US20080226880A1 - Solvent Borne Polyurethane Composition - Google Patents
Solvent Borne Polyurethane Composition Download PDFInfo
- Publication number
- US20080226880A1 US20080226880A1 US11/994,662 US99466206A US2008226880A1 US 20080226880 A1 US20080226880 A1 US 20080226880A1 US 99466206 A US99466206 A US 99466206A US 2008226880 A1 US2008226880 A1 US 2008226880A1
- Authority
- US
- United States
- Prior art keywords
- isocyanate
- range
- mol
- composition according
- solvent borne
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 132
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 132
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000002904 solvent Substances 0.000 title claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 36
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000005056 polyisocyanate Substances 0.000 claims description 22
- 229920001228 polyisocyanate Polymers 0.000 claims description 22
- 238000007639 printing Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 101150038956 cup-4 gene Proteins 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 5
- 238000007646 gravure printing Methods 0.000 claims description 5
- 239000000976 ink Substances 0.000 description 93
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000010408 film Substances 0.000 description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- -1 polypropylene Polymers 0.000 description 16
- 229940093499 ethyl acetate Drugs 0.000 description 15
- 235000019439 ethyl acetate Nutrition 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
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- 239000004698 Polyethylene Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000009459 flexible packaging Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
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- 150000002009 diols Chemical class 0.000 description 5
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
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- 239000005033 polyvinylidene chloride Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
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- 239000002270 dispersing agent Substances 0.000 description 2
- 229940031098 ethanolamine Drugs 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
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- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
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- 235000019634 flavors Nutrition 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 229940124305 n-propanol Drugs 0.000 description 1
- 239000000978 natural dye Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon 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
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000768 polyamine Chemical group 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the invention relates to a solvent borne polyurethane composition, processes for preparing the solvent borne polyurethane composition and an ink, in particular a printing ink comprising the solvent borne polyurethane composition for use in a laminate.
- Laminates are multi-layered composites where each layer consists of the same or different materials.
- laminates usually comprise plastic and/or metallised films.
- Flexible packaging is used for example in the food industry and has many requirements such as for example eliminating or limiting the transfer of moisture, oxygen, oils and flavours; flexible packaging used for microwave cooking needs to protect the contents during storage but also needs to have good heat resistance; flexible packaging used for beverages needs to have good cold resistance and handling resistance; flexible packaging used in other applications may also need to be resistant to the transfer to perfumes, resistant to surfactants, resistant to oil/water mixtures, and additionally the flexible packaging should be easy to open when required.
- laminates are produced by joining two or more layers using adhesives or by carrying out adhesive-free extrusion coating. Additionally it is often desirable to apply an image to one or more of the layers during the lamination process.
- an image may be printed onto a plastic film substrate, after which an adhesive is applied to the inked substrate, followed by applying a second film to the adhesive (the adhesive could also be applied to the second film).
- an extrusion coating/laminating method an image may be printed onto a plastic film substrate, optionally followed by the application of a primer and then a molten resin is extruded onto the inked substrate to form a second layer followed by the formation of a bond between the two substrates. It is therefore desirable that laminating inks possess excellent adhesion to the printing substrate as well as to the film adhesive and/or film to be laminated.
- Laminated films when used to make packaging, often undergo heat sealing and when used as food packaging must be able to undergo a boiling or retorting treatment for cooking or sterilising the contents. It is therefore also desirable that delamination does not occur during such processes.
- the properties of a laminate therefore depend on the type of films used, the laminating process, the type of adhesive and the ink properties and in particular the properties of any resins used as binders in the ink.
- a range of binders have been used in laminating inks such as modified PVC (polyvinyl chloride), polyvinyl butyral, polyamides, polyesters, nitrocellulose and polyurethanes.
- modified PVC polyvinyl chloride
- polyvinyl butyral polyamides
- polyesters polyurethanes
- binders are incompatible, difficult to clean up from ink printing equipment and many only adhere to certain substrates and even if the binders do adhere, they may be poor in their resistance to boiling or retorting treatments and generally do not achieve desirable bond strength.
- high line speed printing especially at line speeds greater than 200 m/min or even greater than 300 m/min.
- solvents such as ketones or solvents with a slower evaporation rate may be used to solve some of the problems, these solvents may have other inherent issues such as safety and environmental issues as well as that they may be slow to dry which can result in the solvent migrating into the packed material. Therefore the use of solvents with a faster evaporation rate is useful, although if they are too fast then printability failures may also occur.
- a method for overcoming such problems is to use a combination of binders where binders may be chosen to suit particular films and adhesives.
- binders may be chosen to suit particular films and adhesives.
- a disadvantage with such an approach is that a large number of binders need to be prepared and stored for all the different types of inks that may be applied to the laminate films. Additionally if the various inks are not compatible with each other then extensive cleaning of the printing equipment would be required for each change over.
- Elastomeric higher molecular weight polyurethanes are widely used in laminating inks and can give a good balance in properties however they have reduced printability especially in high speed printing processes.
- EP 604890 B1 discloses a printing ink composition for a laminate comprising a polyurethane resin where the polyurethane is prepared with a low and a high molecular weight polyol.
- WO 02/38643 discloses solvent based poly(urethane/urea) resins suitable for laminating printing inks where the polyurethane prepolymer is derived from a blend of a polymeric diol and a diol.
