WO2014031923A1 - Coated substrates and methods for producing the same - Google Patents
Coated substrates and methods for producing the same Download PDFInfo
- Publication number
- WO2014031923A1 WO2014031923A1 PCT/US2013/056321 US2013056321W WO2014031923A1 WO 2014031923 A1 WO2014031923 A1 WO 2014031923A1 US 2013056321 W US2013056321 W US 2013056321W WO 2014031923 A1 WO2014031923 A1 WO 2014031923A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- groups
- group
- colorant
- coated substrate
- active hydrogen
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title description 18
- 239000003086 colorant Substances 0.000 claims abstract description 85
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- -1 isocyanate compound Chemical class 0.000 claims abstract description 36
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 125000001424 substituent group Chemical group 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 239000004970 Chain extender Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Chemical group 0.000 claims description 5
- 125000000565 sulfonamide group Chemical group 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005224 alkoxybenzenes Chemical group 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000007860 aryl ester derivatives Chemical group 0.000 claims description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000004028 organic sulfates Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 239000000049 pigment Substances 0.000 description 23
- 239000002649 leather substitute Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000000975 dye Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 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 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 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 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 235000019239 indanthrene blue RS Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940099800 pigment red 48 Drugs 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ZKSBDEFDWSDNPW-UHFFFAOYSA-N 1-butoxy-2,4-diisocyanatobenzene Chemical compound CCCCOC1=CC=C(N=C=O)C=C1N=C=O ZKSBDEFDWSDNPW-UHFFFAOYSA-N 0.000 description 1
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 description 1
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 description 1
- VXQILLTWRZPRQF-UHFFFAOYSA-N 2,4-diisocyanato-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1N=C=O VXQILLTWRZPRQF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 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 1
- 125000006838 isophorone group Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000000643 oven drying Methods 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000003156 secondary amide group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 238000004383 yellowing Methods 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Definitions
- the present invention is directed to substrates comprising a coating on the surface thereof, such as substrates having a coating thereon intended to mimic the look and feel of leather.
- Synthetic leather typically is produced by coating or laminating an elastic polymer resin, such as a polyurethane resin, a polyvinyl chloride resin, or a blend of such resins, onto the surface of a fibrous base material.
- an elastic polymer resin such as a polyurethane resin, a polyvinyl chloride resin, or a blend of such resins.
- various pigments or dyes have been used to color the resin applied to the surface of the base material.
- pigments usually have low tinting strength and a dull shade, which can limit the aesthetic qualities of synthetic leather produced using them.
- Pigments typically lack solubilizing groups, which frequently allows the pigment particles to aggregate and form larger secondary and tertiary aggregate particles during production processes.
- synthetic leathers colored with conventional pigments often exhibit poor color retention, have a dark or dull shade, or contain unsuitable variations in color depth. While these problems can be partially addressed through the addition of dispersing agents or by utilizing pigment dispersions, these measures often result in increased production costs and still require great care to minimize color variations produced by settling of the pigment(s) and/or incompatibility of these components with the resin.
- Dyes typically contain solubilizing groups that can facilitate dispersion of the dye in a suitable medium. Dyes also typically exhibit relatively high tinting strength, good transparency, good thermal stability, and acceptable resin compatibility. Nevertheless, dyes typically exhibit poor weather durability, poor water resistance, poor oil resistance, and often migrate or bleed through to the transfer substrates, such as a release paper, used to produce the synthetic leather. In order to address the migration of dyes to the transfer substrate, attempts have been made to utilize nylon or polyurethane overcoats applied to the transfer substrate. However, satisfactory topcoats have not been developed without incurring significantly higher cost.
- the present invention provides such articles and methods for producing the same.
- a coated substrate comprises a substrate and a coating on at least one surface of the substrate.
- the coating comprises a prepolymer, polymer, or resin and a colorant compound.
- the colorant compound can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
- a method for producing a coated substrate comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the
- the colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
- a method for producing a coated substrate comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the
- the colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
- a coated substrate comprises a substrate and a coating on at least one surface of the substrate.
- the coating comprises a prepolymer, polymer, or resin and a colorant compound.
- the coated substrate is a synthetic leather article.
- the substrate can be any suitable substrate, such as a fibrous substrate, a natural leather substrate, thermoplastic resins, thermoset resins, and combinations thereof.
- the substrate is a textile material.
- Suitable textiles include, but are not limited to, woven textiles, knit textiles, and non-wovens.
- the textiles can be made from any suitable natural fibers, synthetic fibers, or combinations thereof.
- the substrate can comprise a precoat layer on the surface to which the coating is applied.
- the precoat layer can comprise any suitable material, such as a material that promotes adhesion between the substrate and the coating.
- the precoat layer can comprise elastomeric polymers.
- the coating can comprise any suitable portion of the coated substrate.
- the coating can be substantially coextensive or coextensive with at least one surface of the substrate.
- substantially coextensive means that the coating covers about 50% or more, preferably about 75% or more, more preferably about 90% or more, and most preferably about 95% or more of the area of the substrate surface on which the coating is disposed.
- the amount of the coating can also be expressed in terms of its contribution to the total weight of the coated substrate.
- the coating comprises about 0.1 % or more, about 0.5% or more, or about 1 % or more of the total weight of the coated substrate.
- the prepolymer, polymer, or resin in the coating can be any suitable prepolymer, polymer, or resin.
- the prepolymer, polymer, or resin typically will be selected to provide an article that is flexible and durable, while providing the properties necessary or desirable for mimicking, for example, real leather.
- the prepolymer, polymer, or resin is selected from the group consisting of polyurethane resins, polyurea resins, and combinations thereof.
- Suitable polyurethanes include linear polyurethanes as well as cross-linked polyurethanes, such as a polyurethane cross-linked with hexamethylene
- the resins suitable for use in the coating can be produced using any suitable polyol.
- suitable polyols include, but are not limited to, glycols of low molecular weight, such as ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,4-butylene glycol, and 1 ,6-hexamethylene glycol; polyester diols obtained from dibasic acids, such as adipic acid, maleic acid, and terephthalic acid; polyester diols, such as polylactones obtained by subjecting lactones to ring-opening polymerization with glycols; polycarbonate diols; and polyether diols, such as polytetramethylene glycol, polyethylene glycol, and polypropylene glycol.
- the resins suitable for use in the coating can be produced using any suitable isocyanate compound.
