
a) ΡΟΗ
b) K2CO3/ NMP
C) Δ
R4 as defîned in the claims and the spécification
R4 as defined in the daims and the spedfication [0063] In this regard, it is to be appreciated that in the présent spécification and the appended daims the letter “P” is used to dénoté two different entities: in one case an unreacted polymer and in the other case the polymer in which one or more groups thereof hâve reacted with one or more corresponding groups of one or more perylene dye molécules to form a (preferably covalent) linkage between the remainder of the polymer and the remainder of the perylene dye.
[0064] A printing ink composition in accordance with the présent invention comprises a (preferably polar) liquid medium and one or more (types of) polymer-bonded perylene dyes as set forth above (e.g., a mixture of two or three different perylene dyes, ail bonded to the same type of polymer, or bonded to more than one type of polymer) dissolved or dispersed in the medium. The concentration of the polymer-bonded perylene dye(s) in the medium dépends on several factors such as, e.g., the polymer(s) to which the perylene dye(s) is/are bonded, the desired color intensity, the liquid medium, the remaining (optional) components of the composition, the intended purpose of the printing ink composition, and the substrate onto which the printing ink composition is to be applied. Often the (total) concentration of the one or more polymer-bonded perylene dyes in the printing ink composition will be at least about 0.01 %, at least about 0.02 %, or at least 0.05 % by weight, and will usually be not higher than about 40 % by weight, e.g. not higher than about 20 %, not higher than about 10 %, or not higher than about 5 % by weight based on the total weight of the composition.
[0065] The intended purpose of the printing ink composition is one of several factors which détermines suitable and désirable concentration ranges for the polymer-bonded perylene dye(s) as well as the types and concentration ranges of suitable or désirable optional components of the composition. There are many different types of printing processes. Non-limiting examples thereof include inkjet printing (thermal, piezoelectric, continuous, etc.), flexography, intaglio printing (e.g., gravure printing), screen printing, letterpress printing, offset printing, pad printing, relief printing, planographic printing and rotogravure printing. In a preferred embodiment, a printing ink composition in accordance with the présent invention is suitable (at least) for inkjet printing. Industrial inkjet printers, commonly used for numbering, coding and marking applications on conditioning lines and printing presses, are particularly suitable. Preferred ink-jet printers include single nozzle continuous ink-jet printers (also called raster or multi level deflected printers) and drop-on-demand ink-jet printers, in particular valve-jet printers. Accordingly, the following discussion of printing ink compositions relates primarily to compositions for inkjet printing. However, it is to be kept in mind that the présent invention is not limited to printing ink compositions for inkjet printing but rather encompasses ail printing ink compositions in which perylene dyes can be employed. Accordingly, the following considérations and statements apply mutatis mutandis to ail printing ink compositions in which the polymer-bonded perylene dyes in accordance with the teaching of the présent invention are useful.
[0066] Printing inks in general comprise coloring agents and liquid vehicles which comprise solutions of resinous binders in solvents. The spécifie choice of binders and solvents dépends on several factors, such as, for example, the polymer-bonded perylene dye(s), the remaining components that are to be présent, and the nature of the substrate to be printed. Non-limiting examples of suitable binders for use in the ink compositions for inkjet printing include binders which are conventionally used in inkjet printing inks, including resins such as nitrocellulose, acrylate resins and polyester resins (such as, e.g, DYNAPOL® L 1203 , L 205, L 206, L 208, L 210, L 411, L 651, L658, L 850, L 912, L 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH 775, LH 818, LH 820, LH 822, LH 912, LH 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH 775, LH 818, LH 820, LH 822, LH 823, LH 826, LH 828, LH 830, LH 831, LH 832, LH 833, LH 838, LH898, LH 908, LS436, LS615, P1500, S1218, S1227, S1247, S1249, S1252, S1272, S1401, S1402, S1426, S1450, S1510, S1606, S1611, S243, S320, S341, S361, S394, and S EPI408 from Evonik). Of course, other suitable resins known to those of skill in the art may be used as well. A typical (total) concentration of the one or more binders in the printing ink composition is from about 0.5 % to about 10 % by weight, based on the total weight of the composition. In this regard, it further is to be taken into account that typical viscosity values for inkjet printing inks are in the range of from about 4 to about 30 mPa.s at 25°C.
X [0067] It further is to be appreciated that the polymer which has one or more perylene dye molécules bonded thereto (and in the case of the perylene dye-doped polymer of the présent invention as set forth above, also the polymer which is not bonded to any perylene dye molécule but is présent in admixture with polymer that has perylene dye bonded thereto) may also act as a binder for the composition. At any rate, the (principal) binder of the ink composition must be compatible with the polymer which a perylene dye bonded thereto, e.g., must no resuit in the formation of any insoluble substance, etc. when combined with the later.
