WO2002033001A1 - Synthetic leather manufacturing method using aqueous polyurethane dispersions - Google Patents
Synthetic leather manufacturing method using aqueous polyurethane dispersions Download PDFInfo
- Publication number
- WO2002033001A1 WO2002033001A1 PCT/KR2001/001724 KR0101724W WO0233001A1 WO 2002033001 A1 WO2002033001 A1 WO 2002033001A1 KR 0101724 W KR0101724 W KR 0101724W WO 0233001 A1 WO0233001 A1 WO 0233001A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- aqueous
- synthetic leather
- acid
- solution
- Prior art date
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 80
- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000000243 solution Substances 0.000 claims abstract description 78
- 230000001112 coagulating effect Effects 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 125000000129 anionic group Chemical group 0.000 claims abstract description 26
- 125000002091 cationic group Chemical group 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
- 239000004814 polyurethane Substances 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- 239000011256 inorganic filler Substances 0.000 claims abstract description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 11
- 239000002585 base Substances 0.000 claims abstract description 9
- 239000005871 repellent Substances 0.000 claims abstract description 8
- 230000002940 repellent Effects 0.000 claims abstract description 7
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- YWQIGRBJQMNGSN-UHFFFAOYSA-M sodium;1,4-dioxo-1,4-di(tridecoxy)butane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCCCCCCCCC YWQIGRBJQMNGSN-UHFFFAOYSA-M 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 239000000945 filler Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 230000015271 coagulation Effects 0.000 description 22
- 238000005345 coagulation Methods 0.000 description 22
- 239000010985 leather Substances 0.000 description 14
- 239000004745 nonwoven fabric Substances 0.000 description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 239000004970 Chain extender Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- -1 dicarboxylic acid compound Chemical class 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000003512 tertiary amines Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004049 embossing Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003254 anti-foaming effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-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
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GXXKZNABQGUBCX-UHFFFAOYSA-N 2-piperazin-1-yl-n-(2-piperazin-1-ylethyl)ethanamine Chemical compound C1CNCCN1CCNCCN1CCNCC1 GXXKZNABQGUBCX-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 101100408464 Caenorhabditis elegans plc-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000361255 Diogenes Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- GKEMUBZAKCZMKO-UHFFFAOYSA-N ethane-1,2-diol;ethene Chemical group C=C.OCCO GKEMUBZAKCZMKO-UHFFFAOYSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- FGDMJJQHQDFUCP-UHFFFAOYSA-M sodium;2-propan-2-ylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(C(C)C)=CC=C21 FGDMJJQHQDFUCP-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Definitions
- the present invention relates to a synthetic leather manufacturing method using an anionic or cationic aqueous polyurethane dispersions and. more particularly. i n to a synthetic leather manufacturing method, in which a composition comprising an anionic or cationic aqueous polyuiethane dispersion, a water repellent, an emulsifier. an antifoamer and an inorganic filler is impregnated into a substrate such as nonwoven or woven fabric etc. and/or coated on the impregnated substrate, and then coagulated to form a s ⁇ nthetic leather internally provided with numerous closed cells
- synthetic leathers arc prepared from a polyurethane. which is excellent in chemical and physical properties, inter alia, chemical resistance and - ⁇ t ) softness.
- U.S. Patent No. 3.208.875 discloses a method for preparing a synthetic leather internally piovided with numerous closed cells and ing a coagulated sui face layer. in which a solution of poh urethanc in an organic solvent is coated on a nonwoven fabric and the poh urethane-coated nonw oven fabric is then passed through a A ' ⁇ coagulation bath normalh containing water as a coagulating solution compatible w ith the organic solvent used to dissolve the polyurethane but incompatible with the polyurethane. allow ing the organic solvent included in the solution coating to be diffused into the coagulating solution of the coagulation bath.
- This method uses an excess of an organic solvent that is relatively toxic and has a high boiling point to cause environmental pollution.
- U.S. Patent No 4.1 71.391 discloses a method for preparing a synthetic leather using an aqueous polyurethane dispersions. This method is. however, undesirable since it has a limit on controlling the structure of cells (e.g . size and density of cells) and utilizes acetic acid as a coagulating solution whose unique spicy odor is not to remo ⁇ e but has to be separate!) ed from the final product. Ivloreo . er. the method takes too much time in coagulation that the ma> be deteriorated.
- U.S. Patent No. 4.332.710 Another method for preparing a synthetic leather w ith reduced complexity of the process, especially, reduced time for coagulation is disclosed in U.S. Patent No. 4.332.710. characterized by using a heat-coagulating agent that generates an acid by heat to promote coagulation. This method is disadvantageous in that the use of the heat-coagulating agent deteriorates the storage stability of aqueous polyurethane dispersions
- U.S. Patent No. 5.460.873 discloses still another method for preparing a synthetic leather using a physical foaming machine to cause production of cells under mechanical stirring at high speed. This method, how ewer, involves some problems in that the open cells er the surface of the pioduct. such product being inadequate for use as a s ⁇ nthetie leather due to its coarse surface, and that the conventional piocess of manufacturing the synthetic leather is unusable since the method requires a separate drying facility.
- an aqueous polyurethane dispersion composition for a synthetic leather comprising: 100 parts by weight of an aqueous polyurethane dispersion, of which the main chain is covalently bonded to anionic groups including a carboxyl group or a sulfonate group, or cationic groups including a tertiary amine group : 0.1 to 5 parts by weight of a water repellant 0 0.1 to 8 parts by weight of an emulsifier: 0.1 to 1 part by weight of an antifoamer; and 0.1 to 5 parts by weight of an inorganic filler.
- aqueous polyurethane-based synthetic leather that is obtained by impregnating the composition comprising 100 parts by weight of an aqueous poh urethane dispersion. 0.1 to 5 parts by weight of a water repellant. 0.1 to 8 parts by weight of an emulsifier. 0.1 to 1 part by weight of an antifoamer.
- aqueous polyurethane dispersion is obtained by dispersing a polyurethane in water of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertian' amine group, wherein the coagulating solution is selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
- a method for preparing a synthetic leather from an aqueous polyurethane dispersions comprising the steps of: (a) preparing the composition comprising 100 parts by
- Figures 1 to 19 present microscopic photographs showing enlarged cross sections of the synthetic leathers prepared in accordance with Examples 1 to 19 of the present invention. I t )
- An aqueous polyurethane dispersion composition for sy nthetic leather comprises 100 parts by weight of an aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic 1.
- An aqueous polyurethane-based synthetic leather according to the present _,t) invention is prepared by impregnating a substrate with a composition comprising 100 parts by weight of the aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group .
- a composition comprising 100 parts by weight of the aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group .
- 0.1 to 1 part by weight of an antifoamer is prepared by impregnating a substrate with a composition comprising 100 parts by weight of the aqueous polyurethane dispersion
- a coagulating solution selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and -acid, a mixed solution of salt and base, a . mixed solution of acid and base, and mixtures thereof.
- the anionic or cationic polyurethane dispersion is an aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group, as disclosed in U.S. Patent Nos. 2.968.575 and 4.171.391 that are incorporated
- the aqueous polyurethane dispersion is obtained by a method in which an aqueous dispersion t> pe polvisocyanate including an ionic- charged group to allow self-emuls ⁇ fication is prepared by the condensation reaction between isocyanate. clioL polyol. and ionic chain extender . dispersed in water, and then subjected to polymerization reaction using a polyamine type chain extender.
- the l-o isocyanate as used in preparation of the polvisocyanate includes aromatic or aliphatic diisocyanates and a mixture thereof. Specifically, the isocyanate is selected from the group consisting of tolylene-2.4-diisocyanate.
- tolylene-2,6-diisocyanate meta- phenylene diisocyanate.
- biphenylene-4.4'-cl ⁇ socyanatc. methylenebis(4-phenyl diisocyanate), 4-chloro- 1.3-phenylene diisocyanate.
- tetrahy ronuphtl lene diisocyanate meta- phenylene diisocyanate.
- biphenylene-4.4'-cl ⁇ socyanatc. methylenebis(4-phenyl diisocyanate)
- isophoron diisocyanate 4.4'- methylenebis(eyclohexyl isocyanate). and mixtures thereof.
- the isocyanate is preferably hexamethylene- 1 .6-dusocyanatc. isophoron diisocyanate. cyclohexylene 1 .4-diisocyanate. or 4,4'-methylenebis(cyclohexyl isocyanate).
- Examples of the polyol as used in preparation of the polvisocyanate include a polyester polyol or a polyether polyol.
- the polyester polyol is usually obtained by condensation reaction between a dicarboxylic acid compound and a diol compound.
- Examples of the dicarboxylic acid compound as used herein include succinic acid, glutaric acid, adipic acid, suberic acid, azelanic acid, sebacic acid, dodecane dicarboxylic acid, hcxahulrophthalic acid, isophthalic acid, terephthalic acid, ortho- phthalic acid, tetrachlorophtha ⁇ c acid. 1.5-naphthalene dicarbox ⁇ lic acid, fumaric acid, male ⁇ c acid, itaconic acid, citraconic acid, mesaconic acid, and
- telrahydrophthalic acid examples include ethyleneglycol. propylenegh eol. 1 .3-propanediol. 1.3-butanediol. 1.4-butaned ⁇ ol. 1 .5- pentanediol. 1 .6-hexanedioI. neopentylglycol. cliethylenegh col. dipropylcnegK col. triethyleneglycol. tetraetln leneglycol. dibutylenegKcol. 2-methyl-1.3-pcntanediol. 2.2.4-trimethyl- 1.3-pentanecliol. and 1.4-cyclohexaneclimethanol.
- Suitable polyether polyol examples include polyethylenegh col. polypropyleneglycol. and polytetramethyleneglycol.
- the molecular weight of the polyol is in the range from 400 to 10.000 and preferably from 400 to 3.000.
- the ionic chain extender for self-emulsification of the polvisocyanate can be either an anionic chain extender or a cationic chain extender.
- the suitable anionic chain extender as 0 used herein is a compound containing a carboxyl group or a sulfonate group, such as 2.4-diamino-5-methylbenzenesul Ionic acid and 2.2-dimethylolpropionic acid.
- the suitable cationic chain extender as used herein is a tertiary amine diol or diamine compound, such as ldiethanolamine.
- the amount of the ionic chain extender is in the range of 1 to 25 wi i and preferably 1 .5 to 5 wtA> based on the total weight of the polyurethane.
- a neutralizing agent is used to convert the anionic or cationic groups co . alently bonded to the main chain of the polyurethane to a salt in order to increase dispersability in water for self-emulsification.