- WO 01/14442 discloses a polyurethane resin obtained by preparing an isocyanate-terminated prepolymer which is then reacted with a diamine which suitable for formulating printing ink compositions.
- EP 1229090 A1 discloses a polyurethane resin, soluble in organic solvents, where the polyurethane is prepared with at least three polyols within different molecular weight ranges and where the polyurethane resin can be used in a printing ink for making laminates.
- a disadvantage of such polyurethanes is that they often still require combining with other binders to get a good balance of properties such as for example adhesion, block resistance, flexibility and heat resistance. Furthermore the prior art does not describe a polyurethane binder that provides a good bond strength whilst maintaining printability at high line speeds.
- a solvent borne polyurethane composition comprising:
- the composition comprises 10 to 85 wt %, more preferably 10 to 60 wt %, most preferably 10 to 50 wt % and especially 10 to 40 wt % of at least a polyurethane A.
- the composition comprises 90 to 15 wt %, more preferably 90 to 40 wt %, most preferably 90 to 50 wt % and especially 90 to 60 wt % of at least a polyurethane B.
- the Mw is the weight average molecular weight usually determined using Gel Permeation Chromatography (GPC) with polystyrene as a standard and tetrahydrofuran as an eluent.
- GPC Gel Permeation Chromatography
- polyurethane A has a Mw in the range of from 4,000 to 25,000 g/mol, more preferably 5,000 to 23,000 g/mol and even more preferably 5,500 to 22,000 g/mol.
- polyurethane B has a Mw in the range of from 25,000 to 100,000 g/mol, more preferably 30,000 to 80,000 g/mol, most preferably 31,000 to 70,000 g/mol and especially 32,000 to 60,000 g/mol.
- 15 to 85 wt % of the polyurethanes in the composition of the invention have a Mw at least 10,000 g/mol greater than the Mw of the remaining 85 to 15 wt % of the polyurethanes.
- the composition of the invention comprises 90 to 10 wt % of polyurethane A and 10 to 90 wt % of polyurethane B with the proviso that 35 to 70 wt % of polyurethanes in the composition have a Mw of at least 5,000 g/mol and more preferably 10,000 g/mol greater than the Mw of 20 to 50 wt % of the polyurethanes in the composition.
- the Mp is the molecular weight with the highest signal (i.e. the apex of the peak) in a chromatogram resulting from the measuring of the molecular weight of the invention composition using Gel Permeation Chromatography (GPC) with polystyrene as a standard and tetrahydrofuran as an eluent.
- GPC Gel Permeation Chromatography
- the Mp is also known as the peak Mw.
- Mp values are discussed in Modern Size Exclusion Liquid Chromatography, W. W. Yau, J. K. Kirkland and D. D. Bly, John Wiley & Sons, USA, 1997.
- the Mp of the polyurethanes in the composition of the invention is in the range of from 6,000 to 60,000 g/mol, more preferably 20,000 to 60,000 g/mol, most preferably 25,000 to 60,000 g/mol, and especially 30,000 to 60,000 g/mol.
- the composition of the invention comprises at least 10 to 90 wt %, more preferably 50 to 90 wt % and most preferably 75 to 90 wt % of a polyurethane having an Mp in the range of from 6,000 to 60,000 g/mol, more preferably 25,000 to 55,000 g/mol and most preferably 32,000 to 50,000 g/mol.
- the polyurethanes in the composition have a polymodal molecular weight distribution.
- the polydispersity index (PDi) is defined as the weight average molecular weight (Mw) divided by the number average molecular weight (Mn).
- the PDi is calculated on the total molecular weight of the polyurethanes A and B of the invention composition.
- the PDi of the polyurethanes in the composition of the invention is in the range of from 1.3 to 10.0, more preferably 2.8 to 6.0, most preferably 3.0 to 6.0 and especially 3.0 to 5.0.
- composition of the invention comprises polyurethanes having an Mp in the range of from 6,000 to 60,000 g/mol and a PDi in the range of from 2.8 to 6.
- polyurethane A is non-film forming.
- polyurethane B is film-forming.
- the composition of the invention is film-forming.
- film-forming is meant that on removal of most or all of the liquid medium from the polyurethane composition a cohesive film is formed. Furthermore it has a minimum level of strength and is dry to touch i.e. it can be slightly tacky but the material will not transfer to when it is touched. A non-film-forming polyurethane will even in the absence of any liquid medium remain very tacky and like a paste.
- the solvent based polyurethane composition comprises 80 to 25 wt %, more preferably 70 to 30 wt %, most preferably 60 to 35% and especially 50 to 40 wt % of III) the liquid medium.
- solvent based composition substantially comprises solvents.
- the liquid medium substantially comprises solvents.
- the liquid medium comprises ⁇ 20 wt % of water, more preferably ⁇ 6 wt % and most preferably ⁇ 1 wt % of water. If the liquid medium comprises any water, then preferably the water is added after the preparation of the polyurethanes is complete.
- the liquid medium comprises ⁇ 75 wt %, more preferably ⁇ 90 wt %, most preferably ⁇ 98 wt % and especially 100 wt % of fast evaporating solvents.
- Fast evaporating solvents may be defined as solvents having a molecular weight ⁇ 125 g/mol and more preferably ⁇ 105 g/mol.