[0068] Suitable solvents for inkjet printing inks are known to those of skill in the art. Nonlimiting examples thereof include low-viscosity, slightly polar and aprotic organic solvents, such as, e.g., methyl ethyl ketone (MEK), acetone, ethyl acetate, ethyl 3-ethoxypropionate, toluene and mixtures of two or more thereof.
[0069] In particular if the printing ink composition of the présent invention is to be applied by continuous inkjet printing the composition will usually also comprise at least one conductivity imparting agent (for example, a sait). The conductivity imparting agent will hâve a nonnegligible solubility in the composition. Non-limiting examples of suitable conductivity imparting agents include salts such as, e.g., tetraalkyl ammonium salts (e.g., tetrabutyl ammonium nitrate, tetrabutyl ammonium perchlorate and tetrabutyl ammonium hexafluorophosphate), alkali métal thiocyanates such as potassium thiocyanate, akali potassium salts such as KPFô and alkali métal perchlorates such as lithium perchlorate. The conductivity imparting agent will be présent in a concentration which is sufficient to provide the conductivity which is required or désirable. Of course, mixtures of two or more different conductivity imparting agents (salts) can be used. Often the one or more conductivity imparting agents will be présent in a total concentration of from about 0.1 % to 2 % by weight, based on the total weight of the composition.
[0070] The printing ink composition according to the présent invention may furthermore comprise one or more customary additives, such as, for example, fungicides, biocides, surfactants, sequestering agents, pH adjusters, etc. in the amounts customary for these additives. Further, the printing ink composition may comprise one or more additional colorants and/or components which impart a spécifie optical property (i.e., components which are different from the polymer-bonded perylene dyes of the présent invention). These additional components may be selected from, for example, conventional pigments and dyes, luminescent (e.g., fluorescent) pigments and dyes, and cholesteric and/or nematic liquid crystals. Examples of luminescent pigments include certain classes of inorganic compounds such as the sulphides, oxysulphides, phosphates, vanadates, garnets, spinels, etc. of non luminescent cations, which are doped with at least one luminescent transition-métal or a rare-earth métal cation. In order to strengthen the security of the ink composition may further comprise one or more pigments and/or dyes which absorb in the visible or invisible région of the electromagnetic spectrum and/or may further comprise one or more pigments and/or dyes which are luminescent. Non-limiting examples of suitable pigments and/or dyes which absorb in the visible or invisible région of the electromagnetic spectrum include phthalocyanine dérivatives. Non-limiting examples of suitable luminescent pigments and/or dyes include lanthanide dérivatives. The presence of pigment(s) and/or dye(s) will enhance and reinforce the security of the marking against counterfeiting.
[0071] The substrate or article which is to be provided with a marking and/or security feature in accordance with the présent invention is not particulariy limited and can be of various types. The substrate or article may, for example, consist (essentially) of or comprise one or more of a métal (for example, in the form of a container such as a can for holding various items such as, e.g., beverages or foodstuffs), optical fibers, a woven, a coating, and équivalents thereof, a plastic material, a ceramic material, glass (for example, in the form of a capsule or container such as a bottle for holding various items such as, e.g., beverages or foodstuffs), cardboard, packaging, paper, and a polymeric material. It is pointed out that these substrate materials are given exclusively for exemplifying purposes, without restricting the scope of the invention.
[0072] The substrate may furthermore already carry at least one marking or security element which comprises a substance selected from, e.g., inorganic luminescent compounds, organic luminescent compounds, IR-absorbers, magnetic materials, forensic markers, and combinations thereof. The marking or security element can be présent in the form of indicia or a data matrix, on the substrate surface or be incorporated (embedded) in the substrate itself. The marking can be présent also in the form of a cloud of dots or a spécifie pattern visible and/or invisible to the naked eye, randomly or not distributed in the item or article or goods or security documents or what is described in the paragraph [0035] or [0037] it is intended to protect and/or authenticate.
EXAMPLES [0073] The following example illustrâtes a general procedure for making polymer-bonded perylene dyes according to the présent invention.