- the neutralizing agent for an anionic polyurethane include trimethylamine. triethylamine. ⁇ triisopropylamine.
- the neutralizing agent for a cationic polyurethane include acids such as phosphoric acid and acetic acid.
- the amount of the neutralizing agent is stoichiometrically more than 80% based on the ionic group, fhe isocx anatc
- polvisocyanate 10 and the polyol are reacted w ith each other at a mole ratio of 1 . 1 : 1 to 4: 1 to form the polvisocyanate.
- polvisocyanate dispersed in water is reacted with a chain extender for posl-polymei ization.
- chain extender for posl-polymei ization.
- suitable chain extender as used herein is polyamines. the example of which include hydrazine. ethylenediamine. pipeiazine. diethylenetriamine. t ⁇ ethylenetetramine. ietraethylenepenta ine.
- N.N-bis(2-aminoethyl)-N-(2-piperazinoethyl)amine N,N-bis(2- piperazinoethyl )amine. guanidine. mclamine. N-(2-aminoethyl)- 1.3-propanediamine. 3.3'-diaminobenzidine. 2.4.6-trian.inopyrimidine. dipropylcnetriamine. lenepentamine. t ⁇ prop ⁇ lenetetramine. N.N-bis(6-aminohe.xyl )amine. N.N'- bis(3-aminoprop ⁇ Dethylenediamine. 2.4-bis(4'-am ⁇ nobenzyl)aniline.
- Ihus obtained is the aqueous polvuiethane dispeision which has piepeiably a solid lesm content ol 20 to 50% and moie Strategiciabl) 20 to 30% and a paiticle size ol 50 to 200 run fhe aqueous polv methane dispeisio s is commeicialh av ailablc fhe aqueous pohuiclhanc dispeision composition foi leathei pieieiabh has a ol UO k.5000 cps and moie piefeiabh 1000 to 3000 cps l ⁇ i being used as an lmpiegnatmg composition oi pieieiabh has a iscositv ol 5000 to 15000 tps and moic pieieiabh 5000 to 10000 cps loi being used as a coating composition 1 oi the conttol of the a thickening agent
- he watei lepellent as used heiem is a lluoune compound oi a silicon compound which aie commeicialh av ilable as well known to those skilled in the ait and the specific example oi the watei lepellent include Zon>l (e g 8412 I oi RN I ) supplied b ⁇ Co Scotch guaid (e g FC255 oi FC214-230 1 ) supplied bv 3M Co and fefion (e g 8070 ,M oi 8787 ⁇ l ) supplied bv Dupon Co
- the watei lepellent enhances watei lepellent piopeih and watei lesistance and aids loimation of the cells in the svnthetic leathti thus obtained II the amount ol the watei lepellent is less than 01 pait b ⁇ weight the svnthetic leathei obtained has
- the emulsifier has a function of aiding formation of cells in the coating layer in the preparation of the svnthetic leather. If the amount oi ' the emulsifier is less than 0.1
- the cells in the synthetic leather may crash during the drying step.
- the synthetic leather has the surface with ci acks and a deterioration of the anti foaming effect when the synthetic leather being dried.
- the antifoamer as used herein is a silicon-based antifoamer. preferably in
- Suitable antifoamer is an organically modified polysiloxane. which is commercially available as well known to those skilled in the art. The antifoamer prevents the formation such as small crater on the surface of synthetic leather and controls the
- the inorganic filler as used herein is a commercially available inorganic filler, the example of which is a powder of modified silica, titanium oxide, alumina, ferric oxide, calcium oxide or magnesium oxide w ith an average diameter of around 1 ⁇ m. 7 and mixtures thereof.
- An amount of the inorganic filler less than 0.1 part bv weight deteriorates the abrasion resistance and prevents formation of cells in the coating layer, whereas an excess of the inorganic filler greater than 5 parts by weight deteriorates the softness of the sv nthetic leather.
- aqueous polyurethane resin composition according to the present 10 inv ention as obtained by mixing additives including water-repellent, emulsifier. antifoamer and inorganic filler with an aqueous polyurethane dispersion is impregnated into a substrate, mechanically foamed or defoamed and then coated on the substrate. Subsequently, the coated substrate is coagulated with a coagulating solution, which is selected from the group consisting of an aqueous solution of i n various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
- the mechanical foaming step is effected with a known stirring machine called “mechanical stirrcr " .
- the defoaming step is also effected with a commercially available pressure container operating under vacuum.
- the mechanical stirrcr and the 0 pressure container are both well known to those skilled in the art.
- the impregnation prior to the coating step and the coating of the aqueous polyurethane dispeision composition on the substrate are achieved by a known method such as dipping or glazing coating (e.g.. embossing coating), which is well known to those skilled in the art.
- the coagulating solution as used herein is preferably selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
- the salts contained in the aqueous solution of salts as a coagulating solution include: (a) all general salts including sodium chloride (NaCl ). silver chloride (AgCl).
- silver bromide AgBr. silver iodide (Agl), silver chromate (AgCr0 4 ). barium carbonate (BaCO,). barium fluoride (BaF ; ). calcium carbonate (CaCO;). mercury chloride (PbCL). magnesium carbonate (MgCO - lead chloride ( PbCL). silver nitrate (AgNO,). copper sulfate (CuS0 4 ). copper chloride (CuCL). and lead sulfate (PbSO . ; (b) sodium chloride, potassium chloride, calcium chloride, sodium sulfate and calcium sulfate. which are obtained by neutralization between a strong acid (e.g..
- hydrochloric acid sulfurie acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, etc.
- a strong base e.g.. sodium hydroxide, potassium hydroxide, calcium hydroxide. magnesium hydroxide, ammonia, etc.
- w hich are obtained by neutralization between a weak acid and a weak base as defined above, ' fhe coagulating solution ay have a pl-1 v alue variable depending on the tv pe and amount of the salt used therein and preferably controlled in the range from 3 to 1 1.
- a weak acid e.g.. fluoric acid, hydrogen sulfide. carbonic acid, sodium carbonate, carboxylic acids such as CH-C ⁇ H and Cfl .CH-COOH; and (e) CH-C ⁇ ONHj and CI I-CTLCOONH j.
- w hich are obtained by neutralization between a weak acid and a weak base as defined above, ' fhe coagulating solution ay have a pl-1 v alue variable depending on the tv pe and amount of the salt used therein and preferably controlled in the range from 3 to 1 1.
- the pl-l value of the coagulating solution can be controlled by adding an acid or base to the aqueous solution of the salt, or regulating the equivalent weight of the acid and base used in the preparation of the aqueous solution of the salt. 7
- the temperature of the coagulating solution in the coagulation bath is preferably in the range of 10 to 50 °C.
- the substrate is subjected to a post-treatment including washing, drying, embossing, buffing and weight reducing to produce the complete synthetic leather, the post-treatment method being well known to those
- the method for preparing a synthetic leather from an aqueous polyurethane dispersion according to the present invention includes the steps of: (a) preparing a coaling composition comprising 100 parts by weight of an aqueous polyurethane dispersion. 0.1 to 5 parts by weight of a water repellent. 0. 1 to 8 parts by weight of an
- emulsifier 0.1 to 1 part by weight of an antifoamer. and 0. 1 to 5 parts by weight of an inorganic filler, and subjecting the coating composition to mechanical foaming or defoaming.
- aqueous polyurethane dispersion is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group;
- the above-described aqueous polyurethane dispersion is mixed with additives such as water repellent. emulsifier. antifoamer and inorganic filler and the mixture is subjected to a mechanical foaming or e foaming step.
- the foamed or defoamed coating composition is applied to the substrate taken immediately after step (b) by a known coating method and passed through a coagulation bath containing the coagulating solution in the subsequent coagulation step, allowing the polyurethane dispersion to be coagulated into a synthetic leather.
- the thickness of the coating is in the range of 0. 1 to 3 mm. If the thickness of the coating is less than 0. 1 mm.
- the aqueous polyurethane dispersion is mixed with additives such as water repellent, emulsifier. antifoamer and inorganic filler, and the mixture is thickened with a thickening agent to have a viscosity of 500 to 5.000 cps and preferably 1.000 to 3.000 cps.
- the mixture is then impregnated into a woven or nonwoven fabric, which is applied to the subsequent coating step.
- the impregnation rate is in the range of 5 to 90% and preferably 5 to 50% based on the total weight of the woven or nonwoven fabric.
- An impregnation rate of less than 5%> deteriorates the mechanical properties of the synthetic leather including tensile strength and abrasion resistance, whereas an impregnation rate exceeding 90% deteriorates the softness of the svnthetic leather.
- the coagulation step (d) controls the shape. size and density of cells depending on the type, pl-l value and concentration of the aqueous solution of the salt to prevent formation such as small craters on the surface. which allows production of a synthetic leather with good properties such as coating property.
- the coagulating solution can be an aqueous solution of any general salt including silver chloride, silver bromide, silver iodide, silver chromate. barium carbonate, barium fluoride, calcium carbonate, mercury chloride, magnesium carbonate, lead chloride, silver nitrate, copper sulfate. copper chloride and lead sulfate.
- the coagulating solution can also be an aqueous solution of salts including sodium chloride, potassium chloride, calcium chloride, sodium sulfate and calcium sulfate. which are obtained by neutralization between a strong acid (e.g.. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide. nitrous acid, hypochlorous acid, etc.) and a strong base (e.g.. sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, etc.).
- a strong acid e.g. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide. nitrous acid, hypochlorous acid, etc.
- a strong base e.g. sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, etc.
- the coagulating solution can also be an aqueous solution of salts including ammonium chloride, ammonium sulfate. ammonium bromide and sodium carbonate, which are obtained by neutralization between a strong acid (e.g.. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, etc.) and a weak base including almost all water soluble amines.
- a strong acid e.g. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, etc.
- a weak base including almost all water soluble amines.
