EP0515426B1 - Method of preparing salts of sulphonated phosphoric acid esters and their use as leather-oiling agents - Google Patents
Method of preparing salts of sulphonated phosphoric acid esters and their use as leather-oiling agents Download PDFInfo
- Publication number
- EP0515426B1 EP0515426B1 EP91903401A EP91903401A EP0515426B1 EP 0515426 B1 EP0515426 B1 EP 0515426B1 EP 91903401 A EP91903401 A EP 91903401A EP 91903401 A EP91903401 A EP 91903401A EP 0515426 B1 EP0515426 B1 EP 0515426B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphoric acid
- acid esters
- alkyl
- represent
- salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 14
- 239000008041 oiling agent Substances 0.000 title claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000010985 leather Substances 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- -1 ester salts Chemical class 0.000 claims abstract description 22
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 230000002349 favourable effect Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract description 2
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- WUFSRLQSIDFFMT-UHFFFAOYSA-N oxirane;phosphoric acid Chemical compound C1CO1.OP(O)(O)=O WUFSRLQSIDFFMT-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 150000005691 triesters Chemical class 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 2
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- 241001494479 Pecora Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- MEESPVWIOBCLJW-KTKRTIGZSA-N [(z)-octadec-9-enyl] dihydrogen phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(O)=O MEESPVWIOBCLJW-KTKRTIGZSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical group CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Definitions
- the invention relates to a process for the production of leathers with favorable water behavior and the use of sulfonated phosphoric acid ester salts for the production of leathers with favorable water behavior.
- the hydrophobizing effect of the phosphoric acid alkyl esters is due to their poor emulsifiability and their low level Resistance to emulsions.
- alkyl phosphates and / or alkyl polyoxyalkylene phosphates with 12 to 14 carbon atoms in the alkyl radicals are often used in practice, which are easier to emulsify in the alkyl radicals than the corresponding phosphoric acid esters with 16 and more carbon atoms.
- none of these measures to improve the emulsifiability and the resistance to emulsion lead to satisfactory performance properties of the leather. Due to the insufficient emulsion resistance, the leather is only insufficiently greased and the result is a hard grip.
- Combinations of the phosphoric acid esters with other fatliquoring agents for example sulfonated paraffins, sulfonated fats and / or sulfonated oils, result in an improved grip, but lead to a reduction in the hydrophobizing effect.
- the object on which the invention is based was therefore to develop a method for greasing leather which gives leather a favorable water behavior combined with good usage properties, such as grip, grain resistance and / or fullness. Furthermore, the fatliquors to be developed should have good emulsifying power and high emulsion resistance.
- the subject of the invention is therefore a process for the preparation of leathers with favorable water behavior, which is characterized in that leather is obtained after the tanning, retanning or dyeing with alkali metal, amine and / or ammonium salts of sulfonated phosphoric acid esters, by reaction of phosphoric acid esters general formula I.
- the radicals R1 are an alkyl or alkenyl group with 8 to 22 C atoms and R2 and R3 are the same or different and each represent hydrogen or an alkyl or alkenyl group with 8 to 22 C atoms
- the indices m, n and p are identical or different and each represent a number between 2 and 4 and the indices x, y and z are identical or different and each represent a number from 0 to 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali metal hydroxides, ammonium hydroxide and / or Amines, greases, then, in a manner known per se, the treatment liquor containing the lubricants is adjusted to a pH of between 3.5 and 4.1 and the sulfonated phosphoric acid ester salts are fixed on and in the leather by adding chromium and / or aluminum tanning agents.
- the invention furthermore relates to the use of alkali metal, amine and / or ammonium salts of sulfonated phosphoric acid esters, obtainable by reacting phosphoric acid esters of the general formula I.
- the radicals R1 are an alkyl or alkenyl group with 8 to 22 C atoms and R2 and R3 are identical or different and each represent H or an alkyl or alkenyl group with 8 to 22 C atoms
- the indices m, n and p are identical or different and each represent a number between 2 and 4
- the indices x, y and z are identical or different and each represent a number from 0 to 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali hydroxides, ammonium hydroxide and / or amines, for the production of leathers with favorable water behavior.
- leathers with favorable water behavior are understood to mean leathers in which the passage of water through the leather cross section is significantly delayed under dynamic conditions and which absorb only small amounts of water in a certain time unit (penetrometer test according to DIN 53 338).