- fast evaporating solvents are defined as solvents having an evaporation rate of at ⁇ 1.0, more preferably ⁇ 1.4 and preferably ⁇ 1.6. Values for evaporation rates were published by Texaco Chemical Company in a bulletin Solvent Data: Solvent Properties (1990). (The values given are relative to the evaporation rate (ER) of butyl acetate which is defined as 1.00). Determination of evaporation rates of solvents that are not listed in the Texaco bulletin is as described in ASTM D3539. Fast evaporating solvents are particularly useful where fast drying times are required, especially when printing onto hydrophobic and non-absorbent substrates, for example plastics, metal and glass.
- solvents examples include alcohols (such as ethanol, isopropanol, n-butanol, n-propanol), esters (such as ethyl acetate, propyl acetate), aromatic solvents (such as toluene), ketone solvents (such as acetone, methyl ethyl ketone, methyl isobutyl ketone) cyclohexanone, diacetone alcohol; aliphatic hydrocarbons; chlorinated hydrocarbons (such as CH 2 Cl 2 ); ethers (such as diethyl ether, tetrahydrofuran) and mixtures thereof.
- alcohols such as ethanol, isopropanol, n-butanol, n-propanol
- esters such as ethyl acetate, propyl acetate
- aromatic solvents such as toluene
- ketone solvents such as acetone, methyl ethyl ketone,
- the liquid medium comprises a solvent selected from the group comprising ethanol, isopropanol, ethylacetate and or a mixture thereof.
- the liquid medium may also comprise other organic solvents such as ethoxy propanol and propylene glycol n-propyl ether.
- the polyurethane composition of the invention also preferably has a viscosity ⁇ 18,000 mPa ⁇ s, more preferably ⁇ 12,000 mPa ⁇ s, most preferably ⁇ 10,000 mPa ⁇ s and especially ⁇ 5,000 mPa ⁇ s at any solids content in the range of from 20 to 75 wt %, more preferably 35 to 75 wt %, most preferably 45 to 75 wt % and especially 50 to 75 wt % in a solvent comprising ⁇ 70 wt %, more preferably ⁇ 90 wt % and most preferably 100 wt % of at least one solvent having an evaporation rate ⁇ 1. All viscosities are measured according to ISO 2555-1989 at 25° C. Preferred solvents used to measure the viscosity of the polyurethane in, include ethanol, isopropanol, n-propanol, ethyl acetate, propyl acetate and or mixtures thereof.
- the polyurethane A and polyurethane B of the invention composition are preferably obtained by reacting components comprising (i) at least one polyisocyanate; (ii) optionally at least one isocyanate-reactive polyol with a weight-average molecular weight in the range of from 50 to 200 g/mol; (iii) at least one isocyanate-reactive polyol with a weight-average molecular weight in the range of from 201 to 20,000 g/mol; (iv) a chain-extending and/or chain-terminating component not comprised by (i), (ii), or (iii); and optionally (v) an isocyanate-reactive polyol not comprised by (ii), (iii) or (iv); optionally in the presence of a liquid medium.
- the polyisocyanate component (i) may be an aliphatic polyisocyanate, an aromatic isocyanate or mixtures thereof.
- aromatic polyisocyanate (for the sake of clarity) is intended to mean compounds in which all the isocyanate groups are directly bonded to an aromatic group, irrespective of whether aliphatic groups are also present.
- suitable aromatic polyisocyanates include but are not limited to p-xylylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-methylene bis(phenyl isocyanate), polymethylene polyphenyl polyisocyanates, 2,4′-methylene bis(phenyl isocyanate) and 1,5-naphthylene diisocyanate.
- Preferred aromatic isocyanates include 2,4′-methylene bis(phenyl isocyanate) and 4,4′-methylene bis(phenyl isocyanate).
- Aromatic polyisocyanates provide chemical resistance and toughness but may yellow on exposure to UV light.
- aliphatic polyisocyanate (for the sake of clarity) is intended to mean compounds in which all the isocyanate groups are directly bonded to aliphatic or cycloaliphatic groups, irrespective of whether aromatic groups are also present.
- Examples include but are not limited to ethylene diisocyanate, para-tetra methylxylene diisocyanate (p-TMXDI), meta-tetra methylxylene diisocyanate (m-TMXDI), 1,6-hexamethylene diisocyanate, isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.
- ethylene diisocyanate para-tetra methylxylene diisocyanate
- p-TMXDI para-tetra methylxylene diisocyanate
- m-TMXDI meta-tetra methylxylene diisocyanate
- IPDI isophorone diisocyanate
- cyclohexane-1,4-diisocyanate and 4,4′-dicyclohexylmethane diisocyanate 4,4′
- Preferred aliphatic iscocyanates include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,6-hexamethylene diisocyanate.
- At least 70 wt %, more preferably at least 85 wt % and most preferably at least 95 wt % of the polyisocyanate in component (i) has two isocyanate groups.
- Aromatic or aliphatic polyisocyanates which have been modified by the introduction of, for example, urethane, allophanate, urea, biuret, uretonimine and urethdione or isocyanurate residues may be used for component (i).
- polyurethane A comprises 2 to 50 wt %, more preferably 5 to 45 wt % and most preferably 8 to 45 wt % of component (i).
- polyurethane B comprises 4 to 50 wt %, more preferably 10 to 35 wt % and most preferably 12 to 20 wt % of component (i).
- the isocyanate-reactive components (ii) to (iv) will normally consist of a polyol component bearing isocyanate-reactive groups which may also bear other reactive groups.