- fhe coagulating solution can also be an aqueous solution A salts including CH.COONa. CI LCI LCOONa. CH .COOK and C,ELNa. which are obtained by neutialization between a stiong base (e g . sodium hydioxide. potassium hydioxide. calcium h) di xide, magnesium hvdioxide. ammonia, etc.) and a weak acid (e g.. Iluoi ic acid, hvdiogen sulfide. caibo c acid, sodium carbonate, caiboxv'hc acids such as Cl-LC ⁇ OH aiuLCI-LCELCOOH 7 I he coagulating solution can also be an aqueous solution ol salts including
- CH-COONH CH-COONH
- CEECI-LCOONH 4 which aie obtained by neutialization between a weak acid (e g . lluonc acid, hv diogen sulfide. caibomc acid, sodium caibonate. caiboxv hc acids such as CELCOOH and CH-CFLCOOH and a w eak base including almost all watei soluble amines
- the coagulating solution can be a mixed aqueous solution obtained by adding an acid oi base to the aqueous solution oi the salt, or legulat g the equiv alent weight ol the acid and base used in the pi epaiation of the aqueous solution of the salt
- the salt content in the coagulating solution is piefetabh m the lange of 5 to 50 wt % and moic pieiei abh' in the lange of 20 to 40
- the coagulating solution is m the lange ol 3 to 7 fot an anionic po methane dispeision and 7 lo 1 1 foi a cationic poh in ethane dispeision If the pH v alue of the coagulating solution is less than 3 foi the anionic polyui ethane dispei sion oi gieatei than 1 1 ioi the cationic o methane dispeision. the cells aie scatceh iuin.ed in the sv nthetic leathei
- the present invention will be described in detail by way of the following examples, which are not intended to limit the scope of the present invention.
- a coating composition and an impregnating composition were prepared at the composition ratio shown in fables 1 and 2.
- Aqueous polyurethane dispersion is available from Nanopol Inc.. in Korea by the trade name NPL-5000(solicl contents 25% by weight, ion contents 3.5%/sohd by weight, anionic polyurethane emulsion).
- ⁇ queous pohuicthane dispeision is available liom Nan ⁇ pol Inc in Is-oi i bv the tiade name NPI -5200(s ⁇ hd contents 25% bv weight ion contents 18%/sohd bv weight anionic poh uiethane emulsion)
- the coating composition piepaied accoid g to lable 1 was cleloamed with a piessuie containei and coated on a nonwoven labile which was pievious dipped in the lmpiegnatmg composition as piepaied accoidmg to fable 2 using a glazing coating loi an embossing piocess I he coated nonwoven iabiie was lmmeised in a coagulation bath containing a coagulating solution loi 5 minutes Heie the coagulating solution was obtained bv adding ammonia (Nil ) to 30 wt % of an aqueous solution ol phosphoiic acid and contiollcd to have a pll value ol 4 Removed liom the coagulation bath, the coated nonwoven labile was washed and dned to obtain a svnthetic leathei I 1G 1 piesents a miuostopic p
- Aqueous poh uiethane dispeision is available fiom Nanopol Inc in Koiea bv the tiade name NPL-5100(sohd contents 25% by weight ion contents 2 5%/sohd bv weight anionic polvui ethane emulsion)
- I he coating composition piepaied accoidmg to 1 able 3 was foamed w ith a ioamei to hav e uniloi open cells and coated on a nonwov en iabiie which was dipped in the impiegnating composition piepaied m
- Example 1 I he coated nonwov en labnc was immei sed in a coagulation bath containing a coagulating solution loi 5 minutes I Lie the coamilatinu solution was obtained bv addmu ammonia (NH,) to 30 wt.%) of an aqueous solution of phosphoric acid and controlled to have a pl-l value of 4.
- FIG. 2 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As is apparent from FIG. 2. numerous closed cells are uniformly provided in the synthetic leather and the surface of the synthetic leather become smooth.
- Aqueous polyurethane dispersion is available from Nanopol Inc.. in Korea by the trade name NPL-53Q0(solid contents 25% by weight, ion contents 2%/solid by weight, anionic polyurethane emulsion.
- the impregnating composition prepared according to Table 4 was impregnated into a superfine nonwoven fabric for suede-like synthetic leather without a coating step, and the impregnated nonwoven fabric was heated and passed between pressure rollers to provide an impregnation rate of 45%> with respect to the nonwoven 7 fabric, " fhe impregnated nonwoven fabric was immersed in a coagulation bath containing a coagulating solution for 5 minutes.
- the coagulating solution was obtained by adding ammonia (NH-) to 30 wt.% of an aqueous solution of phosphoric acid and controlled to have a pl-l value of 4.
- NH- ammonia
- the coated nonwoven fabric was washed and dried to obtain a synthetic leather.
- FIG. 3 10 presents a microscopic photograph showing an enlarged cross section of the synthetic leather.
- the polyurethane resin is uniformed distributed over the nonwoven fabric other than the surface and has a space from the fiber unit to provide sufficient softness and bulkiness to the suede-like synthetic leather for suede.
- Example 4 1.7 The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 10 wt.% of an aqueous solution of sodium chloride was used as a coagulating solution.
- FIG. 4 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 4, the use of sodium chloride in the coagulating solution caused an increase in 0 formation of the cell-free region,
- FIG. 5 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 5. an increased concentration of the aqueous sodium chloride solution used as a coagulating solution caused an increase in formation of the cell-free region.
- a coating composition and an impregnating composition were prepared at the composition ratio shown in Tables 5 and 6.
- Aqueous polyurethane dispersion is a cationic polv urethane emulsion havinu solid contents 25% bv weiuht and ion contents 10%/solid bv wciuht.
- Aqueous pohuiethane dispeision is a cationic pohuiethane emulsion hav ⁇ m solid contents 25% bv wemht and ion contents 10% sohd bv weitzht
- FIG. 7 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 7. an increased concentration of the aqueous solution of the salt reduced the number of porous cells to almost zero.
- Example 8
- FIG. 8 presents a microscopic photograph show ing an enlarged cross section of the sv nthetic leather.
- the cells had a more apparent cylindrical form relative to those of Example 1 , That is. the shape of the cells can be varied depending on the type of the salt used in the coagulating solution.
- FIG. 9 presents a microscopic photograph showing an enlarged cross section of the synthetic leather.
- an increased content of the salt in the coagulation solution allowed a production of the cell-free synthetic leather, " fhis demonstrates that the content of the salt is an important factor in controlling the shape of the cells.
- FIG 11 piesents a macoscopic photogiaph showing an enlaiged cioss section ol the s>nthet ⁇ c leathei As shown in FIG 11 an mcieased content oi the salt in the coagulating solution caused an mciease in foimation of the cell-fiee legion
- Example 12 I he pioceduies wcie peiioimed to obtain a svnthetic leathei in the same mannei as clesciibed in Example 1 excepting that a 20% aqueous mixed solution ol phosphoiic acid and tiibutvlam e at the mole latio ol 1 1 was used as a coagulating solution
- FIG 12 piesents a macoscopic photogiaph showing an enlaiged cioss section of the svnthetic leathei Compaied to I xun.plc 1 this example used tributylamine as a base in phosphoric acid instead of ammonia and showed that the shape of the cells can be varied depending on the type of the salt.
- the use of tributylamine entirely reduced the uniformity of the cells but increased the size of the cells.
- FIG. 13 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 13. an increased content of the salt in the coagulating solution caused an increase in formation of a cell-free region and reduced the thickness of the surface coating.
- FIG. 14 presents a microscopic photograph showing an enlarged cross section of the synthetic leather.
- FIG. 15 presents a microscopic photograph show ing an enlarged cross section of the synthetic leather.
- a decreased phi value of the coagulating solution i.e.. acidification caused an increase in formation of the cell-free synthetic leather.
- Example 17 presents a microscopic photograph showing an enlarged cross section of the sv nthetic leather.
- FIG. 17 presents a microscopic photograph showing an enlarged cross section ol " the synthetic leather.
- an increased pFI value of the coagulating solution i.e.. alkalization caused a sharp increase in the size of the cells.
- Example 18 fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 20 wt.% of an aqueous phosphoric acid solution was mixed with ammonia to provide a coagulating solution having a controlled pl l value of 4, FIG. 1 8 presents a microscopic photograph showing an enlari-ed cross section of the svnthetic leather.
- Example 19
- FIG. 19 presents a microscopic photograph showing an enlarged cross section of the synthetic leather.
- the use of a mixed solution of acid and base instead of the solution of salt also provided numerous and uniform cells as in Example 1.
- the present invention provides a
- the use of various coagulating solutions allows a control of the shape, size and density of cells and thereby effectively provides a synthetic leather of various qualities.
- the synthetic leather may have large- diameter cells with a very low density as well as those having a very small size.
- the 0 density and size of the cells have an effect mainly on the texture and softness of the synthetic leather obtained so that the present invention provides a synthetic leather of v arious properties and makes it possible to prepare a sv nthetic leather of desired properties.
- Consequenlh. the present inv ention provides a en ironment-friendly method for preparing a synthetic leather with excellent properties and high productivity, and a synthetic leather obtained thereby, " fhe invention also provides a method for effectively preparing a synthetic leather of various qualities in which the shape, size and density of cells are controllable depending on the coagulating solution.
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Abstract
Disclosed is a method for preparing a synthetic leather, in which a composition including an anionic or cationic aqueous polyurethane dispersion, a water repellent, an emulsifier, an antifoamer and an inorganic filler is impregnated into a substrate, and coated on the substrate, the impregnated and/or coated substrate being then coagulated to form a synthetic leather internally provided with numerous closed cells and having a smooth surface.The aqueous polyurethane-based synthetic leather is obtained by impregnating a composition comprising 100 parts by weight of an aqueous polyurethane dispersion, 0.1 to 5 parts by weight of a water repellant, 0.1 to 8 parts by weight of an emulsifier, 0.1 to 1 part by weight of an antifoamer, and 0.1 to 5 parts by weight of an inorganic filler into a substrate, coating the foamed or defoamed composition on the substrate, and coagulating the coated substrate with a coagulating solution, wherein aqueous polyurethane dispersion is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group, wherein the coagulating solution is selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
Description
SYNTHETIC LEATH ER MANUFACTURING M ETHOD USING AQUEOUS POLYURETHANE DISPERSIONS
T ECHNICAL FIELD
The present invention relates to a synthetic leather manufacturing method using an anionic or cationic aqueous polyurethane dispersions and. more particularly. i n to a synthetic leather manufacturing method, in which a composition comprising an anionic or cationic aqueous polyuiethane dispersion, a water repellent, an emulsifier. an antifoamer and an inorganic filler is impregnated into a substrate such as nonwoven or woven fabric etc. and/or coated on the impregnated substrate, and then coagulated to form a s\ nthetic leather internally provided with numerous closed cells
1 r> and having a smooth surface,
BACKG OUD ART Generally, synthetic leathers arc prepared from a polyurethane. which is excellent in chemical and physical properties, inter alia, chemical resistance and -^t) softness.