- the fatliquors to be used in the process according to the invention preferably contain alkali metal salts of sulfonated phosphoric acid esters and particularly preferably alkali metal salts of sulfonated phosphoric acid esters which are obtainable by reacting those phosphoric acid esters of the general formula I in which the radicals R 1 are an alkyl or alkenyl group having 12 to 18 C atoms and R2 and R3 are identical or different and each represent H or an alkyl or alkenyl group having 12 to 18 C atoms, the indices m, n and p stand for the number 2 and the indices x, y and z are identical or different and each represent a number between 0 and 10.
- the sulfonation of the phosphoric acid esters of the general formula I are carried out analogously to the processes described in DE-OS 38 02 815 and DE-OS 38 12 718, preferably at temperatures between 20 and 120 ° C, particularly preferably at temperatures between 30 and 100 ° C, for example performed with sulfuric acid, oleum, chlorosulfonic acid or SO3-containing gas mixtures.
- Gas mixtures of SO3 and air or inert gases, for example nitrogen, in which the SO3 content is between 1 and 10 vol .-%, are particularly preferred as sulfonating agents.
- the molar ratio of the double bond equivalents contained in the starting material to be used SO3 is preferably between 20 and 0.5, particularly preferably between 10 and 0.6.
- the sulfonations are carried out continuously or batchwise in conventional reactors suitable and customary for the sulfation of fatty alcohols or the sulfonation of fatty acid esters, alkylbenzenes or olefins, for example of the falling film reactor type (Kirk-Othmer: “Encyclopedia of Chemical Technology” 22 , 28 ff (1983)).
- reaction mixture After sulfonation has ended, it may be expedient to subject the reaction mixture to an aging process.
- the reaction mixture is left to stand or stirred for more than 0 to 240 minutes, particularly preferably within 1 to 30 minutes, preferably at 10 to 120 ° C., particularly preferably at 60 to 100 ° C. It is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines or with anhydrous amines by adding the reaction mixture to the aqueous solution or the anhydrous amines or the aqueous solution or the anhydrous amines to the reaction mixture.
- the optionally aged sulfonation product is preferably added to an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, 1 to 1.5 moles of hydroxides and / or amines being used per mole of sulfur trioxide added.
- Sodium hydroxide, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine and / or pyridine are preferably used for neutralization. It is particularly preferred to hydrolyze with aqueous solutions of sodium and / or potassium hydroxide.
- the concentration of the hydroxides and / or amines in the aqueous solutions is preferably chosen so that the end product forms a still flowable or pumpable aqueous solution.
- Alkali, amine and / or ammonium salts of sulfonated phosphoric acid esters are in the form of dark to light yellow solutions. If desired, these solutions can be bleached with hydrogen peroxide solution or alkali hypochlorite solution (chlorine solution) in a manner known per se at 40 to 55 ° C.
- the phosphoric esters of the general formula I required for the preparation of sulfonated phosphoric acid ester salts are obtainable by processes known from the literature. Their production is based on alkyl and / or alkenyl alcohols with 8 to 22 carbon atoms, for example octyl, decyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl and / or behenyl alcohol. Alkyl and / or alkenyl alcohols having 12 to 18 carbon atoms are preferably used.
- the alkoxylations of saturated and / or unsaturated alcohols with ethylene oxide, propylene oxide and / or butylene oxide, preferably with ethylene oxide, are carried out by known industrial processes ("Chemical Technology", Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Kunststoff-Vienna ( 1986)).
- the average degree of alkoxylation x, y or z of the mixtures of homologous alkoxylates obtained corresponds to the molar amount of the alkylene oxides attached and is preferably between 0 and 10.
- the phosphating of optionally alkoxylated alkyl and / or alkenyl alcohols is carried out in a manner known per se ("Chemische Technologie", Volume 7, page 123 ff, Carl-Hanser-Verlag, Kunststoff-Vienna (1986)), in which the alcohols contain phosphorus pentoxide or Polyphosphoric acid are implemented. In these processes, mixtures of phosphoric acid mono-, di- and triesters are formed. When using water entraining agents, such ester mixtures can also be obtained directly using orthophosphoric acid.
- reaction conditions above 160 ° C this does not involve conventional esterification, but primarily the formation of di- and polyphosphoric acid, which react in a known manner with alcohols and / or alcohol polyoxyalkylene ethers.
- the optionally alkoxylated alcohols can be reacted with phosphorus oxychloride to produce high-purity phosphoric acid mono-, di- and triesters.