- Suitable isocyanate compounds include, but are not limited to, aromatic diisocyanates, such as toluene-2,4-diisocyanate (TDI), a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, 4-methoxy-1 ,3-phenylene diisocyanate, 4-isopropyl-1 ,3-phenylene diisocyanate, 4-chloro-1 ,3-phenylene diisocyanate, 4-butoxy-1 ,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4'-methylenebis(phenyl-isocyanate) (MDI), 2,4'-methylenebis(phenyl-isocyanate), a mixture of 4,4'-methylenebis(phenyl-isocyanate) and 2,
- mefa-tetramethylxylylene diisocyanate isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI ; and polyurethane prepolymers obtained by reacting any of the aforementioned diisocyanates with polyols or polyamines of low molecular weights such that the resulting prepolymers have isocyanate groups at ends thereof.
- aromatic diisocyanates particularly, aromatic diisocyanates, particularly
- diphenylmethane-4,4'-diisocyante (4,4'-MDI) or polymeric MDI are preferred for obtaining articles exhibiting good physical characteristics such as thermal stability, solution stability, and fracture strength.
- Alicyclic diisocyanates, such as isophorones, are preferred for obtaining polyurethanes that exhibit anti-yellowing properties and are not easily discolored upon exposure to sunlight.
- the resins or prepolymers suitable for use in the coating can be produced using suitable chain extenders. These include, but are not limited to, water; low-molecular diols, such as ethylene glycol and propylene glycol; aliphatic diamines, such as ethylenediamine; aromatic diamines, such as
- 4,4'-diaminodicyclohexylmethane and isophoronediamine alkanolamines, such as ethanolamine; hydrazines; and dihydrazides, such as succinic dihydrazide.
- the diamine compounds are preferable, with 4,4'-diaminodiphenylmethane being particularly preferred due to its heat resistance and 4,4'-diaminodicyclohexylmethane being preferred for light resistance.
- the aforementioned chain extenders can, of course, be used alone or in any suitable combination.
- the coating can comprise one or more polymers or resins selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, alkylpolyacrylate, polymethacrylic acid, alkylpolymethacrylate, and copolymers thereof.
- PVC polyvinyl chloride
- polyvinylidene chloride polyvinyl acetate
- polyacrylic acid alkylpolyacrylate
- polymethacrylic acid alkylpolymethacrylate
- copolymers thereof copolymers thereof.
- the coating further comprises a colorant compound.
- the colorant compound can be produced, for example, by the reaction of an isocyanate compound (e.g., a polyisocyanate compound) with an active hydrogen-terminated colorant.
- the isocyanate compound used to produce the colorant compound can be any suitable isocyanate compound.
- the isocyanate compound comprises two or more isocyanate groups (i.e., the isocyanate compound is a polyisocyanate compound).
- compound used to produce the colorant compound can be any of the isocyanate compounds described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating.
- the active hydrogen-terminated colorant can be any colorant possessing one or more (preferably, three or more) active hydrogen atoms.
- active hydrogen refers to a hydrogen atom that is capable of reacting with an isocyanate compound in a condensation reaction.
- Active hydrogen-terminated colorants suitable for use in the invention include, but are not limited to, those colorants conforming to the structure of Formula (I) below:
- Ri or Ri— [E] a is an organic chromophore.
- the chromophore can be any suitable chromophore, such as an azo, bisazo,
- the chromophore exhibits a color selected from the group consisting of blue, cyan, red, magenta, and yellow.
- Each E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group.
- Each R 2 is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups.
- the variable a is a positive integer, such as an integer from 1 to 4.
- the variables b and c are independently selected from the group consisting of integers from 0 to 2.
- the colorant conforming to the structure of Formula (I) contains three or more— Z— X substituents bound to R-i . It is believed that utilizing a colorant comprising three or more— Z— X substituents will reduce migration of the colorant in the coating, which has been one of the deficiencies of certain coated substrates (e.g., colored synthetic leather articles).
- each Z is a divalent organic moiety independently selected from the group consisting of alkanediyl groups, arenediyl groups, and R 5 .
- R5 is a divalent substituent selected from the group consisting of:
- divalent substituents comprising two or more divalent repeating units independently selected from repeating units conforming to the structure of Formula (XX)
- R 0 i and R-102 are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, and aryloxyalkyl;
- Rm and Rn 2 are independently selected from the group consisting of hydrogen, hydroxyl, and C-i-C-io alkyl, c is an integer from 1 to 12, and d is an integer greater than zero (e.g., an integer from 1 to 100);
- R 2 i and R- 122 are independently selected from the group consisting of hydrogen, hydroxyl, and C 1 -C 1 0 alkyl, e is an integer from 1 to 12, and f is an integer greater than zero (e.g., an integer from 1 to 100);
- R 5 is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
- s, t, and v are zero or positive integers (e.g., integers from 0 to 150); and the sum of s, t, and v is 2 or more.
- the sum of s, t, and v is from 2 to about 100, from 2 to about 50, from 2 to about 40, from 2 to about 30, or from 2 to about 20.
- the divalent substituent R 5 is depicted as comprising a series of repeating units arranged in a block configuration. While such an arrangement of the repeating units is possible and potentially preferred, the repeating units comprising the divalent substituent R 5 can also be arranged in a random configuration or in any suitable combination of a block configuration and a random configuration.
- R 5 can be a divalent substituent comprising a series of two or more repeating units conforming to the structure of Formula (XX) arranged in a random configuration or a divalent substituent comprising a series of two more repeating units conforming to the structure of Formula (XX) and one or more repeating units conforming to the structure of Formula (XXI) all arranged in a random configuration.
- R 5 can be a divalent substituent comprising a series of two or more repeating units conforming to the structure of Formula (XX) arranged in a random configuration followed by a block of repeating units conforming to the structure of Formula (XXI).
- each X is an end group independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups.
- At least one— Z— X substituent of the colorant conforming to the structure of Formula (I) terminates in a group selected from the group consisting of a hydroxyl group, a sulfhydryl group, thiol groups, primary amine groups, secondary amine groups, primary amide groups, and secondary amide groups.
- at least one— Z— X substituent comprises an R 5 substituent as defined above.
- the active hydrogen terminated colorant conforms to the structure of Formula (V)
- each Rn is independently selected from the group consisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amide groups, and sulfonamide groups, and q is an integer from 0 to 4.
- R-I2 is selected from the group consisting of aromatic groups and heteroatom- containing aromatic groups.
- Q is a divalent linking group selected from the group consisting of oxygen, sulfur, a carbonyl group, a sulfonyl group, substituted and unsubstituted 1 ,3-benzothiazole groups, Ci-C 8 alkanediyl groups, C 2 -C 8 alkenediyi groups, a p-phenylenediamine group, a m-hydroxybenzene group, and a m-di(CrC 4 ) alkoxybenzene group, and r is equal to 2.