U.S. Patent No. 3.208.875 discloses a method for preparing a synthetic leather internally piovided with numerous closed cells and
ing a coagulated sui face layer. in which a solution of poh urethanc in an organic solvent is coated on a nonwoven fabric and the poh urethane-coated nonw oven fabric is then passed through a A ' ~ coagulation bath normalh containing water as a coagulating solution compatible w ith
the organic solvent used to dissolve the polyurethane but incompatible with the polyurethane. allow ing the organic solvent included in the solution coating to be diffused into the coagulating solution of the coagulation bath. This method, however, uses an excess of an organic solvent that is relatively toxic and has a high boiling point to cause environmental pollution.
To solve this problem, a growing interest has been taken in the methods for preparing a synthetic leather using an aqueous polyurethane dispersions.
U.S. Patent No 4.1 71.391 discloses a method for preparing a synthetic leather using an aqueous polyurethane dispersions. This method is. however, undesirable since it has a limit on controlling the structure of cells (e.g . size and density of cells) and utilizes acetic acid as a coagulating solution whose unique spicy odor is not
to remo\ e but has to be separate!)
ed from the final product. Ivloreo . er. the method takes too much time in coagulation that the
ma> be deteriorated.
Another method for preparing a synthetic leather w ith reduced complexity of the process, especially, reduced time for coagulation is disclosed in U.S. Patent No. 4.332.710. characterized by using a heat-coagulating agent that generates an acid by heat to promote coagulation. This method is disadvantageous in that the use of the heat-coagulating agent deteriorates the storage stability of aqueous polyurethane dispersions U.S. Patent No. 5.460.873 discloses still another method for preparing a synthetic leather using a physical foaming machine to cause production of cells under mechanical stirring at high speed. This method, how ewer, involves some problems in that the open cells
er the surface of the pioduct. such product being inadequate for use as a s\ nthetie leather due to its coarse surface, and that the conventional piocess of manufacturing the synthetic leather is unusable since the
method requires a separate drying facility.
Accordingly, there is till a need of a novel method for preparing a synthetic leather environment-friendly and excellent in properties and productivity.
r» DISCLOSURE OF THE INVENTION
It is an object of the present invention to provide a aqueous polyurethane dispersion composition suitable for a synthetic leather.
It is another object of the present invention to provide a method for preparing a synthetic leather of good properties which is internally provided with numerous K> closed cells and almost destitute of open cells on the surface.
It is still another object of the present invention to provide a method for preparing a synthetic leather internally provided with cells of which the size, shape and distribution are controllable depending on the condition of the coagulation bath containing coagulation solution. I ." To achieve the objects of the present invention, there is provided an aqueous polyurethane dispersion composition for a synthetic leather, comprising: 100 parts by weight of an aqueous polyurethane dispersion, of which the main chain is covalently bonded to anionic groups including a carboxyl group or a sulfonate group, or cationic groups including a tertiary amine group : 0.1 to 5 parts by weight of a water repellant 0 0.1 to 8 parts by weight of an emulsifier: 0.1 to 1 part by weight of an antifoamer; and 0.1 to 5 parts by weight of an inorganic filler.
In another aspect of the present invention, there is provided aqueous polyurethane-based synthetic leather that is obtained by impregnating the composition comprising 100 parts by weight of an aqueous poh urethane dispersion.
0.1 to 5 parts by weight of a water repellant. 0.1 to 8 parts by weight of an emulsifier. 0.1 to 1 part by weight of an antifoamer. and 0.1 to 5 parts by weight of an inorganic filler into a substrate, and/or coating the defoamed or foamed composition on the substrate, and then coagulating the impregnated and/or coated substrate with a coagulating solution, wherein the aqueous polyurethane dispersion is obtained by dispersing a polyurethane in water of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertian' amine group, wherein the coagulating solution is selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
In further another aspect of the present invention, there is provided a method for preparing a synthetic leather from an aqueous polyurethane dispersions. α :omprising the steps of: (a) preparing the composition comprising 100 parts by
W ."e( ight of an aqueous polyurethane dispersions. 0.1 to 5 parts by weight of a water repellent. 0.1 to 8 parts by weight of an emulsifier. 0.1 to 1 part by weight of an antifoamer. and 0.1 to 5 parts by weight of an inorganic filler, and subjecting the composition to mechanical foaming or defoaming, wherein aqueous polyurethane dispersions of which the main chain is covalently bonded to anionic groups including _.() carboxyl group or sulfonate group, or cationic groups including a tertiary amine group; (b) impregnating the aqueous polyurethane dispersion composition into a substrate including a woven or nonwoven fabric: (c ) coating the substrate obtained in step (b) w ith the foamed or defoamed composition in step (a): (d) coagulating the substrate obtained in step(c ) with a coagulating solution selected from the group
consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution oi' acid and base, and mixtures thereof: and (e) subjecting the coagulated substrate to a post-treatment including washing, and drying, etc.
, i
BRIEF DESCRIPTION OF DRAWINGS Figures 1 to 19 present microscopic photographs showing enlarged cross sections of the synthetic leathers prepared in accordance with Examples 1 to 19 of the present invention. I t )
BEST MODE FOR CARRYING OUT THE INVENTION An aqueous polyurethane dispersion composition for sy nthetic leather according to the present invention comprises 100 parts by weight of an aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic 1." groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group: 0.1 to 5 parts by weight of a water repellant; 0.1 to 8 parts by weight of an emulsifier: 0.1 to 1 part by weight of an antifoamer: and 0.1 to 5 parts by weight of an inorganic filler.
An aqueous polyurethane-based synthetic leather according to the present _,t) invention is prepared by impregnating a substrate with a composition comprising 100 parts by weight of the aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group . 0.1 to 5 parts by weight of a water repellant. 0. 1 to 8 parts by weight of an emulsifier. 0.1 to 1 part by weight of an
antifoamer. and 0.1 to 5 parts by weight of an inorganic filler, coating the foamed or defoamed composition on the substrate, and coagulating the coated substrate with a coagulating solution selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and -acid, a mixed solution of salt and base, a . mixed solution of acid and base, and mixtures thereof.
The anionic or cationic polyurethane dispersion is an aqueous polyurethane dispersion of which the main chain is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group, as disclosed in U.S. Patent Nos. 2.968.575 and 4.171.391 that are incorporated
... herein by reference. That is. the aqueous polyurethane dispersion is obtained by a method in which an aqueous dispersion t> pe polvisocyanate including an ionic- charged group to allow self-emulsϊfication is prepared by the condensation reaction between isocyanate. clioL polyol. and ionic chain extender . dispersed in water, and then subjected to polymerization reaction using a polyamine type chain extender. The l-o isocyanate as used in preparation of the polvisocyanate includes aromatic or aliphatic diisocyanates and a mixture thereof. Specifically, the isocyanate is selected from the group consisting of tolylene-2.4-diisocyanate. tolylene-2,6-diisocyanate. meta- phenylene diisocyanate. biphenylene-4.4'-clϋsocyanatc. methylenebis(4-phenyl diisocyanate), 4-chloro- 1.3-phenylene diisocyanate. naphthalene- 1.5- diisocyanate. 0 tetramethylene- 1.4- diisocyanate. hexamethylene 1.6- diisocyanate. decamethylcne- 1.10- diisocyanate. cyelohexylene- 1.4- diisocyanate.
isocyanate). tetrahy ronuphtl lene diisocyanate. isophoron diisocyanate. 4.4'- methylenebis(eyclohexyl isocyanate). and mixtures thereof. The isocyanate is preferably hexamethylene- 1 .6-dusocyanatc. isophoron diisocyanate. cyclohexylene
1 .4-diisocyanate. or 4,4'-methylenebis(cyclohexyl isocyanate).
Examples of the polyol as used in preparation of the polvisocyanate include a polyester polyol or a polyether polyol. The polyester polyol is usually obtained by condensation reaction between a dicarboxylic acid compound and a diol compound. ." Examples of the dicarboxylic acid compound as used herein include succinic acid, glutaric acid, adipic acid, suberic acid, azelanic acid, sebacic acid, dodecane dicarboxylic acid, hcxahulrophthalic acid, isophthalic acid, terephthalic acid, ortho- phthalic acid, tetrachlorophthaϋc acid. 1.5-naphthalene dicarbox\ lic acid, fumaric acid, maleϊc acid, itaconic acid, citraconic acid, mesaconic acid, and
10 telrahydrophthalic acid. Examples of the diol compound as used herein include ethyleneglycol. propylenegh eol. 1 .3-propanediol. 1.3-butanediol. 1.4-butanedϊol. 1 .5- pentanediol. 1 .6-hexanedioI. neopentylglycol. cliethylenegh col. dipropylcnegK col. triethyleneglycol. tetraetln leneglycol. dibutylenegKcol. 2-methyl-1.3-pcntanediol. 2.2.4-trimethyl- 1.3-pentanecliol. and 1.4-cyclohexaneclimethanol. The customary
1.1 example of the suitable polyether polyol include polyethylenegh col. polypropyleneglycol. and polytetramethyleneglycol. The molecular weight of the polyol is in the range from 400 to 10.000 and preferably from 400 to 3.000. The ionic chain extender for self-emulsification of the polvisocyanate can be either an anionic chain extender or a cationic chain extender. The suitable anionic chain extender as 0 used herein is a compound containing a carboxyl group or a sulfonate group, such as 2.4-diamino-5-methylbenzenesul Ionic acid and 2.2-dimethylolpropionic acid. The suitable cationic chain extender as used herein is a tertiary amine diol or diamine compound, such as
ldiethanolamine. The amount of the ionic chain extender is in the range of 1 to 25 wi i and preferably 1 .5 to 5 wtA> based on the total weight of
the polyurethane. A neutralizing agent is used to convert the anionic or cationic groups co . alently bonded to the main chain of the polyurethane to a salt in order to increase dispersability in water for self-emulsification. Examples of the neutralizing agent for an anionic polyurethane include trimethylamine. triethylamine. π triisopropylamine. tributylamine, N.N-dimethylcyclohexyl, N.N-dimethylaniline. N- mcthylmorphorine. N-methylpiperazine. N- ethylpyrrolidine. and N- methylpipericlinc. Examples of the neutralizing agent for a cationic polyurethane include acids such as phosphoric acid and acetic acid. The amount of the neutralizing agent is stoichiometrically more than 80% based on the ionic group, fhe isocx anatc
10 and the polyol are reacted w ith each other at a mole ratio of 1 . 1 : 1 to 4: 1 to form the polvisocyanate. fhe polvisocyanate dispersed in water is reacted with a chain extender for posl-polymei ization. 'fhe suitable chain extender as used herein is polyamines. the example of which include hydrazine. ethylenediamine. pipeiazine. diethylenetriamine. tπethylenetetramine. ietraethylenepenta ine.