- Sulfonated Phosphor yarnestersalze can be used alone or in combination with other oiling agents, for example mineral oils, paraffins and / or silicones, preferably soap-forming in emulsified form, with polyvalent metal ions emulsifiers, such as fatty acid sarcosides, partial esters of polybasic carboxylic acids such as Monooleylzitronen Textreestern, Alkenylbernstein Textreestern and / or sulfited fats and / or Oils are used.
- the weight ratio of sulfonated phosphoric acid ester salts to other fatliquoring agents is preferably between 0.1 and 9.
- the fatliquoring agents according to the invention are used in amounts of preferably 1 to 20% by weight, particularly preferably 2 to 14% by weight, in each case based on the shaved weight of the leather - used.
- the process according to the invention for the production of leathers with favorable water behavior is carried out in such a way that the sulfonated phosphoric acid ester salts are used as a licker, if appropriate in combination with other fatliquoring agents following tanning or retanning and optionally coloring and after removal of excess tanning agents by washing .
- the temperatures during the greasing are typically between 30 and 50 ° C.
- the pH of the liquor liquor is adjusted to 3.5 to 4.1, preferably to 3.8 to 4.0, using acids, preferably formic acid, acetic acid and / or sulfuric acid.
- the liquor based on the shaved weight, is 2 to 6% by weight of chromium and / or aluminum tanning agents added to fix the salts of the sulfonated phosphoric acid esters by forming the appropriate chromium and / or aluminum soaps. Then work continues in a manner known per se.
- the sulfonated phosphoric acid ester salts to be used according to the invention have good emulsifying power and high emulsion resistance.
- All types of leather for example cowhide leather, pig leather or sheep leather, can be treated with the fatliquoring agents according to the invention.
- the leathers treated with the fatliquoring agents according to the invention show better leather properties, in particular a better grip and better grain resistance, as well as a significantly improved impregnation effect due to a delayed water penetration and a lower water absorption.
- the greasing was carried out with one of the following greasing agents:
- the following table contains the tests carried out on the leathers treated with the various greasing agents specified above and the test results.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Ledern mit günstigem Wasserverhalten sowie die Verwendung von sulfonierten Phosphorsäureestersalzen zur Herstellung von Ledern mit günstigem Wasserverhalten.The invention relates to a process for the production of leathers with favorable water behavior and the use of sulfonated phosphoric acid ester salts for the production of leathers with favorable water behavior.
Es ist bekannt, zur Herstellung wasserdichter Leder diese im Anschluß an die Nachgerbung und gegebenenfalls Färbung mit Phosphorsäurealkylestern in Form ihrer Alkali- oder Ammoniumsalze zu fetten ("Leder- und Häutemarkt" 38, 5 (1986)). Um eine möglichst vollständige Flottenauszehrung zu erzielen, wird die Flotte gegen Ende der Fettung mit Säuren, beispielsweise Ameisensäure, auf einen pH-Wert zwischen 3,8 und 4,0 eingestellt. Anschließend wird mit Chrom- und/oder Aluminiumgerbstoffen fixiert, d.h., die Phosphorsäurealkylestersalze werden in die entsprechenden Chrom- und/oder Aluminiumseifen überführt.It is known for the production of waterproof leather to be greased after the retanning and optionally dyeing with phosphoric acid alkyl esters in the form of their alkali metal or ammonium salts ("Leather and Skin Market" 38 , 5 (1986)). In order to achieve as complete a liquor consumption as possible, the liquor is adjusted to a pH between 3.8 and 4.0 towards the end of the greasing with acids, for example formic acid. It is then fixed with chrome and / or aluminum tanning agents, ie the phosphoric acid alkyl ester salts are converted into the corresponding chrome and / or aluminum soaps.