- Polyol components also include compounds with one or more isocyanate-reactive groups such as —OH, —CHR 1 —COOH where R 1 can be H, alkyl (more preferably C 1 to C 8 alkyl); —SH, —NH— and —NH 2 .
- component (ii) examples include but are not limited to 1,4-cyclohexyldimethanol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, furan dimethanol, cyclohexane dimethanol, glycerol, trimethylolpropan, dimethylol propanoic acid (DMPA) and dimethylol butanoic acid (DMBA).
- DMPA dimethylol propanoic acid
- DMBA dimethylol butanoic acid
- component (ii) has an average of 1.8 to 3 isocyanate-reactive groups and more preferably component (ii) has an average of 1.8 to 2.5 isocyanate-reactive groups.
- component (ii) may comprise a mixture of a triol and a diol which together have an average of 1.8 to 2.5 isocyanate-reactive groups.
- the weight average molecular weight of component (ii) is in the range of from 62 to 200 g/mol and more preferably 84 to 200 g/mol.
- polyurethane A comprises 0 to 20 wt %, more preferably 0 to 10 wt % and most preferably 0 to 5 wt % of component (ii).
- polyurethane B comprises 0 to 20 wt %, more preferably 0 to 10 wt % and most preferably 0 to 5 wt % of component (ii).
- component (iii) and optional component (v) include but are not limited to polyols such as polypropylene glycols, poly(propylene oxide/ethylene oxide) copolymers, polytetrahydrofuran, polybutadiene, hydrogenated polybutadiene, polysiloxane, polyamide polyesters, isocyanate-reactive polyoxyethylene compounds, polyester, polyether, polyether ester, polycaprolactone, polythioether, polycarbonate, polyethercarbonate, polyacetal and polyolefin polyols.
- polyols such as polypropylene glycols, poly(propylene oxide/ethylene oxide) copolymers, polytetrahydrofuran, polybutadiene, hydrogenated polybutadiene, polysiloxane, polyamide polyesters, isocyanate-reactive polyoxyethylene compounds, polyester, polyether, polyether ester, polycaprolactone, polythioether, polycarbonate, polyethercarbonate, polyacetal and polyolef
- polyester polyols provide good weathering, good adhesion, improved chemical resistance and toughness; polyether polyols provide good flexibility, elasticity and storage stability; polycaprolactone polyols provide improved weathering and better heat resistance than polyether polyols and better water resistance than adipate polyester polyols.
- Polyester amides may be obtained by the inclusion of amino-alcohols such as ethanolamine in polyesterification mixtures. Polyesters which incorporate carboxy groups may be used, for example polyesters where DMPA and/or DMBA are used during the synthesis.
- Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example ethylene oxide, propylene oxide or tetrahydrofuran or by the addition of one or more such oxides to polyfunctional initiators, for example water, methylene glycol, ethylene glycol, propylene glycol, diethylene glycol, cyclohexane dimethanol, glycerol, trimethylopropane, pentaerythritol or Bisphenol A.
- a cyclic oxide for example ethylene oxide, propylene oxide or tetrahydrofuran
- polyfunctional initiators for example water, methylene glycol, ethylene glycol, propylene glycol, diethylene glycol, cyclohexane dimethanol, glycerol, trimethylopropane, pentaerythritol or Bisphenol A.
- polyether polyols include polyoxypropylene diols and triols, poly (oxyethylene-oxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to appropriate initiators and polytetramethylene ether glycols obtained by the polymerisation of tetrahydrofuran. Particularly preferred are polypropylene glycols.
- Components (iii) and (v) may also include crosslinking groups.
- Crosslinking groups are well known in the art and include groups which crosslink at ambient temperature (20 ⁇ 3° C.) or at elevated temperatures by a number of mechanisms including but not limited to Schiff base crosslinking (for example the reaction of carbonyl functional groups with carbonyl reactive amine and/or hydrazine functional groups); silane crosslinking (for example the reaction of alkoxy silane groups in the presence of water) and epoxy groups crosslinking with epoxy-reactive functional groups or isocyanate curing, where hydroxy or amine (primary or secondary) functional polyurethanes are combined with polyisocyanates.
- Schiff base crosslinking for example the reaction of carbonyl functional groups with carbonyl reactive amine and/or hydrazine functional groups
- silane crosslinking for example the reaction of alkoxy silane groups in the presence of water
- epoxy groups crosslinking with epoxy-reactive functional groups or isocyanate curing, where hydroxy or amine (
- the weight average molecular weight of component (iii) is in the range of from 350 to 11,000 g/mol, more preferably 350 to 6,000 g/mol and especially 350 to 5,000 g/mol.
- polyurethane A comprises 0 to 95 wt %, more preferably 30 to 95 wt % and most preferably 40 to 92 wt % of component (iii).
- polyurethane B comprises 0 to 95 wt %, more preferably 60 to 90 wt % and most preferably 70 to 80 wt % of component (iii)
- polyurethane A comprises 0 to 95 wt %, more preferably 0 to 6 wt %, most preferably 0 to 3 wt % and especially 0 wt % of component (v).
- polyurethane B comprises most preferably 0 to 95 wt %, more preferably 0 to 6 wt %, most preferably 0 to 3 wt % and especially 0 wt % of component (v).
- Component (iv) comprises a chain-extending and/or chain-terminating component.