I n pentaethylenehexamine. N.N.N'-tris(2-aminocthyl)aminc. N-(2- piperazinoethyl )ethylenediamϊne. N.N'-bis(2-aminoethyl )piperazine. N,N.N'-tris(2- aminoethyDethylenediamine. N-[N-(2-aminoethyl)-2-aminoethyl]-N'-(2- aminoethyOpiperazine. N-(2-aminoethyl)-N'-(2-piperazinoεthyl)ethylenedϊamine. N.N-bis(2-aminoethyl)-N-(2-piperazinoethyl)amine. N,N-bis(2- piperazinoethyl )amine. guanidine. mclamine. N-(2-aminoethyl)- 1.3-propanediamine. 3.3'-diaminobenzidine. 2.4.6-trian.inopyrimidine. dipropylcnetriamine. lenepentamine. tπprop\ lenetetramine. N.N-bis(6-aminohe.xyl )amine. N.N'- bis(3-aminoprop\ Dethylenediamine. 2.4-bis(4'-amϊnobenzyl)aniline. 1.4- butanediamine. 1.6-hexanediamine. 1.8-oetanediamine, 1.10-decanediamine. 2-
1 12-dodecancdιamιne isophoiondiamine (01 1- amιno-3-amιnometh\l-355 tnmeth l-tytlohexane) and bιs(4-
Ihus obtained is the aqueous polvuiethane dispeision which has piepeiably a solid lesm content ol 20 to 50% and moie pieleiabl) 20 to 30% and a paiticle size ol 50 to 200 run fhe aqueous polv methane dispeisio s is commeicialh av ailablc fhe aqueous pohuiclhanc dispeision composition foi
leathei pieieiabh has a
ol UO k.5000 cps and moie piefeiabh 1000 to 3000 cps lυi being used as an lmpiegnatmg composition oi pieieiabh has a iscositv ol 5000 to 15000 tps and moic pieieiabh 5000 to 10000 cps loi being used as a coating composition 1 oi the conttol of the
a thickening agent commeicialh available tmch us methane
oi cellulose-based thickening agent
1 he watei lepellent as used heiem is a lluoune compound oi a silicon compound which aie commeicialh av ilable as well known to those skilled in the ait and the specific example oi the watei lepellent include Zon>l (e g 8412I oi RNI ) supplied b\
Co Scotch guaid (e g FC255 oi FC214-2301 ) supplied bv 3M Co and fefion (e g 8070 ,M oi 8787 ι l) supplied bv Dupon Co The watei lepellent enhances watei lepellent piopeih and watei lesistance and aids loimation of the cells in the svnthetic leathti thus obtained II the amount ol the watei lepellent is less than 01 pait bλ weight the svnthetic leathei obtained has a significant detenoiation oi watei lesistance and watei lepellent piopeih An excess ol the watei iepellcnt moic than 5 paits bv weight has undesnable ellects on the s nthetic leathei such as detenoiation mechanical piopeities textuie and appeaiance (eg -it easiness)
fhe emulsifier as used herein is an anionic or non-ionic emulsifier and preferably selected from the group consisting of sodium bis(2- cthylhexyl )sullbsuccinate. sodium laurylsulphate. sodium isopropyl naphthalene sulfonate. sodium bis(tridecyl)sulfosuccinate. n-octadecyldisodium sulfosuccinate. 7) oetylphenoxypoly(ethyleneoxy)ethanol, trimethylnonyloxypoly(ethyleneoxy)ethanol. nonylphenoxypoly(ethv leneoxy)ethanol. glyceryltriolate, ethylene glycol ethylene monoslearatc. sorbilanetriolate. sorbitanetristearate and mixtures thereof. The emulsifier has a function of aiding formation of cells in the coating layer in the preparation of the svnthetic leather. If the amount oi' the emulsifier is less than 0.1
10 part by weight, the cells in the synthetic leather may crash during the drying step. With an excess of the emulsifier more than 8 parts by weight, the synthetic leather has the surface with ci acks and a deterioration of the anti foaming effect when the synthetic leather being dried.
The antifoamer as used herein is a silicon-based antifoamer. preferably in
1.7 combination with lipophilic particles (e.g.. polyurea) in order to enhance the dispersability and antifoaming characteristic of the silicon oil. An example of the suitable antifoamer is an organically modified polysiloxane. which is commercially available as well known to those skilled in the art. The antifoamer prevents the formation such as small crater on the surface of synthetic leather and controls the
20 number and size of the internal cells in the synthetic leather. Less than 0.1 part by weight of the antifoamer deteriorates the antifoaming effect and makes it hard to control the number and size of the cells in the coating layer, whereas an excess of the antifoamer more than 8 parts by weight deteriorates the mechanical properties of the complete sv nthetic leather and inhibits formation of cells in the s nthetic leather, as a
result of which the softness of the synthetic leather is deteriorated.
The inorganic filler as used herein is a commercially available inorganic filler, the example of which is a powder of modified silica, titanium oxide, alumina, ferric oxide, calcium oxide or magnesium oxide w ith an average diameter of around 1 μm. 7 and mixtures thereof. An amount of the inorganic filler less than 0.1 part bv weight deteriorates the abrasion resistance and prevents formation of cells in the coating layer, whereas an excess of the inorganic filler greater than 5 parts by weight deteriorates the softness of the sv nthetic leather.
The aqueous polyurethane resin composition according to the present 10 inv ention as obtained by mixing additives including water-repellent, emulsifier. antifoamer and inorganic filler with an aqueous polyurethane dispersion is impregnated into a substrate, mechanically foamed or defoamed and then coated on the substrate. Subsequently, the coated substrate is coagulated with a coagulating solution, which is selected from the group consisting of an aqueous solution of i n various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
The mechanical foaming step is effected with a known stirring machine called "mechanical stirrcr". The defoaming step is also effected with a commercially available pressure container operating under vacuum. The mechanical stirrcr and the 0 pressure container are both well known to those skilled in the art.
The impregnation prior to the coating step and the coating of the aqueous polyurethane dispeision composition on the substrate are achieved by a known method such as dipping or glazing coating (e.g.. embossing coating), which is well known to those skilled in the art.
The coagulating solution as used herein is preferably selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof. Examples of the salts contained in the aqueous solution of salts as a coagulating solution include: (a) all general salts including sodium chloride (NaCl ). silver chloride (AgCl). silver bromide (AgBr). silver iodide (Agl), silver chromate (AgCr04). barium carbonate (BaCO,). barium fluoride (BaF;). calcium carbonate (CaCO;). mercury chloride (PbCL). magnesium carbonate (MgCO - lead chloride ( PbCL). silver nitrate (AgNO,). copper sulfate (CuS04). copper chloride (CuCL). and lead sulfate (PbSO. ; (b) sodium chloride, potassium chloride, calcium chloride, sodium sulfate and calcium sulfate. which are obtained by neutralization between a strong acid (e.g.. hydrochloric acid, sulfurie acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, etc.) and a strong base (e.g.. sodium hydroxide, potassium hydroxide, calcium hydroxide. magnesium hydroxide, ammonia, etc. ): (c) ammonium chloride, ammonium sulfate. ammonium bromide and sodium carbonate, which are obtained by neutralization between a strong acid as defined above and a weak base including almost all water soluble amines: (d) CFLCOONa. CH,CH2COONa. CH-COO and C,,H,Na. which are obtained by neutralization between a strong base as defined above and a weak acid (e.g.. fluoric acid, hydrogen sulfide. carbonic acid, sodium carbonate, carboxylic acids such as CH-CϋϋH and Cfl .CH-COOH; and (e) CH-CϋONHj and CI I-CTLCOONH j. w hich are obtained by neutralization between a weak acid and a weak base as defined above, 'fhe coagulating solution ay have a pl-1 v alue variable depending on the tv pe and amount of the salt used therein and preferably controlled
in the range from 3 to 1 1. The pl-l value of the coagulating solution can be controlled by adding an acid or base to the aqueous solution of the salt, or regulating the equivalent weight of the acid and base used in the preparation of the aqueous solution of the salt. 7 The temperature of the coagulating solution in the coagulation bath is preferably in the range of 10 to 50 °C.
Following the coagulation step, the substrate is subjected to a post-treatment including washing, drying, embossing, buffing and weight reducing to produce the complete synthetic leather, the post-treatment method being well known to those
10 skilled in the art.
The method for preparing a synthetic leather from an aqueous polyurethane dispersion according to the present invention includes the steps of: (a) preparing a coaling composition comprising 100 parts by weight of an aqueous polyurethane dispersion. 0.1 to 5 parts by weight of a water repellent. 0. 1 to 8 parts by weight of an
I ." emulsifier. 0.1 to 1 part by weight of an antifoamer. and 0. 1 to 5 parts by weight of an inorganic filler, and subjecting the coating composition to mechanical foaming or defoaming. wherein aqueous polyurethane dispersion is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group; (b) impregnating the aqueous polyurethane dispersion 0 composition into a substrate including a woven or nonwoven fabric; (c) coating the substrate obtained in step (b) with the polyurethane dispersion foamed or defoamed in step (a): (d) coagulating the coated substrate with a coagulating solution selected from the group consisting of an aqueous solution of various salts, a mixed solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and
mixtures thereof: and (e) subjecting the coagulated substrate to a post-treatment including washing, and drying, etc.
In the step (a) of preparing the coating composition, the above-described aqueous polyurethane dispersion is mixed with additives such as water repellent. emulsifier. antifoamer and inorganic filler and the mixture is subjected to a mechanical foaming or e foaming step. The foamed or defoamed coating composition is applied to the substrate taken immediately after step (b) by a known coating method and passed through a coagulation bath containing the coagulating solution in the subsequent coagulation step, allowing the polyurethane dispersion to be coagulated into a synthetic leather. The thickness of the coating is in the range of 0. 1 to 3 mm. If the thickness of the coating is less than 0. 1 mm. the leather layer of the synthetic leather is too thin to provide the properties peculiar to the leather. On the other hand, the thickness of coating greater than 3 mm deteriorates the properties of the synthetic leather. In the step (b) of preparing the substrate, the aqueous polyurethane dispersion is mixed with additives such as water repellent, emulsifier. antifoamer and inorganic filler, and the mixture is thickened with a thickening agent to have a viscosity of 500 to 5.000 cps and preferably 1.000 to 3.000 cps. The mixture is then impregnated into a woven or nonwoven fabric, which is applied to the subsequent coating step. The impregnation rate is in the range of 5 to 90% and preferably 5 to 50% based on the total weight of the woven or nonwoven fabric. An impregnation rate of less than 5%> deteriorates the mechanical properties of the synthetic leather including tensile strength and abrasion resistance, whereas an impregnation rate exceeding 90% deteriorates the softness of the svnthetic leather.