Der hydrophobierenden Wirkung der Phosphorsäurealkylester steht jedoch deren schlechte Emulgierbarkeit und deren geringe Emulsionsbeständigkeit gegenüber. Um diese Nachteile aufzuheben, werden in der Praxis häufig Alkylphosphate und/oder Alkylpolyoxyalkylenphosphate mit 12 bis 14 C-Atomen in den Alkylresten eingesetzt, die im Vergleich zu den entsprechenden Phosphorsäureestern mit 16 und mehr C-Atomen in den Alkylresten leichter zu emulgieren sind. Zur Verbesserung der geringen Emulsionsbeständigkeit, insbesondere bei niedrigen pH-Werten, besteht ferner die Möglichkeit, die Fettung bei pH-Werten größer 5 durchzuführen. Keine dieser Maßnahmen zur Verbesserung der Emulgierbarkeit sowie der Emulsionsbeständigkeit führt jedoch zu befriedigenden Gebrauchseigenschaften der Leder. Bedingt durch die zu geringen Emulsionsbeständigkeiten wird das Leder nur ungenügend durchfettet, und es resultiert ein harter Griff.However, the hydrophobizing effect of the phosphoric acid alkyl esters is due to their poor emulsifiability and their low level Resistance to emulsions. In order to overcome these disadvantages, alkyl phosphates and / or alkyl polyoxyalkylene phosphates with 12 to 14 carbon atoms in the alkyl radicals are often used in practice, which are easier to emulsify in the alkyl radicals than the corresponding phosphoric acid esters with 16 and more carbon atoms. To improve the low emulsion resistance, especially at low pH values, there is also the possibility of carrying out the greasing at pH values greater than 5. However, none of these measures to improve the emulsifiability and the resistance to emulsion lead to satisfactory performance properties of the leather. Due to the insufficient emulsion resistance, the leather is only insufficiently greased and the result is a hard grip.
Kombinationen der Phosphorsäureester mit anderen Fettungsmitteln, beispielsweise sulfierten Paraffinen, sulfierten Fetten und/oder sulfierten Ölen, ergeben zwar einen verbesserten Griff, führen jedoch zu einer Reduzierung des Hydrophobierungseffektes.Combinations of the phosphoric acid esters with other fatliquoring agents, for example sulfonated paraffins, sulfonated fats and / or sulfonated oils, result in an improved grip, but lead to a reduction in the hydrophobizing effect.
Die der Erfindung zugrundeliegende Aufgabe, bestand daher in der Entwicklung eines Verfahrens zur Fettung von Leder, das Ledern ein günstiges Wasserverhalten kombiniert mit guten Gebrauchseigenschaften, wie Griff, Narbenfestigkeit und/oder Fülle, verleiht. Des weiteren sollen die zu entwickelnden Fettungsmittel ein gutes Emulgiervermögen sowie eine hohe Emulsionsbeständigkeit besitzen.The object on which the invention is based was therefore to develop a method for greasing leather which gives leather a favorable water behavior combined with good usage properties, such as grip, grain resistance and / or fullness. Furthermore, the fatliquors to be developed should have good emulsifying power and high emulsion resistance.
Es wurde nun gefunden, daß die an Fettungsmittel gestellten hohen Anforderungen von sulfonierten Phosphorsäureestersalzen erfüllt werden.It has now been found that the high demands placed on fatliquoring agents are met by sulfonated phosphoric acid ester salts.
Erfindungsgegenstand ist daher ein Verfahren zur Herstellung von Ledern mit günstigem Wasserverhalten, welches dadurch gekennzeichnet ist, daß man Leder im Anschluß an die Gerbung, Nachgerbung oder Färbung mit Alkali-, Amin- und/oder Ammoniumsalzen von sulfonierten Phosphorsäureestern, erhältlich durch Umsetzung von Phosphorsäureestern der allgemeinen Formel I
in der die Reste R¹ eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen und R² und R³ gleich oder verschieden sind und jeweils Wasserstoff oder eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen bedeuten, die Indices m, n und p gleich oder verschieden sind und jeweils eine Zahl zwischen 2 und 4 darstellen und die Indices x, y und z gleich oder verschieden sind und jeweils eine Zahl von 0 bis 30 bedeuten, mit Sulfonierungsmitteln und anschließende Hydrolyse der erhaltenen Produkte mit Alkalihydroxiden, Ammoniumhydroxid und/oder Aminen,
fettet, anschließend in an sich bekannter Weise die die Fettungsmittel enthaltende Behandlungsflotte mit Säuren auf einen pH-Wert zwischen 3,5 und 4,1 einstellt und durch Zugabe von Chrom- und/oder Aluminiumgerbstoffen die sulfonierten Phosphorsäureestersalze am und im Leder fixiert.The subject of the invention is therefore a process for the preparation of leathers with favorable water behavior, which is characterized in that leather is obtained after the tanning, retanning or dyeing with alkali metal, amine and / or ammonium salts of sulfonated phosphoric acid esters, by reaction of phosphoric acid esters general formula I.
in which the radicals R¹ are an alkyl or alkenyl group with 8 to 22 C atoms and R² and R³ are the same or different and each represent hydrogen or an alkyl or alkenyl group with 8 to 22 C atoms, the indices m, n and p are identical or different and each represent a number between 2 and 4 and the indices x, y and z are identical or different and each represent a number from 0 to 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali metal hydroxides, ammonium hydroxide and / or Amines,
greases, then, in a manner known per se, the treatment liquor containing the lubricants is adjusted to a pH of between 3.5 and 4.1 and the sulfonated phosphoric acid ester salts are fixed on and in the leather by adding chromium and / or aluminum tanning agents.