- chain-terminating compounds examples include mono-alcohols, amino-alcohols, primary or secondary amines and mono-functional hydrazines as are well known in the art.
- Di- or poly-functional isocyanante-reactive compounds may be used as a chain-terminating compound If only one isocyanante-reactive group reacts under the given conditions. Examples of such difunctional compounds include ethanol amine and diethanolamine.
- the chain-terminating compound may also be a mono-functional isocyanate.
- chain-extending compounds include amino-alcohols, primary or secondary diamines or polyamines such as ethylene diamine, propylene diamine and cyclic amines such as isophorone diamine and 4,4′-dicyclohexylmethane diamine; hydrazine and substituted hydrazines such as, for example, dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine, carbodihydrazine, hydrazides of dicarboxylic acids and sulphonic acids such as adipic acid dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, hydrazides made by reacting lactones with hydrazine, bis-semi-carbazide, and bis-hydrazide carbonic esters of glycols; azines such as acetone azine, and or mixtures thereof.
- hydrazine and substituted hydrazines such as,
- chain-extending compounds are the so-called “Jeffamine” compounds with a functionality of 2 or 3 (available from Huntsman). These are PPO or PEO-based di or triamines, e.g. “Jeffamine” T403 and “Jeffamine” D-400.
- a chain-extending compound may also be a difunctional isocyanate.
- polyurethane A comprises 0 to 40 wt %, more preferably 0 to 20 wt %, most preferably 0 to 10 wt % and especially 0 to 9 wt % of component (iv).
- polyurethane B comprises 0 to 40 wt %, more preferably 0.5 to 25 wt %, most preferably 1 to 10 wt % and especially 3 to 8 wt % of component (iv).
- the polyurethane A of the invention composition is most preferably obtained by reacting components comprising:
- the polyurethane B of the invention composition is most preferably obtained by reacting components comprising:
- the polyurethanes A and B of the invention composition may each comprise one or more than one polyurethane.
- the invention composition may be prepared by blending two or more polyurethanes and or by preparing one polyurethane in the presence of another (which is also known as an in situ preparation). Both routes may provide a composition comprising polyurethanes with a polymodal molecular weight distribution.
- the solvent borne polyurethane composition comprising polyurethane A and polyurethane B may be obtained by blending polyurethane A and polyurethane B.
- the solvent borne polyurethane composition comprising polyurethane A and polyurethane B may be obtained by a number of in-situ processes.
- polyurethane A may be prepared in the presence of polyurethane B or polyurethane B may be prepared in the presence of polyurethane A.
- the polyurethanes of the invention composition may be prepared conventionally by reacting the organic polyisocyanate (component (i)) with the isocyanate-reactive compounds (components (ii), (iii) and (v)) under substantially anhydrous conditions at a temperature between about 30° C. and about 130° C., more preferably about 45° C. to about 85° C. until reaction between the isocyanate groups and the isocyanate-reactive groups is substantially complete.
- the reactants are generally used in proportions corresponding to a ratio of isocyanate groups to isocyanate-reactive groups of from about 0.45:1 to about 2:1, more preferably from about 1.2:1 to about 2:1, most preferably from about 1.3:1 to 2.0:1 and especially 1.45:1 to 2:1.
- catalysts such as dibutyltin dilaurate and stannous octoate, zirconium or titanium based catalysts may be used to assist the polyurethane formation.
- no catalyst is added.
- no tin based catalyst is added.
- the catalyst if used, may be added immediately to a mixture of components (i) (ii), (iii) and (v) or the mixture of components (i) (ii), (iii) and (v) may be allowed to react for a period of time before the addition of a catalyst. The reaction between the components may be carried out in any order.
- the reaction is usually carried out in the presence of an organic solvent to control the viscosity.
- organic solvents include but are not limited to acetone, tetrahydrofuran, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and other solvents well known in the art.
- an isocyanate-terminated prepolymer may be reacted with a chain-extending and/or chain-terminating component (iv).
- a hydroxyl-terminated prepolymer may be formed which may also be reacted with a chain-extending and/or chain-terminating component or used directly with another polyurethane.
- steps 2a) and/or 2b) may be repeated.
- a further isocyanate-terminated prepolymer may be prepared and then blended with the isocyanate-terminated prepolymer obtained in step 2b) or a further isocyanate-terminated prepolymer may be prepared in the presence of the prepolymer obtained in step 2b).
- the isocyanate-terminated prepolymer A in step 1) has an isocyanate group content in the range of from 0.5 to 5.5 wt %, more preferably 0.5 to 4.5 wt % and most preferably 0.5 to 3.5 wt %.
- the isocyanate-terminated compound B may be a polyisocyanate as described above (for convenience called polyisocyanate B).
- the isocyanate-terminated compound B may also be an isocyanate-terminated prepolymer. If the isocyanate-terminated compound B is an isocyanate-terminated prepolymer (for convenience described as isocyanate-terminated prepolymer B) it is preferably obtained by reacting components as described above for isocyanate-terminated prepolymer A.
- the isocyanate-terminated compound B may comprise one or more than one isocyanate-terminated prepolymer B and/or polyisocyanate B. If isocyanate-terminated compound B is an isocyanate-terminated prepolymer B, it may also be partially chain-terminated and or chain-extended before being introduced in step 3.
- Step 2a) and step 2b) of the process of the invention may be in any order.