- Z is an R 5 substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred.
- X preferably is hydrogen.
- the colorant preferably conforms to the structure of one of Formulae (VI), (VII), (VIII), (IX), or (X) below:
- Z preferably is an R 5 substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred.
- X preferably is hydrogen.
- the isocyanate compound and the active hydrogen-terminated colorant can be reacted in any suitable amounts.
- the isocyanate compound and the colorant can be reacted in the initial step so that the ratio of isocyanate groups (from the isocyanate compound) to active hydrogen groups (from the colorant) is about 10 to about 1 , preferably about 8 to about 1 .5, and more preferably about 6 to about 2.5.
- the ratio of isocyanate groups (from the isocyanate compound) to active hydrogen groups (from the colorant) is about 10 to about 1 , preferably about 8 to about 1 .5, and more preferably about 6 to about 2.5.
- no other active hydrogen containing reactants e.g., chain extenders or chain terminators
- the isocyanate compound and the colorant can be reacted so that the ratio of isocyanate groups to active hydrogen groups is about 1 .8 to about 0.8, preferably about 1 .6 to about 0.9, and more preferably about 1 .3 to about 0.95.
- the colorant compound can be produced using other reactants.
- the colorant compound can be produced using chain extenders, chain terminators, and mixtures thereof.
- additional reactants are added to the reactant mixture after the isocyanate compound and the active hydrogen- terminated colorant have been allowed to react alone for a desired period of time.
- the isocyanate compound and the active hydrogen-terminated colorant are first reacted for a desired amount of time, the product of this first reaction is then reacted with a suitable chain extender, and then the product of this second reaction is then reacted with a suitable chain terminator.
- the chain extenders used in this context can be any suitable chain extender, include those chain extenders described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating.
- the chain extenders typically are used to increase the molecular weight of the compound produced by the reaction of the isocyanate compound and the active hydrogen-terminated colorant.
- the chain terminators used in this context can be any compound capable of terminating the propagation of the polymer chain in a condensation reaction involving an isocyanate compound.
- suitable chain terminators typically are compounds comprising a single active hydrogen atom including, but not limited to, monofunctional alcohols, monofunctional amines, and mixtures thereof.
- the chain terminators typically are used to react with any remaining free isocyanate groups, thereby reducing the propensity for the colorant compound to undergo further condensation reactions.
- the chain extenders and/or chain terminators can be used in any suitable amounts.
- the chain extenders and/or chain terminators are used in an amount necessary to yield a ratio of isocyanate groups to total active hydrogen groups (from the colorant and the chain extenders and/or chain terminators) of about 1 .8 to about 0.8, preferably about 1 .6 to about 0.9, and more preferably about 1 .3 to about 0.95.
- coloring agents can be incorporated into the coated substrate in order to control the color hue.
- coloring agents include conventionally known pigments and dyes.
- blue pigments include, but are not limited to, phthalocyanine C.I. Pigment Blue 15:3 and indanthrone C.I. Pigment Blue 60;
- red pigments include, but are not limited to, quinacridone C.I. Pigment Red 122, azo C.I. Pigment Red 22, C.I. Pigment Red 48:1 , C.I. Pigment Red 48:3 and C.I. Pigment Red 57:1 ;
- yellow pigments include, but are not limited to, azo C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 155,
- black pigments include, but are not limited to, carbon black.
- suitable dyes include, but are not limited to, solvent dyes, such as Yellow 82, Orange 5, Orange 62, Red 8, Red 62, Red 122, Blue 70, Black 27, and Black 34.
- any pigments used preferably are in added in the form of a dispersion or in resin pallet/flake forms, and any dyes used preferably are added in the form of a in solution or in resin pallet/flake forms.
- coated substrates e.g., synthetic leather articles
- the coated substrates can be produced using any suitable method.
- the coated substrates can be produced using both "a direct coating process” and “a transfer coating process", or "dry” and “wet” methods.
- the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive onto the resin coating produced in step (d), (f) applying a backing substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the fibrous backing substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a coated substrate (e.g., a synthetic leather article).
- a coated substrate e.g., a synthetic leather article
- the substrate, prepolymer, polymer, resin, and olgiomer used in the first method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrate according to the invention.
- the transfer substrate used in the first method embodiment can be any substrate that permits the formation of a resin coating thereon, while still enabling that resin coating to be released from the substrate without damaging the coating. Suitable transfer substrates include, but are not limited to, a release paper, such as a silicone-treated, mirror-surface release paper.
- a coated substrate e.g., a synthetic leather article
- a coated substrate can be produced, for example, by thoroughly mixing a polyurethane resin solution in methyl ethyl ketone/dimethylformamide with at least one colorant compound as described above and, optionally, with other additives.
- the mixture is then directly coated onto a release paper.
- a thin layer of adhesive is applied onto the resin coating.
- a suitable substrate is then applied to the adhesive layer, and the resulting assembly is heated.
- the release paper is then peeled off of the assembly to reveal a coated substrate (e.g., a synthetic leather article).
- the release paper typically is not discolored by the colorants employed and, therefore, can be reused.
- the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a backing substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution to cure the resin or prepolymer and form a coating on the surface thereof, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a coated substrate (e.g., a synthetic leather article).
- a coated substrate e.g., a synthetic leather article
- the substrate, prepolymer, polymer, resin, and colorant compound used in the second method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrates (e.g., synthetic leather articles) according to the invention.
- a coated substrate e.g., a synthetic leather article
- a coated substrate can be produced, for example, by thoroughly mixing a polyurethane resin or prepolymer solution in dimethylformamide with at least one colorant compound as described above and, optionally, with other additives.
- the mixture is then coated onto a suitable substrate, and the coated substrate is then immersed in an aqueous medium. While immersed in the aqueous medium, the solvent (e.g., dimethylformamide) is extracted from the mixture, which causes the polymer in the mixture to coagulate and form a film.
- the resulting substrate is then dried to produce a coated substrate (e.g., a synthetic leather article).
- This example describes the production of a red active hydrogen- terminated colorant (Tetra-functional Red 05) suitable for use in the invention.
- a Bis(4-aminophenyl)sulfone diamine was charged portionwise to a cold solution of approximately 217.96 g of 93% sulfuric acid and approximately 40.02 g of water. The mixture was cooled to approximately 0-5 °C with agitation and approximately 0.6 g of 2-ethylhexanol was added to control the foaming if necessary. Approximately 202.01 g of 40% nitrosylsulfuric acid (NSA) in sulfuric acid was slowly added into the reactor and the temperature was maintained at 0-5 °C. The mixture was stirred for approximately 2 hours after addition.