According to the present invention, the coagulation step (d) controls the shape. size and density of cells depending on the type, pl-l value and concentration of the aqueous solution of the salt to prevent formation such as small craters on the surface. which allows production of a synthetic leather with good properties such as coating property.
The coagulating solution can be an aqueous solution of any general salt including silver chloride, silver bromide, silver iodide, silver chromate. barium carbonate, barium fluoride, calcium carbonate, mercury chloride, magnesium carbonate, lead chloride, silver nitrate, copper sulfate. copper chloride and lead sulfate.
The coagulating solution can also be an aqueous solution of salts including sodium chloride, potassium chloride, calcium chloride, sodium sulfate and calcium sulfate. which are obtained by neutralization between a strong acid (e.g.. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide. nitrous acid, hypochlorous acid, etc.) and a strong base (e.g.. sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, etc.).
The coagulating solution can also be an aqueous solution of salts including ammonium chloride, ammonium sulfate. ammonium bromide and sodium carbonate, which are obtained by neutralization between a strong acid (e.g.. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, etc.) and a weak base including almost all water soluble amines.
"fhe coagulating solution can also be an aqueous solution A salts including CH.COONa. CI LCI LCOONa. CH .COOK and C,ELNa. which are obtained by
neutialization between a stiong base (e g . sodium hydioxide. potassium hydioxide. calcium h) di xide, magnesium hvdioxide. ammonia, etc.) and a weak acid (e g.. Iluoi ic acid, hvdiogen sulfide. caibo c acid, sodium carbonate, caiboxv'hc acids such as Cl-LCϋOH aiuLCI-LCELCOOH 7 I he coagulating solution can also be an aqueous solution ol salts including
CH-COONH , and CEECI-LCOONH4. which aie obtained by neutialization between a weak acid (e g . lluonc acid, hv diogen sulfide. caibomc acid, sodium caibonate. caiboxv hc acids such as CELCOOH and CH-CFLCOOH and a w eak base including almost all watei soluble amines
J O Besides, the coagulating solution can be a mixed aqueous solution obtained by adding an acid oi base to the aqueous solution oi the salt, or legulat g the equiv alent weight ol the acid and base used in the pi epaiation of the aqueous solution of the salt
In the coagulation step (cl). the salt content in the coagulating solution is piefetabh m the lange of 5 to 50 wt % and moic pieiei abh' in the lange of 20 to 40
17 vvt % fhe salt content of less than 5 wt.% causes the cells clashed din ing the diving step, vvheteas the salt content of gieatei than 50 wt.% involves a pioblem in the washing step In contiolhng the pH value of the coagulating solution with an addition of an acid oi base to the aqueous solution of the salt, the pH value is picfeiably in the lange of 3 to 1 1 and moie pieleiably in the lange of 4 to 10 Foi example, the pH
20 v alue ot the coagulating solution is m the lange ol 3 to 7 fot an anionic po methane dispeision and 7 lo 1 1 foi a cationic poh in ethane dispeision If the pH v alue of the coagulating solution is less than 3 foi the anionic polyui ethane dispei sion oi gieatei than 1 1 ioi the cationic o methane dispeision. the cells aie scatceh iuin.ed in the sv nthetic leathei
Hereinafter, the present invention will be described in detail by way of the following examples, which are not intended to limit the scope of the present invention.
Example 1
A coating composition and an impregnating composition were prepared at the composition ratio shown in fables 1 and 2.
Table 1
* Aqueous polyurethane dispersion is available from Nanopol Inc.. in Korea by the trade name NPL-5000(solicl contents 25% by weight, ion contents 3.5%/sohd by weight, anionic polyurethane emulsion).
Table 2
\queous pohuicthane dispeision is available liom Nanυpol Inc in Is-oi i bv the tiade name NPI -5200(sυhd contents 25% bv weight ion contents 18%/sohd bv weight anionic poh uiethane emulsion)
The coating composition piepaied accoid g to lable 1 was cleloamed with a piessuie containei and coated on a nonwoven labile which was pievious dipped in the lmpiegnatmg composition as piepaied accoidmg to fable 2 using a glazing coating loi an embossing piocess I he coated nonwoven iabiie was lmmeised in a coagulation bath containing a coagulating solution loi 5 minutes Heie the coagulating solution was obtained bv adding ammonia (Nil ) to 30 wt % of an aqueous solution ol phosphoiic acid and contiollcd to have a pll value ol 4 Removed liom the coagulation bath, the coated nonwoven labile was washed and dned to obtain a svnthetic leathei I 1G 1 piesents a miuostopic phologiaph showing Δn enlaiged cioss section ol the svnthetic leathei Λs is appaient horn ! 1G 1 numcious closed cells aie uniloimlv
piovided in the sv nthetic leathei and the sui face of the sv nthetic leathei become smooth
Example 2
Λ. coating composition was piepaied at the composition latio shown in I able 7
Table 3
~ Aqueous poh uiethane dispeision is available fiom Nanopol Inc in Koiea bv the tiade name NPL-5100(sohd contents 25% by weight ion contents 2 5%/sohd bv weight anionic polvui ethane emulsion)
I he coating composition piepaied accoidmg to 1 able 3 was foamed w ith a ioamei to hav e uniloi open cells and coated on a nonwov en iabiie which was dipped in the impiegnating composition piepaied m Example 1 I he coated nonwov en labnc was immei sed in a coagulation bath containing a coagulating solution loi 5 minutes I Lie the coamilatinu solution was obtained bv addmu
ammonia (NH,) to 30 wt.%) of an aqueous solution of phosphoric acid and controlled to have a pl-l value of 4. Removed from the coagulation bath, the coated nonwoven fabric was washed and dried to obtain a synthetic leather. FIG. 2 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As is apparent from FIG. 2. numerous closed cells are uniformly provided in the synthetic leather and the surface of the synthetic leather become smooth.
Example 3
An impregnating composition was prepared at the composition ratio shown in Table 4.
Table 4
* Aqueous polyurethane dispersion is available from Nanopol Inc.. in Korea by the trade name NPL-53Q0(solid contents 25% by weight, ion contents 2%/solid by weight, anionic polyurethane emulsion.
The impregnating composition prepared according to Table 4 was impregnated into a superfine nonwoven fabric for suede-like synthetic leather without a coating step, and the impregnated nonwoven fabric was heated and passed between pressure rollers to provide an impregnation rate of 45%> with respect to the nonwoven 7 fabric, "fhe impregnated nonwoven fabric was immersed in a coagulation bath containing a coagulating solution for 5 minutes. Here, the coagulating solution was obtained by adding ammonia (NH-) to 30 wt.% of an aqueous solution of phosphoric acid and controlled to have a pl-l value of 4. Removed from the coagulation bath, the coated nonwoven fabric was washed and dried to obtain a synthetic leather. FIG. 3 10 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As is apparent from FIG. 3. the polyurethane resin is uniformed distributed over the nonwoven fabric other than the surface and has a space from the fiber unit to provide sufficient softness and bulkiness to the suede-like synthetic leather for suede.
Example 4 1.7 The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 10 wt.% of an aqueous solution of sodium chloride was used as a coagulating solution. FIG. 4 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 4, the use of sodium chloride in the coagulating solution caused an increase in 0 formation of the cell-free region,
Example 5
"fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 20 wt,%> of an aqueous solution of sodium chloride was used as a coagulating solution. FIG. 5 presents a microscopic
photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 5. an increased concentration of the aqueous sodium chloride solution used as a coagulating solution caused an increase in formation of the cell-free region.
Example 6
A coating composition and an impregnating composition were prepared at the composition ratio shown in Tables 5 and 6.
Table 5
* Aqueous polyurethane dispersion is a cationic polv urethane emulsion havinu solid contents 25% bv weiuht and ion contents 10%/solid bv wciuht.
Table 6
Aqueous pohuiethane dispeision is a cationic pohuiethane emulsion havπm solid contents 25% bv wemht and ion contents 10% sohd bv weitzht
1 he coating composition piepaied accoidmg lo Iable 5 was defoamed with a deloamei and coated on a nonwoven labile which was picvioush dipped in the nnptegnating composition as piepaied accoidmg to Iable 6 using a glazing coating foi an embossing piocess The coated nonwoven labile was lmmcised in a coagulation bath containing a coagulating solution foi 5 minutes Fleie the coagulating solution was obtained bv mixing a 20% aqueous mixed solution ol nitric acid with potassium hvdioxide at the mole latio ol 1 1 Removed horn the coagulation bath the coated nonwoven fabnc was washed and dned to obtain a svnthetic leathei 1 IG 6 picsents a micioscopic photogiaph showing an enlaiged cioss section ol the svnthetic leathei As is uppaienl horn 1 IG 6 the cationic pohuiethane les emulsion is also coagulated bv the action of salt to pioduce the svnthetic leathti
Example 7
"fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 6 excepting that a 30%> aqueous mixed solution of nitric acid and potassium hydroxide at the mole ratio of 1 : 1 was used as a coagulating solution. FIG. 7 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 7. an increased concentration of the aqueous solution of the salt reduced the number of porous cells to almost zero. Example 8
The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that a 20% aqueous mixed solution of nitric acid and ammonia at the mole ratio of 1 : 1 was used as a coagulating solution.
FIG. 8 presents a microscopic photograph show ing an enlarged cross section of the sv nthetic leather. As shown in FIG. 8. the cells had a more apparent cylindrical form relative to those of Example 1 , That is. the shape of the cells can be varied depending on the type of the salt used in the coagulating solution.
Example 9
The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that a 30%o aqueous mixed solution of nitric acid and ammonia at the mole ratio of 1 : 1 was used as a coagulating solution. FIG. 9 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 9. an increased content of the salt in the coagulation solution allowed a production of the cell-free synthetic leather, "fhis demonstrates that the content of the salt is an important factor in controlling the shape of the cells.