[0074] Under an inert gas atmosphère 1.4 g of K2CO3 was added to a solution of 10 g of phénol formaldéhyde resin and 0.68 g of PEG 500 in 62.5 ml of NMP. The résultant mixture was heated for about 1 hour at 120 °C. Then 0.12 g of bromo-perylene dye or chloro-perylene dye of the above formula (A) or (B) was added to the mixture, whereafter heating at 120 °C was continued for about 2 to about 5 hours. Following the completîon of the reaction about half of the volume of the NMP was distilled off. The réaction mixture was allowed to cool to room température and thereafter poured into 33 g of iced water to which 2 ml of conc. HCl had been added. The résultant precipitate was filtered off and washed 3 times with water and then dried. This afforded about 10 g of crude powder comprising polymer-bonded perylene dye.
[0075] The crude powder was used without further purification in the following ink formulations for ink-jet printing.
Ink Formulation l
| Component | Function | % b.w. |
| Nitrocellulose | Binder resin | 1.5 |
| Lithium Perchlorate | Sait for conductivity | 0.5 |
| Polymer-bonded Perylene Dye | Dye | 0.8 |
| Black Microlith® | Pigment | l.O |
| Acetone | Solvent | 96.2 |
Ink Formulation 2
| Component | Function | % b.w. |
| Dynapol L4l l (Polyester resin) | Binder resin | 1.5 |
| Lithium Perchlorate | Sait for conductivity | 0.3 |
| Polymer-bonded Perylene Dye | Dye | l.O |
| Black Microlith® | Pigment | 1.2 |
| Methyl ethyl ketone | Solvent | 96 |
Ink Formulation 3
| Component | Function | % b.w. |
| Dynapol L4l 1 (Polyester resin) | Binder resin | 1.5 |
| Lithium Perchlorate | Sait for conductivity | 0.3 |
| Polymer-bonded Perylene Dye | Dye | 2.2 |
| Methyl ethyl ketone | Solvent | 96 |
[0076] It is noted that the foregoing examples hâve been provided merely for the purpose of explanation and are in no way to be construed as limiting of the présent invention. While the présent invention has been described with reference to an exemplary embodîment, it is understood that the words which hâve been used herein are words of description and illustration, rather than words of limitation. Changes may be made, within the purview of the appended daims, as presently stated and as amended, without departing from the scope and spirit of the présent invention in its aspects. Although the présent invention has been described herein with 10 reference to particular means, materials and embodiments, the présent invention is not intended to be limited to the particulars disclosed herein; rather, the présent invention extends to ail functionally équivalent structures, methods and uses, such as are within the scope of the appended daims.
Claims (19)
- WHAT IS CLAIMED IS:1. A method of increasing at least one of the solubility and dispersibility of a perylene dye in a liquid medium, wherein the method comprises binding the perylene dye to a polymer which is soluble in the liquid medium.
- 2. The method of any one of claim 1, wherein the polymer comprises a phenolic resin of formula ‘4 (IV) wherein the groups R4 may be the same or different and are selected from alkyl groups having from 1 to about 10 carbon atoms and the average number of m is from about 1 to about 30.
- 3. The method of claim 1, wherein the perylene dye comprises a compound of formula (A) or (B):whereinCK .OO zO (A) (B) the groups Z, the same or different from each other, represent O, S or N-R, provided that a unit -CO-Z-CO- may be replaced by -CS-Z-CO-, -CS-Z-CS-, or [-COOH HOOC-] and for Z = N-R a unit -CO-Z-CO- may be replaced by a unit -C(=NR’)-NR-CO-;R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;the groups X may be the same or different and represent halogen, isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms and may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7membered ring;n and p each represent 0 or an integer of from 1 to 8, provided that (n+p) is not higher than 8 and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent.
- 4. A perylene dye whose solubility or dispersibility in a polar liquid medium has been increased by the method of claim 1.
- 5. A polymer-bonded perylene dye of formulae (A) or (B):(B) wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that a unit -CO-Z-CO- may be replaced by -CS-Z-CO-, -CS-Z-CS-, or [-COOH HOOC-] and for Z = N-R a unit -CO-Z-CO- may be replaced by a unit -C(=NR’)-NR-CO-;R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;the groups X may be the same or different and represent halogen, isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms and may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7membered ring;n and p each represent 0 or an integer of from 1 to 8, provided that (n+p) is not higher than 8 and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent;provided that at least one group X represents a group of formula -L-P wherein L represents a covalent bond or a bridging group and P represents a polymer molécule.
- 6. The polymer-bonded perylene dye of claim 5, wherein the perylene dye is a compound of formula (A).5 Ί. The polymer-bonded perylene dye of claim 5, wherein the perylene dye is a compound of formula (B) wherein the groups Z may be the same or different and represent O or N-R.