- NSA nitrosylsulfuric acid
- This example describes the production of a yellow active hydrogen- terminated colorant (Tetra-functional Yellow 01 ) suitable for use in the invention.
- the synthetic procedure of Example 1 was repeated, except that Bisaniline P was used as the diamine and Aniline 10EO was used as the coupler.
- the recovered product was a dark brown liquid exhibiting a maximum absorption at approximately 414 nm in methanol.
- This example describes the production of a yellow active hydrogen- terminated colorant (Tetra-functional Yellow 02) suitable for use in the invention.
- a yellow active hydrogen- terminated colorant (Tetra-functional Yellow 02) suitable for use in the invention.
- the synthetic procedure of Example 1 was repeated, except that 2,2-Bis[4-(4- aminophenoxy)phenyl]propane was used as the diamine and Aniline 10EO was used as the coupler.
- the recovered product was a dark brown liquid exhibiting a maximum absorption at approximately 416 nm in methanol.
- This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored coated substrates.
- Approximately 18.2 grams of Tetra-functional Red 05 (described above), approximately 37.5 grams of methylene diphenyl diisocyanate, and approximately 120 grams of dimethylformamide were charged into a reactor equipped with an agitator and temperature control. The reactants were charged into the reactor under a nitrogen blanket, and the resulting mixture was heated to a temperature of approximately 55 °C for approximately two hours.
- This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored coated substrates. Approximately 17.9 grams of Tetra-functional Yellow 01
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Abstract
Novel coated substrates comprise a substrate and a coating thereon. The coating comprises a polymeric component and a colorant compound. The colorant compound is produced by reacting an isocyanate compound and an active hydrogen-terminated colorant.
Description
COATED SUBSTRATES AND
METHODS FOR PRODUCING THE SAME
FIELD OF THE INVENTION
[0001] The present invention is directed to substrates comprising a coating on the surface thereof, such as substrates having a coating thereon intended to mimic the look and feel of leather.
BACKGROUND OF THE INVENTION
[0002] Synthetic leather typically is produced by coating or laminating an elastic polymer resin, such as a polyurethane resin, a polyvinyl chloride resin, or a blend of such resins, onto the surface of a fibrous base material. In order to produce a synthetic leather in a variety of colors and/or shades, various pigments or dyes have been used to color the resin applied to the surface of the base material.
However, the use of such pigments and dyes has not been without its disadvantages and drawbacks.
[0003] For example, pigments usually have low tinting strength and a dull shade, which can limit the aesthetic qualities of synthetic leather produced using them. Pigments typically lack solubilizing groups, which frequently allows the pigment particles to aggregate and form larger secondary and tertiary aggregate particles during production processes. Owing to these difficulties, synthetic leathers colored with conventional pigments often exhibit poor color retention, have a dark or dull shade, or contain unsuitable variations in color depth. While these problems can be partially addressed through the addition of dispersing agents or by utilizing pigment dispersions, these measures often result in increased production costs and still require great care to minimize color variations produced by settling of the pigment(s) and/or incompatibility of these components with the resin.
[0004] Dyes, on the other hand, typically contain solubilizing groups that can facilitate dispersion of the dye in a suitable medium. Dyes also typically exhibit relatively high tinting strength, good transparency, good thermal stability, and acceptable resin compatibility. Nevertheless, dyes typically exhibit poor weather durability, poor water resistance, poor oil resistance, and often migrate or bleed
through to the transfer substrates, such as a release paper, used to produce the synthetic leather. In order to address the migration of dyes to the transfer substrate, attempts have been made to utilize nylon or polyurethane overcoats applied to the transfer substrate. However, satisfactory topcoats have not been developed without incurring significantly higher cost.
[0005] A need therefore remains for novel colored synthetic leather articles that address the deficiencies of articles produced with conventional pigments and dyes, while still exhibiting the desired aesthetic qualities. The present invention provides such articles and methods for producing the same.
BRIEF SUMMARY OF THE INVENTION
[0006] A coated substrate comprises a substrate and a coating on at least one surface of the substrate. The coating comprises a prepolymer, polymer, or resin and a colorant compound. The colorant compound can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
[0007] A method for producing a coated substrate (e.g., synthetic leather article) comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the
prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive onto the resin coating produced in step (d), (f) applying a backing substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the fibrous backing substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a synthetic leather article. The colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
[0008] A method for producing a coated substrate (e.g., synthetic leather article) comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the
prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in
step (c) onto a backing substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution to cure the prepolymer, polymer, or resin and form a coating on the surface thereof, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a synthetic leather article. The colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
DETAILED DESCRIPTION OF THE INVENTION
[0009] A coated substrate comprises a substrate and a coating on at least one surface of the substrate. The coating comprises a prepolymer, polymer, or resin and a colorant compound. In certain embodiments of the coated substrate, the coated substrate is a synthetic leather article.
[0010] The substrate can be any suitable substrate, such as a fibrous substrate, a natural leather substrate, thermoplastic resins, thermoset resins, and combinations thereof. In certain possibly preferred embodiments, the substrate is a textile material. Suitable textiles include, but are not limited to, woven textiles, knit textiles, and non-wovens. The textiles can be made from any suitable natural fibers, synthetic fibers, or combinations thereof.
[0011] In order to promote adhesion between the substrate and the coating, the substrate can comprise a precoat layer on the surface to which the coating is applied. The precoat layer can comprise any suitable material, such as a material that promotes adhesion between the substrate and the coating. For example, the precoat layer can comprise elastomeric polymers.
[0012] The coating can comprise any suitable portion of the coated substrate. In certain possibly preferred embodiments, the coating can be substantially coextensive or coextensive with at least one surface of the substrate. As utilized herein, the term "substantially coextensive" means that the coating covers about 50% or more, preferably about 75% or more, more preferably about 90% or more, and most preferably about 95% or more of the area of the substrate surface on which the coating is disposed. The amount of the coating can also be expressed in terms of its contribution to the total weight of the coated substrate. In certain
possibly preferred embodiments, the coating comprises about 0.1 % or more, about 0.5% or more, or about 1 % or more of the total weight of the coated substrate.