Example 10
I he pioceduies weie peiioimed to obtain a svnthetic leathei in the same mannei as clesciibed in Example 1 excepting that a 20%> aqueous mixed solution ol phosphoiic acid and potassium hvdioxide at the mole latio ol 1 1 was used as a coagulating solution f IG 10 piesents a micioscopic photogiaph showing an enlaigcd cioss section ol the svnthetic leathei Compaied to Example 1 this example used potassium hvdioxide as a base in phosphoiic acid instead ol ammonia and showed that the shape ol the cells can be vaned depending on the tvpe of the salt I he use of potassium hvdioxide entuelv l educed the umfoimitv ol the cells but mcieased the size of the cells
Example 11
1 he pioceduies weic pcifoimecl to obtain a svnthetic leathei in the same mannei as clesciibed in Example 1 excepting that a 7()% aqueous mixed solution of phosphoiic acid and potassium hvdioxide at the mole latio ol 1 1 was used as a coagulating solution FIG 11 piesents a micioscopic photogiaph showing an enlaiged cioss section ol the s>nthetιc leathei As shown in FIG 11 an mcieased content oi the salt in the coagulating solution caused an mciease in foimation of the cell-fiee legion
Example 12 I he pioceduies wcie peiioimed to obtain a svnthetic leathei in the same mannei as clesciibed in Example 1 excepting that a 20% aqueous mixed solution ol phosphoiic acid and tiibutvlam e at the mole latio ol 1 1 was used as a coagulating solution FIG 12 piesents a micioscopic photogiaph showing an enlaiged cioss section of the svnthetic leathei Compaied to I xun.plc 1 this example used
tributylamine as a base in phosphoric acid instead of ammonia and showed that the shape of the cells can be varied depending on the type of the salt. The use of tributylamine entirely reduced the uniformity of the cells but increased the size of the cells.
Example 13
"fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that a 30%) aqueous mixed solution of phosphoric acid and tributylamine at the mole ratio of 1 : 1 w as used as a coagulating solution. FIG. 13 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. As shown in FIG. 13. an increased content of the salt in the coagulating solution caused an increase in formation of a cell-free region and reduced the thickness of the surface coating.
Example 14
"fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 10 wt.% of an aqueous sodium chloride solution was mixed with 30 wt.% of aqueous phosphoric acid solution to provide a coagulating solution having a controlled pH value of 5. FIG. 14 presents a microscopic photograph showing an enlarged cross section of the synthetic leather.
Example 15
The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 20 wt.%) of an aqueous sodium chloride solution was mixed w ith 30 wt.% of aqueous phosphoric acid solution to prov ide a coagulating solution hav ing a controlled pl-l value of 5, FIG. 15 presents a microscopic photograph show ing an enlarged cross section of the synthetic leather. In
regard to Examples 14 and 15. a decreased phi value of the coagulating solution, i.e.. acidification caused an increase in formation of the cell-free synthetic leather. Example 16
The procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 10 wt.% of an aqueous sodium chloride solution was mixed w ith 30 wt.% of aqueous potassium hydroxide solution to prov ide a coagulating solution having a controlled pH value of 10. FIG, 16 presents a microscopic photograph showing an enlarged cross section of the sv nthetic leather. Example 17
"fhe procedures were performed to obtain a .synthetic leather in the same manner as described in Example 1 excepting that 20 v\ t.° ό of an aqueous sodium chloride solution was mixed with 30 wt.% of aqueous potassium hv clroxide solution to prov ide a coagulating solution hav ing a controlled pH value of 10. FIG. 17 presents a microscopic photograph showing an enlarged cross section ol" the synthetic leather. In regard to Examples 16 and 17, an increased pFI value of the coagulating solution, i.e.. alkalization caused a sharp increase in the size of the cells. Example 18 fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 20 wt.% of an aqueous phosphoric acid solution was mixed with ammonia to provide a coagulating solution having a controlled pl l value of 4, FIG. 1 8 presents a microscopic photograph showing an enlari-ed cross section of the svnthetic leather.
Example 19
"Fhe procedures were performed to obtain a synthetic leather in the same manner as described in Example 1 excepting that 30 wt.% of an aqueous phosphoric acid solution was mixed with ammonia to provide a coagulating solution having a .7 controlled pl l value of 4. FIG. 19 presents a microscopic photograph showing an enlarged cross section of the synthetic leather. In regard to Examples 18 and 19. the use of a mixed solution of acid and base instead of the solution of salt also provided numerous and uniform cells as in Example 1.
As described in the preceding examples, the present invention provides a
10 synthetic leathers prepared in v arious forms, That is. as shown in FIGS. 1 and 2. the synthetic leather is internally prov ided with closed cells of which the size and distribution are unil rmh controllable, and thus feels smooth w ith good texture, It is also shown in FIG. 3 that the present invention provides a suede-like synthetic leather with sufficient softness and bulkiness in which the polyurethane resin is uniformly
1.7 distributed all over the nonwoven fabric other than the surface layer. As is apparent from FIGS. 4 to 1 1. the use of various coagulating solutions allows a control of the shape, size and density of cells and thereby effectively provides a synthetic leather of various qualities. According to these figures, the synthetic leather may have large- diameter cells with a very low density as well as those having a very small size. The 0 density and size of the cells have an effect mainly on the texture and softness of the synthetic leather obtained so that the present invention provides a synthetic leather of v arious properties and makes it possible to prepare a sv nthetic leather of desired properties.
Consequenlh. the present inv ention provides a en ironment-friendly method
for preparing a synthetic leather with excellent properties and high productivity, and a synthetic leather obtained thereby, "fhe invention also provides a method for effectively preparing a synthetic leather of various qualities in which the shape, size and density of cells are controllable depending on the coagulating solution.
It is to be noted that like reference numerals denote the same components in the drawings, and a detailed description of generally known function and structure of the present invention will be avoided lest it should obscure the subject matter of the present invention.
2y
Claims
1. An aqueous type polyurethane dispersion composition for a synthetic leather, comprising: 100 parts by weight of an aqueous polyurethane dispersion obtained from a polyurethane of which the main chain is covalently bonded to anionic groups including a carboxyl group or a sulfonate group, or cationic groups including a tertiary amine group:
0. 1 to 5 parts by weight of a water repellant: 0.1 to 8 parts by weight of an emulsifier:
0.1 to 1 part bv weight of an antifoamer: and 0. 1 to 5 parts bv weight of an inoiganic filler.
2. An aqueous polyurethane-based synthetic leather being characterized in that the synthetic leather is obtained by impregnating a composition comprising
100 parts by weight of aqueous polyurethane dispersion. 0.1 to 5 parts by weight of a water repellant. 0.1 to 8 parts by weight of an emulsifier. 0.1 to 1 part by weight of an antifoamer, and 0.1 to 5 parts by weight of an inorganic filler into a substrate, coating the foamed or defoamed composition on the substrate, and coagulating the coated substrate with a coagulating solution, wherein aqueous polv urethane dispersion is covalently bonded to anionic groups including carboxyl group or sulfonate group, or cationic groups including a tertiary amine group, wherein the coagulating solution is selected from the group consisting of an aqueous solution of various salts, a mixed
solution of salt and acid, a mixed solution of salt and base, a mixed solution of acid and base, and mixtures thereof.
3. The aqueous polyurethane-based synthetic leather as claimed in claim 2. ,7 wherein the water repellent is a fluorine or a silicone compound.
4. The aqueous polyurethane-based synthetic leather as claimed in claim 2. wherein the emulsifier is selected from the group consisting of sodium bis(2- methylhexyOsullbsuceinute. sodium laurylsulphate. sodium isopropyl
10 naphthalene sul fonate. sodium bis(tridecyl )sulfosuccinate. n- octadccyldisodϊum sulfosuccinate. oetylphcno.xypolyf eth leneoxv )ethanol. trimcthylnυnylox poly(ethyleπeoxy)ethanol. nonylphenoxypolyf ethv leneoxv )ethanol. glyceryltriolate. ethylene glv eol ethylene monostcarate. sorbitanetriolate. sorbitanetristearate and
1.7 mixtures thereof.
5. The aqueous polyurethane-based synthetic leather as claimed in claim 2, wherein the antifoamer is a silicon -based antifoamer.
20 6, The aqueous polyurethane-based synthetic leather as claimed in claim 2. wherein the inorganic 111 lei is a powder selected from the group consisting of powders of modified silica, titanium oxide, alumina, ferric oxide, calcium oxide or magnesium oxide with an average diameter of around 1 μm. and mixtmes thereoi.