- Step 4a) and step 4b) of the process of the invention may be in any order.
- step 2a) and 2b), step 3), step 4a) and step 4b) may be repeated.
- step 2a) comprises reacting the isocyanate groups of isocyanate-terminated prepolymer A with 0 to 0.8, more preferably 0.1 to 0.7 and most preferably 0.1 to 0.6 stoichiometric equivalents of at least one active-hydrogen containing chain-terminating compound.
- step 2b comprises reacting the isocyanate groups of isocyanate-terminated prepolymer A with 0 to 0.95, more preferably 0 to 0.9 and most preferably 0 to 0.8 stoichiometric equivalents of at least one active-hydrogen containing chain-extending compound.
- steps 2a) and 2b) together are in the range of from 0.1 to 0.95, more preferably 0.2 to 0.9, most preferably 0.2 to 0.85 and especially 0.3 to 0.85 stoichiometric equivalents.
- step 3) comprises introducing 0 to 1600%, more preferably 0 to 1000%, even more preferably 0 to 500%, especially 0 to 150% and most especially 0 to 100% by weight of isocyanate-terminated prepolymer A of an isocyanate-terminated compound B.
- step 4a) comprises reacting the isocyanate groups of the isocyanate-terminated prepolymer obtained in steps 2a) and 2b) and isocyanate-terminated compound B introduced in step 3) with 0 to 0.55, more preferably 0 to 0.45 and most preferably 0 to 0.42 stoichiometric equivalents of at least one active-hydrogen containing chain-terminating compound.
- step 4b) comprises reacting the isocyanate groups of the isocyanate-terminated prepolymer obtained in steps 2a) and 2b) and the isocyanate-terminated compound B introduced in step 3) with 0 to 1.1, more preferably 0 to 0.95 and most preferably 0 to 0.85 stoichiometric equivalents of at least one active-hydrogen containing chain-extending compound.
- steps 4a) and 4b) together are in the range of from 0.3 to 1.2, more preferably 0.3 to 1.1 and most preferably 0.4 to 1.1 stoichiometric equivalents.
- step 2a) comprises 0.1 to 0.55, more preferably 0.1 to 0.45 and most preferably 0.1 to 0.42 stoichiometric equivalents of at least one active-hydrogen containing chain-terminating compound.
- the final steps in each process embodiment are repeated until the isocyanate group content is ⁇ 1 wt %, more preferably ⁇ 0.5 wt %, most preferably 0.01 wt % and especially is so low that the isocyanate group content is no longer detectable using methods well known in the art.
- the organic solvent may be removed or further organic solvent and or water may be added to give a polyurethane solution with a solids content in the range of from 10 to 90 wt %, preferably 35 to 75 wt %, more preferably 42 to 65 wt % and most preferably 49 to 60 wt %.
- the solvent borne polyurethane composition has a balance between properties such as good solubility in solvents, good adhesion, bond strength, block resistance, heat resistance and printability.
- composition of the invention may be used directly or in combination with, for example, fillers, waxes, thickeners, co-resins and/or colorants.
- composition of the invention may be used as a binder for packaging inks.
- an ink comprising a solvent borne polyurethane composition according to the invention, a colorant and optionally additional organic solvent.
- the ink preferably has a viscosity in the range of from 30 to 1,000 mPa ⁇ s, more preferably 30 to 500 mPa ⁇ s at 20° C.
- the ink viscosity may also be measured using a cup type viscometer where the time it takes a sample to flow out of the orifice of the sample container is measured in seconds.
- a cup type viscometer where the time it takes a sample to flow out of the orifice of the sample container is measured in seconds.
- An example of such a viscometer is a Ford Cup viscometer and a Ford Cup 4 viscometer has an orifice of 4 mm.
- This cup is suitable for ink viscosities in the range of from approximately 30 to 375 mPa ⁇ s and such inks usually flow out in about 10 to 100 seconds.
- the ink preferably has a viscosity in the range of from 10 to 100 seconds, more preferably 10 to 75 seconds and especially 10 to 60 seconds when measured using a Ford Cup 4.
- the ink has a solids content in the range of from 10 to 80 wt %, more preferably 10 to 70 wt % and most preferably 15 to 60 wt %.
- the ink comprises 9 to 79 wt %, more preferably 9 to 70 wt % and most preferably 9 to 60 wt % of the solvent borne polyurethane obtained from the process of the present invention.
- the ink comprises 1 to 50 wt %, more preferably 3 to 40 wt % and most preferably 8 to 40 wt % of a colorant.
- Colorants include dyes, pigments or mixtures thereof.
- the pigment may be any conventional organic or inorganic pigment such as titanium dioxide, carbon black or any coloured pigments well known in the art.
- the dyes may be any conventional dyes selected from acid dyes, natural dyes, cationic or anionic direct dyes, basic dyes and reactive dyes.
- the ink may also contain other ingredients typically used in inks, for example de-foamers, anti-oxidants, corrosion inhibitors, bactericides and viscosity modifiers.
- the ink may be used in a number of printing processes including flexographic and/or gravure printing processes.
- the printing process is a flexographic and/or gravure printing process.
- CE denotes a comparative example. All parts and percentages are by weight unless specified otherwise.