[0013] The prepolymer, polymer, or resin in the coating can be any suitable prepolymer, polymer, or resin. The prepolymer, polymer, or resin typically will be selected to provide an article that is flexible and durable, while providing the properties necessary or desirable for mimicking, for example, real leather. In certain possibly preferred embodiments, the prepolymer, polymer, or resin is selected from the group consisting of polyurethane resins, polyurea resins, and combinations thereof. Suitable polyurethanes include linear polyurethanes as well as cross-linked polyurethanes, such as a polyurethane cross-linked with hexamethylene
diisocyanate trimer.
[0014] The resins suitable for use in the coating can be produced using any suitable polyol. Suitable polyols include, but are not limited to, glycols of low molecular weight, such as ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,4-butylene glycol, and 1 ,6-hexamethylene glycol; polyester diols obtained from dibasic acids, such as adipic acid, maleic acid, and terephthalic acid; polyester diols, such as polylactones obtained by subjecting lactones to ring-opening polymerization with glycols; polycarbonate diols; and polyether diols, such as polytetramethylene glycol, polyethylene glycol, and polypropylene glycol.
[0015] The resins suitable for use in the coating can be produced using any suitable isocyanate compound. Suitable isocyanate compounds include, but are not limited to, aromatic diisocyanates, such as toluene-2,4-diisocyanate (TDI), a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, 4-methoxy-1 ,3-phenylene diisocyanate, 4-isopropyl-1 ,3-phenylene diisocyanate, 4-chloro-1 ,3-phenylene diisocyanate, 4-butoxy-1 ,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4'-methylenebis(phenyl-isocyanate) (MDI), 2,4'-methylenebis(phenyl-isocyanate), a mixture of 4,4'-methylenebis(phenyl-isocyanate) and 2,4'-methylenebis(phenyl- isocyanate), polymeric MDI, durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1 ,5-naphthalene diisocyanate, benzidine diisocyanate, o- nitrobenzidine diisocyanate, and 4,4-diisocyanatodibenzyl; aliphatic diisocyanates, such as methylene diisocyanate, 1 ,4-tetramethylene diisocyanate, 1 ,6- hexamethylene diisocyanate, and 1 ,10-decamethylene diisocyanate; alicyclic
diisocyanates, such as 1 ,4-cyclohexylene diisocyanate, 4,4'-methylene- bis(cyclohexylisocyanate), 1 ,5-tetrahydronaphthalene diisocyanate,
mefa-tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI ; and polyurethane prepolymers obtained by reacting any of the aforementioned diisocyanates with polyols or polyamines of low molecular weights such that the resulting prepolymers have isocyanate groups at ends thereof. Among the aforementioned, aromatic diisocyanates, particularly
diphenylmethane-4,4'-diisocyante (4,4'-MDI) or polymeric MDI, are preferred for obtaining articles exhibiting good physical characteristics such as thermal stability, solution stability, and fracture strength. Alicyclic diisocyanates, such as isophorones, are preferred for obtaining polyurethanes that exhibit anti-yellowing properties and are not easily discolored upon exposure to sunlight.
[0016] The resins or prepolymers suitable for use in the coating can be produced using suitable chain extenders. These include, but are not limited to, water; low-molecular diols, such as ethylene glycol and propylene glycol; aliphatic diamines, such as ethylenediamine; aromatic diamines, such as
4,4'-diaminodiphenylmethane; alicyclic diamines, such as
4,4'-diaminodicyclohexylmethane and isophoronediamine; alkanolamines, such as ethanolamine; hydrazines; and dihydrazides, such as succinic dihydrazide. Among the aforementioned chain extenders, the diamine compounds are preferable, with 4,4'-diaminodiphenylmethane being particularly preferred due to its heat resistance and 4,4'-diaminodicyclohexylmethane being preferred for light resistance. The aforementioned chain extenders can, of course, be used alone or in any suitable combination.
[0017] Other resins or polymers can be used in combinations with the aforementioned resins. Thus, in certain embodiments, the coating can comprise one or more polymers or resins selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, alkylpolyacrylate, polymethacrylic acid, alkylpolymethacrylate, and copolymers thereof.
[0018] In addition to the prepolymer, polymer, or resin, the coating further comprises a colorant compound. The colorant compound can be produced, for example, by the reaction of an isocyanate compound (e.g., a polyisocyanate
compound) with an active hydrogen-terminated colorant. The isocyanate compound used to produce the colorant compound can be any suitable isocyanate compound. Preferably, the isocyanate compound comprises two or more isocyanate groups (i.e., the isocyanate compound is a polyisocyanate compound). The isocyanate
compound used to produce the colorant compound can be any of the isocyanate compounds described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating.
[0019] The active hydrogen-terminated colorant can be any colorant possessing one or more (preferably, three or more) active hydrogen atoms. As utilized herein, the term "active hydrogen" refers to a hydrogen atom that is capable of reacting with an isocyanate compound in a condensation reaction. Active hydrogen-terminated colorants suitable for use in the invention include, but are not limited to, those colorants conforming to the structure of Formula (I) below:
(I)
In the structure of Formula (I), Ri or Ri— [E]a is an organic chromophore. The chromophore can be any suitable chromophore, such as an azo, bisazo,
triphenylmethane, methine, or anthraquinone. In a preferred embodiment, the chromophore exhibits a color selected from the group consisting of blue, cyan, red, magenta, and yellow. Each E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group. Each R2 is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups. The variable a is a positive integer, such as an integer from 1 to 4. The variables b and c are independently selected from the group consisting of integers from 0 to 2. If E is nitrogen or a sulfonamide group, the sum of b and c is 2. If E is oxygen, sulfur, a sulfonyl group, a sulfonate group, or a carbonyl group, the variable b is 0 and c is 1 .
Preferably, the colorant conforming to the structure of Formula (I) contains three or more— Z— X substituents bound to R-i . It is believed that utilizing a colorant comprising three or more— Z— X substituents will reduce migration of the colorant in the coating, which has been one of the deficiencies of certain coated substrates (e.g., colored synthetic leather articles). While not wishing to be bound to any particular theory, it is believed that the presence of three or more— Z— X substituents permits the colorant to react with a sufficient amount of the isocyanate compound to increase the size and/or molecular weight of the colorant compound and reduce the tendency of the colorant compound to migrate in the coating.