I he aqueous polv ui ethane-based svnthetic leathei as claimed in claim 2 wheiein the coagulating solution is selected liom the gioup consisting oi an aqueous solution of vauous salts a mixed solution ol salt and acid a mixed solution oi salt and base a mixed solution ol acid and base and mixtuics theieof
\ method kv p'cpanng a s nthetic leathei bom an aqueous pohuiethane dispeision compnsmg the steps of
(a) picpaπng a coaling composition compnsmg 100 paits bv weight ol an aqueous pohuiethane dispeision 01 to -. paits bv weight ol a watei lepellent
01 to 8 paits bv weight ol an cmulsifiei 01 to 1 pail bv weight ol an antiloamci and 01 to -> paits bv weight oi an moiganic fillei and subletting the coating composition to mechanical foaming oi dtfoaimng wheiem the aqueous pohuiethane dispeision being covalcnth bonded to anionic gioups including cuiboxvl gioup oi sulfonate gioup oi cationic gioups including a teitiaiv amine gioup
(b) lmpiegnatmg the aqueous polvmethane dispeision composition into a substiale including a woven oi nonwoven fabnc
(c) coating the substiale obtained in step (b) with the aqueous pohuiethane dispeision composition foamed oi defoamed in step (a)
(d) coagulating the coated substiale with a coagulating solution selected liom the gioup consisting oi an aqueous solution ol vauous salts a mixed solution
01 salt and acid a mixed solution ol salt and base a mixed solution ol acid and
base, and mixtures thereof; and
(e) subjecting the coagulated substrate to a post-treatment including washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2001294330A AU2001294330A1 (en) | 2000-10-17 | 2001-10-12 | Synthetic leather manufacturing method using aqueous polyurethane dispersions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2000-0060903A KR100416414B1 (en) | 2000-10-17 | 2000-10-17 | Synthetic leather manufacturing method of water emulsion type polyurethane |
| KR2000/60903 | 2000-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002033001A1 true WO2002033001A1 (en) | 2002-04-25 |
Family
ID=19693820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2001/001724 WO2002033001A1 (en) | 2000-10-17 | 2001-10-12 | Synthetic leather manufacturing method using aqueous polyurethane dispersions |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100416414B1 (en) |
| AU (1) | AU2001294330A1 (en) |
| TW (1) | TW583375B (en) |
| WO (1) | WO2002033001A1 (en) |
Cited By (22)
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| WO2004061198A1 (en) * | 2002-12-20 | 2004-07-22 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
| WO2004063457A1 (en) * | 2003-01-09 | 2004-07-29 | Viktor Achter Gmbh & Co. Kg | Printed synthetic suede leather and a process for preparing the same |
| EP2045279A1 (en) * | 2007-10-05 | 2009-04-08 | Bayer MaterialScience AG | Polyurethane foams for treating wounds |
| WO2009066851A1 (en) * | 2007-11-20 | 2009-05-28 | Huh, Young-Woon | Textile coating method with water urethane emulsion |
| CN102433765A (en) * | 2011-11-09 | 2012-05-02 | 四川大学 | Method for manufacturing environment-friendly semi-polyurethane leather |
| CN102493198A (en) * | 2011-12-01 | 2012-06-13 | 浙江深蓝轻纺科技有限公司 | Bright aqueous polyurethane surface finishing agent for synthetic leather and preparation method thereof |
| CN102493199A (en) * | 2011-12-01 | 2012-06-13 | 浙江深蓝轻纺科技有限公司 | Bright aqueous polyurethane surface finishing agent for synthetic leather |
| CN102995409A (en) * | 2012-08-21 | 2013-03-27 | 江苏宝泽高分子材料股份有限公司 | Water-based particular downy sense scraper treating agent for synthetic leather and preparation method thereof |
| US20130183491A1 (en) * | 2010-07-12 | 2013-07-18 | Kuraray Co., Ltd. | Method for forming film, and film |
| US8629195B2 (en) | 2006-04-08 | 2014-01-14 | Bayer Materialscience Ag | Production of polyurethane foams |
| CN104088160A (en) * | 2014-07-06 | 2014-10-08 | 滁州惠智科技服务有限公司 | Basketball leather |
| WO2018015260A1 (en) * | 2016-07-19 | 2018-01-25 | Evonik Degussa Gmbh | Use of polyolesters for producing porous plastic coatings |
| CN107849258A (en) * | 2015-07-21 | 2018-03-27 | Dic株式会社 | The manufacture method of coagulum |
| CN111101386A (en) * | 2019-12-31 | 2020-05-05 | 合肥科天水性科技有限责任公司 | Dry-process breathable moisture-permeable bio-based clothing leather and preparation method thereof |
| EP3686340A1 (en) | 2019-01-23 | 2020-07-29 | Covestro Deutschland AG | Artificial leather and method for producing same |
| CN112661931A (en) * | 2020-12-22 | 2021-04-16 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin for filling and preparation method thereof |
| CN113417151A (en) * | 2021-07-08 | 2021-09-21 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
| WO2021210983A1 (en) * | 2020-04-17 | 2021-10-21 | Betjo Beheer B.V. | Method for the production of a microporous polymer coated fabric |
| CN113874453A (en) * | 2019-06-04 | 2021-12-31 | 陶氏环球技术有限责任公司 | Heat-sensitive aqueous polyurethane dispersion and preparation method thereof |
| CN114716725A (en) * | 2022-03-10 | 2022-07-08 | 陕西科技大学 | Preparation method of microporous hole size-adjustable polyurethane film |
| WO2023149799A1 (en) | 2022-02-03 | 2023-08-10 | Stahl International B.V. | Process for preparing a multi-layered composite suitable for making polyurethane synthetic leather |
| IT202200003428A1 (en) | 2022-02-24 | 2023-08-24 | Lamberti Spa | METHOD OF PRODUCTION OF A LEATHER MATERIAL |
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| KR100416878B1 (en) * | 2000-11-09 | 2004-02-05 | 주식회사 코켐 | Devlopment the process and the additives of wet-method using waterborne polyurethane resins |
| KR20040048229A (en) * | 2002-12-02 | 2004-06-07 | 씨엔이티 주식회사 | Manufacturing device for environment protective artificial leather |
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| KR102151960B1 (en) * | 2018-11-08 | 2020-09-04 | (주)현대식모 | Production method of environment-friendly water-repellent synthetic leather using non-fluorine water repellent agent |
| CN113840871B (en) * | 2019-06-07 | 2023-08-11 | Dic株式会社 | Urethane resin composition and laminate |
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| US4171391A (en) * | 1978-09-07 | 1979-10-16 | Wilmington Chemical Corporation | Method of preparing composite sheet material |
| KR19980014449A (en) * | 1996-08-12 | 1998-05-25 | 이일쇄 | Manufacturing method of synthetic leather using aqueous polyurethane resin |
| KR19990075812A (en) * | 1998-03-25 | 1999-10-15 | 장병주, 이일쇄 | Manufacturing method of synthetic leather using water dispersible polyurethane resin |
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| US4743470A (en) * | 1985-03-02 | 1988-05-10 | Bayer Aktiengesellschaft | Spreading pastes containing polyurethane plastics and a process for the production of polyurethane coatings permeable to water vapor |
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| JP3392017B2 (en) * | 1997-09-16 | 2003-03-31 | 株式会社クラレ | Leather-like sheet with excellent antifouling properties |
| US5916636A (en) * | 1998-03-17 | 1999-06-29 | Milliken & Company | Method of making a polyurethane suede-like fabric/elastomer composite |
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- 2001-10-12 WO PCT/KR2001/001724 patent/WO2002033001A1/en active Application Filing
- 2001-10-12 AU AU2001294330A patent/AU2001294330A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4171391A (en) * | 1978-09-07 | 1979-10-16 | Wilmington Chemical Corporation | Method of preparing composite sheet material |
| KR19980014449A (en) * | 1996-08-12 | 1998-05-25 | 이일쇄 | Manufacturing method of synthetic leather using aqueous polyurethane resin |
| KR19990075812A (en) * | 1998-03-25 | 1999-10-15 | 장병주, 이일쇄 | Manufacturing method of synthetic leather using water dispersible polyurethane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7306825B2 (en) | 2002-12-20 | 2007-12-11 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
| WO2004061198A1 (en) * | 2002-12-20 | 2004-07-22 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
| WO2004063457A1 (en) * | 2003-01-09 | 2004-07-29 | Viktor Achter Gmbh & Co. Kg | Printed synthetic suede leather and a process for preparing the same |
| US8629195B2 (en) | 2006-04-08 | 2014-01-14 | Bayer Materialscience Ag | Production of polyurethane foams |
| EP2045279A1 (en) * | 2007-10-05 | 2009-04-08 | Bayer MaterialScience AG | Polyurethane foams for treating wounds |
| WO2009046855A1 (en) * | 2007-10-05 | 2009-04-16 | Bayer Materialscience Ag | Polyurethane foams for wound treatment |
| WO2009066851A1 (en) * | 2007-11-20 | 2009-05-28 | Huh, Young-Woon | Textile coating method with water urethane emulsion |
| US20130183491A1 (en) * | 2010-07-12 | 2013-07-18 | Kuraray Co., Ltd. | Method for forming film, and film |
| CN102433765A (en) * | 2011-11-09 | 2012-05-02 | 四川大学 | Method for manufacturing environment-friendly semi-polyurethane leather |
| CN102493199A (en) * | 2011-12-01 | 2012-06-13 | 浙江深蓝轻纺科技有限公司 | Bright aqueous polyurethane surface finishing agent for synthetic leather |
| CN102493198A (en) * | 2011-12-01 | 2012-06-13 | 浙江深蓝轻纺科技有限公司 | Bright aqueous polyurethane surface finishing agent for synthetic leather and preparation method thereof |
| CN102995409A (en) * | 2012-08-21 | 2013-03-27 | 江苏宝泽高分子材料股份有限公司 | Water-based particular downy sense scraper treating agent for synthetic leather and preparation method thereof |
| CN104088160A (en) * | 2014-07-06 | 2014-10-08 | 滁州惠智科技服务有限公司 | Basketball leather |
| CN107849258A (en) * | 2015-07-21 | 2018-03-27 | Dic株式会社 | The manufacture method of coagulum |
| EP3327066A4 (en) * | 2015-07-21 | 2019-03-20 | DIC Corporation | Method for producing coagulated article |
| WO2018015260A1 (en) * | 2016-07-19 | 2018-01-25 | Evonik Degussa Gmbh | Use of polyolesters for producing porous plastic coatings |
| US11851583B2 (en) | 2016-07-19 | 2023-12-26 | Evonik Operations Gmbh | Process for producing porous polyurethane coatings using polyol ester additives |
| EP3686340A1 (en) | 2019-01-23 | 2020-07-29 | Covestro Deutschland AG | Artificial leather and method for producing same |
| WO2020152134A1 (en) | 2019-01-23 | 2020-07-30 | Covestro Intellectual Property Gmbh & Co. Kg | Synthetic leather and method for manufacturing synthetic leather |
| CN113874453A (en) * | 2019-06-04 | 2021-12-31 | 陶氏环球技术有限责任公司 | Heat-sensitive aqueous polyurethane dispersion and preparation method thereof |
| CN111101386A (en) * | 2019-12-31 | 2020-05-05 | 合肥科天水性科技有限责任公司 | Dry-process breathable moisture-permeable bio-based clothing leather and preparation method thereof |
| WO2021210983A1 (en) * | 2020-04-17 | 2021-10-21 | Betjo Beheer B.V. | Method for the production of a microporous polymer coated fabric |
| NL2025360B1 (en) * | 2020-04-17 | 2021-11-01 | Betjo Beheer B V | Method for the production of a microporous polymer coated fabric |
| CN112661931A (en) * | 2020-12-22 | 2021-04-16 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin for filling and preparation method thereof |
| CN113417151A (en) * | 2021-07-08 | 2021-09-21 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
| CN113417151B (en) * | 2021-07-08 | 2023-01-03 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
| WO2023149799A1 (en) | 2022-02-03 | 2023-08-10 | Stahl International B.V. | Process for preparing a multi-layered composite suitable for making polyurethane synthetic leather |
| NL2030817B1 (en) * | 2022-02-03 | 2023-08-11 | Stahl Int B V | Process for preparing a multi-layered composite suitable for making polyurethane synthetic leather |
| IT202200003428A1 (en) | 2022-02-24 | 2023-08-24 | Lamberti Spa | METHOD OF PRODUCTION OF A LEATHER MATERIAL |
| EP4234601A1 (en) | 2022-02-24 | 2023-08-30 | Lamberti SPA | Method of producing a leather-like material |
| CN114716725A (en) * | 2022-03-10 | 2022-07-08 | 陕西科技大学 | Preparation method of microporous hole size-adjustable polyurethane film |
| CN114716725B (en) * | 2022-03-10 | 2023-08-25 | 陕西科技大学 | Preparation method of polyurethane film with adjustable micropore size |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001294330A1 (en) | 2002-04-29 |
| TW583375B (en) | 2004-04-11 |
| KR100416414B1 (en) | 2004-01-31 |
| KR20020030320A (en) | 2002-04-25 |
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