- 8. The polymer-bonded perylene dye of claim 5, wherein L is selected from O, COO, OCO, CONH, and NHCOO.
- 9. The polymer-bonded perylene dye of claim 5, wherein the polymer P comprises a
- 10 phenolic resin of formula wherein the groups R4 may be the same or different and are selected from alkyl groups having from 1 to about 10 carbon atoms and the average number of m is from about 1 to 15 about 30.10. A process for making a polymer-bonded perylene dye according to claim 5, wherein the process comprises contacting a perylene dye of formula (A) or (B):wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that a unit -CO-Z-CO- may be replaced by -CS-Z-CO-, -CS-Z-CS-, or [-COOH HOOC-] and for Z = N-R a unit -CO-Z-CO- may be replaced by a unit -C(=NR’)-NR-CO-;R and R’ independently represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substituted and/or fused 5- to 7-membered ring;the groups X may be the same or different and represent halogen, isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2, wherein the groups R” may be the same or different and represent an optionally substituted aliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from l to about 20 carbon atoms and may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7membered ring;n and p each represent 0 or an integer of from l to 8, provided that (n+p) is not higher than 8 and further provided that for n = 0 at least one of R, R’ and R” comprises at least one group X as substituent;with a polymer P under conditions which cause a reaction of a group X of the perylene dye with a functional group of the polymer to covalently bind the polymer to the perylene dye.
- 11. The polymer-bonded perylene dye of claim 5, where the perylene dye comprises a dye of one of formulae (I) to (III):wherein the groups Z, the same or different from each other, represent O, S or N-R, provided that in the case of formula (III) one or both units -CO-Z-CO- may be replaced by -CS-Z-CO-, -CS-Z-CS-, or [-COOH HOOC-] and for Z = N-R a unit -CO-Z-CO- may be replaced by a unit -C(=NR’)-NR-CO-;R and R’ independently represent an optionally substîtuted aliphatîc, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms; and R and R’ may be combined to form, together with the N atoms to which they are attached, an optionally substîtuted and/or fused 5- to 7-membered ring;Ri, R2 and R3 are independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkylCOOH, C1-C4 alkyl-SChH, C1-C4 alkoxy, mono(C]-C4)alkylamino, di(Ci-C4)alkylamino, C1-C4 aminoalkyl, halogen, cyano, nitro, and SO3H, the alkyl groups being optionally substîtuted;the groups X may be the same or different and represent halogen, isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO2, CN, groups of formula R”, OR”, COOR”, OCOR”, CONHR”, CON(R”)2, OCONHR”, OCON(R”)2, COR”, SO3H, SO3R”, SO2NHR”, SO2N(R”)2, NHCOR”, NRCOR”, NHCOOR”, NRCOOR”, NHSO2R”, NRSO2R”, NHR”, and N(R”)2 , wherein the groups R” may be the same or different and represent an optionally substîtuted aliphatîc, cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 to about 20 carbon atoms and may also be combined to form, together with the N atom to which they are attached, an optionally substituted and/or fused 5- to 7membered ring;in the case of formula (II), n and p each represent 0 or an integer of from 1 to 8, provided that (n+p) is not higher than 8; and in the case of formulae (I) and (III) n and p each represent 0 or an integer of from 1 to 7, provided that (n+p) is not higher than 7; andP represents a polymer molécule.
- 12. A printing ink composition, wherein the composition comprises a polar liquid medium and at least one polymer-bonded perylene dye according to claims 5 to 9 dissolved or dispersed in the medium.
- 13. The printing ink composition of claim 12, wherein the composition comprises from about 0.01 % to about 40 % by weight of the at least one polymer-bonded perylene dye based on a total weight of the composition.
- 14. A marking or security feature which is made with the printing ink composition of claim 12.
- 15. A marking or security feature which comprises at least one polymer-bonded perylene dye of claim 5.
- 16. The marking or security feature of claim 15, wherein the marking or security feature comprises at least one of a thread, a label, a barcode, a 2D code, a pattern, indicia and a data matrix.
- 17. An article which comprises the marking or security feature of claim 15.
- 18. A method of authenticating an article, wherein the method comprises providing the article with the marking or security feature of claim 15.
- 19. A method of authenticating an article, wherein the method comprises applying onto the article the printing ink composition of claim 12.
- 20. A dye-doped polymer, wherein at least about 0.1 % of the polymer molécules hâve bonded thereto a perylene dye and wherein the polymer is obtainable by the process of claim 10.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP1005420.4 | 2010-05-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA17344A true OA17344A (en) | 2016-09-21 |
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