[0020] In the structure of Formula (I), each Z is a divalent organic moiety independently selected from the group consisting of alkanediyl groups, arenediyl groups, and R5. R5 is a divalent substituent selected from the group consisting of:
(i) divalent substituents comprising two or more divalent repeating units independently selected from repeating units conforming to the structure of Formula (XX)
wherein R 0i and R-102 are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, and aryloxyalkyl;
(ii) divalent substituents conforming to the structure of Formula
(XXI)
wherein Rm and Rn2 are independently selected from the group consisting of hydrogen, hydroxyl, and C-i-C-io alkyl, c is an integer from 1 to 12, and d is an integer greater than zero (e.g., an integer from 1 to 100);
(iii) divalent substituents conforming to the structure of Formula
(XXII)
wherein R 2i and R-122 are independently selected from the group consisting of hydrogen, hydroxyl, and C1-C10 alkyl, e is an integer from 1 to 12, and f is an integer greater than zero (e.g., an integer from 1 to 100);
(iv) divalent substituents comprising two or more substituents selected from the group consisting of substituents conforming to a structure of Formula (XX), (XXI), or (XXII).
[0021] In a particularly preferred embodiment, R5 is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
In each of these structures, s, t, and v are zero or positive integers (e.g., integers from 0 to 150); and the sum of s, t, and v is 2 or more. Preferably, the sum of s, t, and v is from 2 to about 100, from 2 to about 50, from 2 to about 40, from 2 to about 30, or from 2 to about 20.
[0022] In the structures of Formulae (XXA), (XXB), and (XXC), the divalent substituent R5 is depicted as comprising a series of repeating units arranged in a block configuration. While such an arrangement of the repeating units is possible and potentially preferred, the repeating units comprising the divalent substituent R5 can also be arranged in a random configuration or in any suitable combination of a block configuration and a random configuration. For example, R5 can be a divalent substituent comprising a series of two or more repeating units conforming to the
structure of Formula (XX) arranged in a random configuration or a divalent substituent comprising a series of two more repeating units conforming to the structure of Formula (XX) and one or more repeating units conforming to the structure of Formula (XXI) all arranged in a random configuration. Also, R5 can be a divalent substituent comprising a series of two or more repeating units conforming to the structure of Formula (XX) arranged in a random configuration followed by a block of repeating units conforming to the structure of Formula (XXI).
[0023] In the structure of Formula (I), each X is an end group independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups.
Preferably, at least one— Z— X substituent of the colorant conforming to the structure of Formula (I) terminates in a group selected from the group consisting of a hydroxyl group, a sulfhydryl group, thiol groups, primary amine groups, secondary amine groups, primary amide groups, and secondary amide groups. Preferably, at least one— Z— X substituent comprises an R5 substituent as defined above.
[0024] In certain possibly preferred embodiments, the active hydrogen terminated colorant conforms to the structure of Formula (V)
(V)
In the structure of Formula (V), each Rn is independently selected from the group consisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amide groups, and sulfonamide groups, and q is an integer from 0 to 4. R-I2 is selected from the group consisting of aromatic groups and heteroatom- containing aromatic groups. Q is a divalent linking group selected from the group consisting of oxygen, sulfur, a carbonyl group, a sulfonyl group, substituted and
unsubstituted 1 ,3-benzothiazole groups, Ci-C8 alkanediyl groups, C2-C8 alkenediyi groups, a p-phenylenediamine group, a m-hydroxybenzene group, and a m-di(CrC4) alkoxybenzene group, and r is equal to 2. Preferably, Z is an R5 substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred. X preferably is hydrogen.
[0025] In certain more specific embodiments, the colorant preferably conforms to the structure of one of Formulae (VI), (VII), (VIII), (IX), or (X) below:
(VIII)
(IX)
\ H /
-c I- / / \
(X)
In each of the structures of Formula (VI), (VII), (VIII), (IX), and (X), Z preferably is an R5 substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred. X preferably is hydrogen.
[0026] The isocyanate compound and the active hydrogen-terminated colorant can be reacted in any suitable amounts. For example, when a chain extender is intended to be used in a subsequent step (as described below), the isocyanate compound and the colorant can be reacted in the initial step so that the ratio of isocyanate groups (from the isocyanate compound) to active hydrogen groups (from the colorant) is about 10 to about 1 , preferably about 8 to about 1 .5, and more preferably about 6 to about 2.5. Alternatively, if no other active hydrogen containing reactants (e.g., chain extenders or chain terminators) are to be used in the
production of the colorant compound, the isocyanate compound and the colorant can be reacted so that the ratio of isocyanate groups to active hydrogen groups is about 1 .8 to about 0.8, preferably about 1 .6 to about 0.9, and more preferably about 1 .3 to about 0.95.
[0027] In addition to the isocyanate compound and the active hydrogen- terminated colorant, the colorant compound can be produced using other reactants. For example, the colorant compound can be produced using chain extenders, chain terminators, and mixtures thereof. Typically, such additional reactants are added to the reactant mixture after the isocyanate compound and the active hydrogen- terminated colorant have been allowed to react alone for a desired period of time. Thus, in one preferred embodiment, the isocyanate compound and the active hydrogen-terminated colorant are first reacted for a desired amount of time, the product of this first reaction is then reacted with a suitable chain extender, and then the product of this second reaction is then reacted with a suitable chain terminator. The chain extenders used in this context can be any suitable chain extender, include
those chain extenders described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating. The chain extenders typically are used to increase the molecular weight of the compound produced by the reaction of the isocyanate compound and the active hydrogen-terminated colorant. The chain terminators used in this context can be any compound capable of terminating the propagation of the polymer chain in a condensation reaction involving an isocyanate compound. Thus, suitable chain terminators typically are compounds comprising a single active hydrogen atom including, but not limited to, monofunctional alcohols, monofunctional amines, and mixtures thereof. The chain terminators typically are used to react with any remaining free isocyanate groups, thereby reducing the propensity for the colorant compound to undergo further condensation reactions.
[0028] When used in the production of the colorant compound, the chain extenders and/or chain terminators can be used in any suitable amounts. Typically, the chain extenders and/or chain terminators are used in an amount necessary to yield a ratio of isocyanate groups to total active hydrogen groups (from the colorant and the chain extenders and/or chain terminators) of about 1 .8 to about 0.8, preferably about 1 .6 to about 0.9, and more preferably about 1 .3 to about 0.95.