- NeoRez U-391 is a non reactive polyurethane, 70 wt % solids and 30 wt % solvent (98% ethyl acetate, 2% ethanol) available from DSM NeoResins BV. The Mw is 6000 g/mol. NeoRez U-391 is non-film forming (on removal of all/most of the liquid medium from the polyurethane composition a paste remains).
- NeoRez U-371 is a non tacky, elastomeric, non reactive polyurethane, 42 wt % solids and 68 wt % solvent (23% ethyl acetate, 77% ethanol) available from DSM NeoResins BV. The Mw is 40,500 g/mol.
- NeoRez U-371 is film forming (on removal of all/most of the liquid medium from the polyurethane composition a cohesive film is formed which can be taken out of a mould without tearing the film and on stretching the film it recovers its shape.)
- the detection was performed with a differential refractive index detector (Waters 2410) at 40° C. internal temperature. 25 mg of sample were dissolved in 4 cm 3 of THF, and the mixtures were left undisturbed for at least 1 hour. Calibration was performed with 8 polystyrene standards (Polymer Laboratories, Easical PS-2), ranging from 580 to 377,400 g/mol prepared at a concentration of 0.10% w/v. The calculation was performed with Empower PRO 2002 software (Waters) with a third order calibration curve (R>0.99990) and using a flat and horizontal baseline considering species between 400,000 and 500 g/mol.
- Empower PRO 2002 software Waters
- the molecular weights are expressed in g/mol in this application and it should be understood that this is a molecular weight measured against polystyrene standards and derived using universal calibration as described above.
- the examples and comparative examples were prepared by blending the components and where necessary adjusting the liquid medium to obtain compositions with a similar solids content and a harmonised solvent system of about 30% ethyl acetate and 70% ethanol. This shows that it is possible to get a low viscosity system which indicates a better solvent compatibility, better resolubility and is more suitable for printing. See Table 1 below for the compositions:
- the resultant polyurethane composition had a Mw of 59,850 g/mol, a Mp of 58,150 g/mol and a PDi of 3.9.
- the viscosity of the resultant product was 3450 mPa ⁇ s when measured with a Brookfield LVT viscometer at 60 rpm, spindle 4 and at 25° C.
- a sample of a totally chain terminated (1.0 s.a. of n-butylamine) isocyanate-terminated prepolymer A was prepared and had a Mw of 20,460 g/mol.
- a chain extended (0.80 s.a. of isophorone diamine) isocyanate-terminated prepolymer A was prepared and had a Mw of 75,000 g/mol.
- a blend was prepared by blending the totally chain terminated prepolymer A (polyurethane A) and the chain extended prepolymer A (polyurethane B) in a proportion 10/90 wt %, which is the theoretical wt % corresponding to the degree of chain-terminating conducted in step 2a above.
- the solids (50%) and the solvent system of the resultant blend were the same as in the current example.
- the resultant blend had a Mw of 56,600 g/mol, a Mp of 55000 g/mol, a PDi of 4.0 and a viscosity of 3550 mPa ⁇ s when measured with a Brookfield LVT viscometer at 60 rpm, spindle 4 and at 25° C.
- the polyurethane composition of the current example is made of approximately 10 wt % of a polyurethane A with a Mw of 20460 g/mol and a 90 wt % of a polyurethane B with a Mw of 75,000 g/mol.
- a film was prepared by pouring enough of the example compositions, so as to have 7.5 grams of polyurethane, into a plastic container (8 cm diameter, 1 cm deep). The plastic container with the composition was left in an oven at 45 to 50° C. for one day and then allowed to cool to room temperature. Then the resultant film was taken out from the container. A slight pressure was applied with fingers on the film for a few seconds. On removal of the fingers from the film the tack of the film was compared. Results are shown in Table 2 below and are expressed as follows
- Example 1 2 3 4 5 Tack ++ ++ 0 +++ + Film forming Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes
- Example 6 CE 7 8
- CE 9 CE 10 Tack ++ 0 ++++ 0 0 Film forming Yes Yes Yes Yes NO
- Ingredients 1 to 4 as shown in Table 3 below were mixed into a homogeneous mixture.
- Ingredient 5 was added to the mixture and dispersed using a Cowles Dissolver or the like until a slurry consistency was reached and the pigment particles were smaller than 10 ⁇ m (about 30 minutes).
- Ingredient 6 was added under agitation. The viscosity of the ink was adjusted with ingredient 7 to a viscosity of 18 to 22 seconds as measured by a Ford Cup 4 at 20° C.
- a film of the white ink prepared as described in Table 3 above was cast onto each substrate (6 ⁇ m wet) and dried with a hairdryer for 5 seconds.
- a self adhesive tape (10 cm, type 683 of 3M) was applied under uniform pressure onto the ink layer on each substrate immediately after drying of the layer and torn off the substrate immediately thereafter.
- the quantity of the print adhered to the tape was classified with a scale from 0 to 5, where 0 means more than 95% of the printed layer adhered to the tape, 1 means more than 50% of the layer adhered to the tape, 2 means less than 30%, of the printed layer adhered to the tape, 3 means less than 20% of the printed layer adhered to the tape, 4 means less than 10% of the printed layer adhered to the tape and 5 means less than 2% of the printed film adhered to the tape.
- Table 4 The results are shown in Table 4 below.
- the technique for the production of the laminate is the adhesive based lamination technique.