[0029] In addition to the above-described active hydrogen-terminated colorants, other coloring agents can be incorporated into the coated substrate in order to control the color hue. These coloring agents include conventionally known pigments and dyes. Examples of blue pigments include, but are not limited to, phthalocyanine C.I. Pigment Blue 15:3 and indanthrone C.I. Pigment Blue 60;
examples of red pigments include, but are not limited to, quinacridone C.I. Pigment Red 122, azo C.I. Pigment Red 22, C.I. Pigment Red 48:1 , C.I. Pigment Red 48:3 and C.I. Pigment Red 57:1 ; examples of yellow pigments include, but are not limited to, azo C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 155,
benzimidazolone C.I. Pigment Yellow 151 , C.I. Pigment Yellow 154 and C.I. Pigment Yellow 180; examples of black pigments include, but are not limited to, carbon black. Examples of suitable dyes include, but are not limited to, solvent dyes, such as Yellow 82, Orange 5, Orange 62, Red 8, Red 62, Red 122, Blue 70, Black 27, and Black 34. For ease of handling and mixing in the production of the coated substrate,
any pigments used preferably are in added in the form of a dispersion or in resin pallet/flake forms, and any dyes used preferably are added in the form of a in solution or in resin pallet/flake forms.
[0030] The coated substrates (e.g., synthetic leather articles) of the invention can be produced using any suitable method. For example, the coated substrates can be produced using both "a direct coating process" and "a transfer coating process", or "dry" and "wet" methods.
[0031] In a first method embodiment, the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive onto the resin coating produced in step (d), (f) applying a backing substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the fibrous backing substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a coated substrate (e.g., a synthetic leather article).
[0032] The substrate, prepolymer, polymer, resin, and olgiomer used in the first method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrate according to the invention. The transfer substrate used in the first method embodiment can be any substrate that permits the formation of a resin coating thereon, while still enabling that resin coating to be released from the substrate without damaging the coating. Suitable transfer substrates include, but are not limited to, a release paper, such as a silicone-treated, mirror-surface release paper.
[0033] In accordance with the first method embodiment, a coated substrate (e.g., a synthetic leather article) can be produced, for example, by thoroughly mixing a polyurethane resin solution in methyl ethyl ketone/dimethylformamide with at least one colorant compound as described above and, optionally, with other additives. The mixture is then directly coated onto a release paper. After evaporating the
solvent by oven drying or other drying process to produce a resin coating on the release paper, a thin layer of adhesive is applied onto the resin coating. A suitable substrate is then applied to the adhesive layer, and the resulting assembly is heated. The release paper is then peeled off of the assembly to reveal a coated substrate (e.g., a synthetic leather article). Furthermore, due to the lack of or minimal color migration resulting from the use of the colorant compound described above (i.e., a colorant compound made using an active hydrogen-terminated colorant comprising three or more— Z— X substituents, the release paper typically is not discolored by the colorants employed and, therefore, can be reused.
[0034] In a second method embodiment, the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a backing substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution to cure the resin or prepolymer and form a coating on the surface thereof, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a coated substrate (e.g., a synthetic leather article).
[0035] The substrate, prepolymer, polymer, resin, and colorant compound used in the second method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrates (e.g., synthetic leather articles) according to the invention.
[0036] In accordance with the second method embodiment, a coated substrate (e.g., a synthetic leather article) can be produced, for example, by thoroughly mixing a polyurethane resin or prepolymer solution in dimethylformamide with at least one colorant compound as described above and, optionally, with other additives. The mixture is then coated onto a suitable substrate, and the coated substrate is then immersed in an aqueous medium. While immersed in the aqueous medium, the solvent (e.g., dimethylformamide) is extracted from the mixture, which causes the polymer in the mixture to coagulate and form a film. The resulting
substrate is then dried to produce a coated substrate (e.g., a synthetic leather article).
[0037] The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.
EXAMPLE 1
[0038] This example describes the production of a red active hydrogen- terminated colorant (Tetra-functional Red 05) suitable for use in the invention.
Approximately 71 .76 g of a Bis(4-aminophenyl)sulfone diamine was charged portionwise to a cold solution of approximately 217.96 g of 93% sulfuric acid and approximately 40.02 g of water. The mixture was cooled to approximately 0-5 °C with agitation and approximately 0.6 g of 2-ethylhexanol was added to control the foaming if necessary. Approximately 202.01 g of 40% nitrosylsulfuric acid (NSA) in sulfuric acid was slowly added into the reactor and the temperature was maintained at 0-5 °C. The mixture was stirred for approximately 2 hours after addition. Then, approximately 22.46 g of sulfamic acid was added to kill excess nitrite and yield a diazonium solution. In a separate reactor, approximately 343 g of a 2,5- Dimethylaniline 10EO coupler was mixed with 2,5-Dimethylaniline 10EO 700 g of water, and the mixture was cooled to 2,5-Dimethylaniline 10EO 5-10 °C. The diazonium solution described above was slowly added to the coupler solution while the temperature was kept at approximately 5-10 °C. After addition, the mixture was stirred for approximately 1 hour. The reaction mixture was neutralized with 50% caustic, and the product was further cleaned up by water wash. The recovered product was approximately 390 g of dark red liquid exhibiting a maximum UV absorption at approximately 499 nm in methanol.
EXAMPLE 2
[0039] This example describes the production of a yellow active hydrogen- terminated colorant (Tetra-functional Yellow 01 ) suitable for use in the invention. The synthetic procedure of Example 1 was repeated, except that Bisaniline P was used as the diamine and Aniline 10EO was used as the coupler. The recovered
product was a dark brown liquid exhibiting a maximum absorption at approximately 414 nm in methanol.
EXAMPLE 3
[0040] This example describes the production of a yellow active hydrogen- terminated colorant (Tetra-functional Yellow 02) suitable for use in the invention. The synthetic procedure of Example 1 was repeated, except that 2,2-Bis[4-(4- aminophenoxy)phenyl]propane was used as the diamine and Aniline 10EO was used as the coupler. The recovered product was a dark brown liquid exhibiting a maximum absorption at approximately 416 nm in methanol.
EXAMPLE 4
[0041] This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored coated substrates. Approximately 18.2 grams of Tetra-functional Red 05 (described above), approximately 37.5 grams of methylene diphenyl diisocyanate, and approximately 120 grams of dimethylformamide were charged into a reactor equipped with an agitator and temperature control. The reactants were charged into the reactor under a nitrogen blanket, and the resulting mixture was heated to a temperature of approximately 55 °C for approximately two hours. Next,
approximately 30 grams of dimethylformamide was added to the reactor to dilute the resulting product, and approximately 8 grams of 1 ,4-butanediol was slowly added in portions. The resulting mixture was allowed to react at a temperature of
approximately 55 °C for approximately 30 minutes. Lastly, approximately 8 grams of dibutylamine was added to terminate the reaction. Approximately 150 grams of a red viscous solution was obtained. The solution contained a colorant compound and solvent. The color value of the solution was approximately 2.5 with a maximum absorption at approximately 510 nm.
EXAMPLE 5
[0042] This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored
coated substrates. Approximately 17.9 grams of Tetra-functional Yellow 01
(described above), approximately 37.5 grams of methylene diphenyl diisocyanate, and approximately 120 grams of dimethylformamide were charged into a reactor equipped with an agitator and temperature control. The reactants were charged into the reactor under a nitrogen blanket, and the resulting mixture was heated to a temperature of approximately 55 °C for approximately two hours. Next,
approximately 7.02 grams of 1 ,4-butanediol was slowly added in portions. The resulting mixture was allowed to react at a temperature of approximately 55 °C for approximately 30 minutes. Lastly, approximately 5 grams of dibutylamine was added to terminate the reaction. Approximately 240 grams of a yellow viscous solution was obtained. The solution contained a colorant compound and solvent. The color value of the solution was approximately 1 .7 with a maximum absorption at approximately 416 nm.
[0043] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0044] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly
contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise
claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0045] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Claims
1 . A coated substrate comprising:
(a) a substrate having at least one surface; and
(b) a coating on the surface of the substrate, the coating comprising:
(i) a polymeric component selected from the group consisting of prepolymers, polymers, resins, and mixtures thereof; and
(ii) a colorant compound, the colorant compound comprising a product produced by the reaction of an isocyanate compound and an active hydrogen-terminated colorant, wherein the active hydrogen-terminated colorant conforms to the structure of Formula (I)
(I)
wherein R or R— [E]a is an organic chromophore; E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group; each R2 is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups; the variable a is a positive integer; the variables b and c are independently selected from the group consisting of integers from 0 to 2; each X is an end group
independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups; each Z is a divalent organic moiety independently selected from the group consisting of alkanediyl groups, arenediyl groups, and R5; Rs is a divalent substituent selected from the group consisting of:
(1 ) divalent substituents comprising two or more divalent repeating units independently selected from repeating units conforming to the structure of Formula (XX)
wherein R 0i and R-102 are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyi, aryl, alkoxyalkyi, and aryloxyalkyl;
(2) divalent substituents conforming to the structure of Formula (XXI)
wherein Rm and Rn2 are independently selected from the group consisting of hydrogen, hydroxyl, and C C-m alkyl, c is an integer from 1 to 12, and d is an integer greater than zero (e.g., an integer from 1 to 100);
(3) divalent substituents conforming to the structure of Formula (XXII)
(XXII)
wherein R 2i and R-122 are independently selected from the group consisting of hydrogen, hydroxyl, and C-i-C-io alkyl, e is an integer from 1 to 12, and f is an integer greater than zero (e.g., an integer from 1 to 100); and
(4) divalent substituents comprising two or more substituents selected from the group consisting of substituents conforming to a structure of Formula (XX), (XXI), or (XXII); wherein the colorant comprises three or more— Z— X substituents.
2. The coated substrate of claim 1 , wherein R5 is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
(XXA)
3. The coated substrate of claim 1 , wherein the active hydrogen- terminated colorant conforms to the structure of Formula (V)
wherein each Rn is independently selected from the group consisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amide groups, and sulfonamide groups; q is an integer from 0 to 4; R-|2 is selected from the group consisting of aromatic groups and heteroatom-containing aromatic groups; Q is a divalent linking group selected from the group consisting of oxygen, sulfur, a carbonyl group, a sulfonyl group, substituted and unsubstituted 1 ,3-
benzothiazole groups, Ci-C8 alkanediyl groups, C2-C8 alkenediyi groups, a p-phenylenediamine group, a m-hydroxybenzene group, and a m-di(CrC4) alkoxybenzene group; and r is equal to 2.
4. The coated substrate of claim 3, wherein Z is R5, and R5 is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
5. The coated substrate of claim 3, wherein the active hydrogen- terminated colorant conforms to the structure of one of Formulae (VI), (VII), (VIII), (IX), or (X) below:
(VI)
(VIII)
(X)
X— z z— X
\ / x— z z— X
6. The coated substrate of claim 5, wherein Z is R5, and R5 is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
7. The coated substrate of claim 6, wherein s, t, and v are selected from the group consisting of zero and positive integers from 1 to 150.
8. The coated substrate of claim 6, wherein the sum of s, t, and v is from 2 to about 30.
9 The coated substrate of claim 1 , wherein the colorant is produced from a reaction mixture in which the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant is about 10 to about 1 .
10. The coated substrate of claim 9, wherein the colorant compound is produced by first reacting the isocyanate compound and the active hydrogen- terminated colorant to produce a first product, and then reacting the first product with a chain extender.
1 1 . The coated substrate of claim 10, wherein the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant and the chain extender is about 1 .8 to about 0.8.
12. The coated substrate of claim 1 , wherein the colorant is produced from a reaction mixture in which the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant is about 1 .8 to about 0.8.
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US (1) | US20140058026A1 (en) |
CN (1) | CN104487525A (en) |
WO (1) | WO2014031923A1 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050056189A1 (en) * | 2003-09-12 | 2005-03-17 | Decker Eldon L. | Coating composition having fluorescent colorants |
EP1559751A2 (en) * | 2004-01-28 | 2005-08-03 | Xerox Corporation | Emulsion aggregation process for forming curable powder coating compositions, curable powder coating compositions and method for using the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5731398A (en) * | 1996-05-31 | 1998-03-24 | Milliken Research Corporation | Black colorant composition exhibiting low flairing |
US7662461B2 (en) * | 2006-03-31 | 2010-02-16 | Milliken & Company | Synthetic leather articles and methods for producing the same |
US8431648B2 (en) * | 2006-03-31 | 2013-04-30 | Milliken & Company | Coated substrates and polymer dispersions suitable for use in making the same |
US7872069B2 (en) * | 2006-03-31 | 2011-01-18 | Milliken & Company | Coated substrates and polymer dispersions suitable for use in making the same |
-
2013
- 2013-08-23 WO PCT/US2013/056321 patent/WO2014031923A1/en active Application Filing
- 2013-08-23 US US13/974,161 patent/US20140058026A1/en not_active Abandoned
- 2013-08-23 CN CN201380037800.4A patent/CN104487525A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050056189A1 (en) * | 2003-09-12 | 2005-03-17 | Decker Eldon L. | Coating composition having fluorescent colorants |
EP1559751A2 (en) * | 2004-01-28 | 2005-08-03 | Xerox Corporation | Emulsion aggregation process for forming curable powder coating compositions, curable powder coating compositions and method for using the same |
Also Published As
Publication number | Publication date |
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US20140058026A1 (en) | 2014-02-27 |
CN104487525A (en) | 2015-04-01 |
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