- a film of the white ink prepared as described in Table 3 above was cast onto each substrate (6 ⁇ m wet) and dried with a hairdryer for 5 seconds. After 2 hours an adhesive Novacote 275/Ca 12, 4 ⁇ m wet, 33.3% solids was applied onto the white ink layer and the second substrate was applied to the adhesive layer.
- the laminates were rolled with a 10 kg roller and stored for 2 days at room temperature. Then the bond strength was measured by pulling the substrates apart using dynamo meter JBA model 853.
- the bond strength is expressed as a combination of number value and letters.
- the number value stands for grams needed to separate the laminate of a width of 15 mm and a dynamometer speed of 100 mm/min and is given in Newton/15 mm. The higher the value the greater the bond strength.
- the letters indicate the kind of breakage with regards to the layer of the printing ink. The results are given in Table 5 below.
- a OPP film printed with a white ink layer (6 ⁇ m wet, prepared as described in Table 2 above) and dried with a hairdryer for 5 seconds was overlapped onto an unprinted OPP film which had been subjected to a corona-discharging treatment so that the printed and therefore inked surface of the former was brought into contact with the surface of the latter.
- Heat resistance also known as the thermo resistance
- An area of a printed substrate in contact with aluminium foil was placed between the heat seal jaws previously preset to a temperature of at least 120° C.
- a dwell time of 1 second at a pressure of 3 bars/cm 2 was applied.
- the temperature was increased step by step until failure occurred. For a pass there should be no ink transfer from the print to the foil.
- An acceptable temperature for a fail is 140° C. The results are shown below in Table 7.
- Cob-webbing is one of the causes of printing problems.
- the polyurethane compostions of the examples 1, 3, 6 and 8 and comparative example 9 were formulated into a blue ink to show improvement in the cob-webbing tendency.
- Ingredient 6 was added to the mixture and dispersed using a Cowles Dissolver or the like until a slurry consistency was reached and the pigment particles were reduced to a size less than to 10 ⁇ m (about 30 minutes).
- Ingredients 7, 8 and 9 were added under agitation.
- the viscosity of the ink was adjusted with ingredient 10 to a viscosity of 30 to 40 seconds as measured by a Ford Cup 4 at 20° C.
- the inks were then adjusted with further ethanol to a viscosity of 18 to 22 seconds as measured by a Ford Cup 4 at 20° C.
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US13/829,174 Abandoned US20130202859A1 (en) | 2005-07-14 | 2013-03-14 | Solvent borne polyurethane process |
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US13/829,174 Abandoned US20130202859A1 (en) | 2005-07-14 | 2013-03-14 | Solvent borne polyurethane process |
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DE (1) | DE602006019260D1 (de) |
ES (2) | ES2358922T3 (de) |
HK (2) | HK1122319A1 (de) |
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CN112585225A (zh) * | 2018-08-31 | 2021-03-30 | 巴斯夫欧洲公司 | 聚氨酯嵌段共聚物油墨组合物及其使用和制备方法 |
WO2021156016A1 (de) * | 2020-02-03 | 2021-08-12 | Sika Technology Ag | Polyurethan-zusammensetzung mit guter haftung auf kunststoffen |
CN112279989A (zh) * | 2020-10-30 | 2021-01-29 | 南通高盟新材料有限公司 | 一种醇溶型聚氨酯油墨连接料及其制备方法 |
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- 2006-07-14 EP EP20060762587 patent/EP1910438B1/de active Active
- 2006-07-14 CN CN2006800255733A patent/CN101238159B/zh active Active
- 2006-07-14 CN CN2006800255574A patent/CN101223203B/zh active Active
- 2006-07-14 ES ES06762583.0T patent/ES2564239T3/es active Active
- 2006-07-14 AT AT06762587T patent/ATE493452T1/de active
- 2006-07-14 EP EP06762583.0A patent/EP1907433B1/de active Active
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US20080226881A1 (en) * | 2005-07-14 | 2008-09-18 | Ester Parra Pastor | Solvent Borne Polyurethane Process |
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Also Published As
Publication number | Publication date |
---|---|
WO2007006583A1 (en) | 2007-01-18 |
PL1907433T3 (pl) | 2016-06-30 |
CN101223203B (zh) | 2013-08-14 |
US20080226881A1 (en) | 2008-09-18 |
US8492458B2 (en) | 2013-07-23 |
EP1910438B1 (de) | 2010-12-29 |
US20120189825A1 (en) | 2012-07-26 |
ES2564239T3 (es) | 2016-03-21 |
CN101238159A (zh) | 2008-08-06 |
US20100203301A1 (en) | 2010-08-12 |
HK1123058A1 (en) | 2009-06-05 |
PL1910438T3 (pl) | 2011-05-31 |
CN101238159B (zh) | 2012-06-20 |
CN101223203A (zh) | 2008-07-16 |
US20130202859A1 (en) | 2013-08-08 |
WO2007006586A1 (en) | 2007-01-18 |
ATE493452T1 (de) | 2011-01-15 |
EP1907433A1 (de) | 2008-04-09 |
EP1743911A1 (de) | 2007-01-17 |
WO2007006586A8 (en) | 2008-03-06 |
EP1910438A1 (de) | 2008-04-16 |
US20120263925A1 (en) | 2012-10-18 |
HK1122319A1 (en) | 2009-05-15 |
ES2358922T3 (es) | 2011-05-16 |
DE602006019260D1 (de) | 2011-02-10 |
EP1907433B1 (de) | 2015-12-23 |
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