Ferner ist Erfindungsgegenstand die Verwendung von Alkali-, Amin- und/oder Ammoniumsalzen sulfonierter Phosphorsäureester, erhältlich durch Umsetzung von Phosphorsäureestern der allgemeinen Formel I
in der die Reste R¹ eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen und R² und R³ gleich oder verschieden sind und jeweils H oder eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen bedeuten, die Indices m, n und p gleich oder verschieden sind und jeweils eine Zahl zwischen 2 und 4 darstellen und die Indices x, y und z gleich oder verschieden sind und jeweils eine Zahl von 0 bis 30 bedeuten, mit Sulfonierungsmitteln und anschließende Hydrolyse der erhaltenen Produkte mit Alkalihydroxiden, Ammoniumhydroxid und/oder Aminen,
zur Herstellung von Ledern mit günstigem Wasserverhalten.The invention furthermore relates to the use of alkali metal, amine and / or ammonium salts of sulfonated phosphoric acid esters, obtainable by reacting phosphoric acid esters of the general formula I.
in which the radicals R¹ are an alkyl or alkenyl group with 8 to 22 C atoms and R² and R³ are identical or different and each represent H or an alkyl or alkenyl group with 8 to 22 C atoms, the indices m, n and p are identical or different and each represent a number between 2 and 4 and the indices x, y and z are identical or different and each represent a number from 0 to 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali hydroxides, ammonium hydroxide and / or amines,
for the production of leathers with favorable water behavior.
Unter Ledern mit günstigem Wasserverhalten werden Leder verstanden, bei denen der Wasserdurchtritt durch den Lederquerschnitt unter dynamischen Bedingungen deutlich verzögert ist und die in einer bestimmten Zeiteinheit nur geringe Wassermengen aufnehmen (Penetrometerprüfung nach DIN 53 338).Leathers with favorable water behavior are understood to mean leathers in which the passage of water through the leather cross section is significantly delayed under dynamic conditions and which absorb only small amounts of water in a certain time unit (penetrometer test according to DIN 53 338).
Die beim erfindungsgemäßen Verfahren einzusetzenden Fettungsmittel enthalten bevorzugt Alkalisalze von sulfonierten Phosphorsäureestern und besonders bevorzugt Alkalisalze von sulfonierten Phosphorsäureestern, die durch Umsetzung von solchen Phosphorsäureestern der allgemeinen Formel I zugänglich sind, in der die Reste R¹ eine Alkyl- oder Alkenylgruppe mit 12 bis 18 C-Atomen und R² und R³ gleich oder verschieden sind und jeweils H oder eine Alkyl- oder Alkenylgruppe mit 12 bis 18 C-Atomen bedeuten, die Indices m, n und p für die Zahl 2 stehen und die Indices x, y und z gleich oder verschieden sind und jeweils eine Zahl zwischen 0 und 10 bedeuten.The fatliquors to be used in the process according to the invention preferably contain alkali metal salts of sulfonated phosphoric acid esters and particularly preferably alkali metal salts of sulfonated phosphoric acid esters which are obtainable by reacting those phosphoric acid esters of the general formula I in which the radicals R 1 are an alkyl or alkenyl group having 12 to 18 C atoms and R² and R³ are identical or different and each represent H or an alkyl or alkenyl group having 12 to 18 C atoms, the indices m, n and p stand for the number 2 and the indices x, y and z are identical or different and each represent a number between 0 and 10.
Die Sulfonierung der Phosphorsäureester der allgemeinen Formel I werden analog den in DE-OS 38 02 815 und DE-OS 38 12 718 beschriebenen Verfahren, vorzugsweise bei Temperaturen zwischen 20 und 120 °C, besonders bevorzugt bei Temperaturen zwischen 30 und 100 °C, beispielsweise mit Schwefelsäure, Oleum, Chlorsulfonsäure oder SO₃-haltigen Gasgemischen durchgeführt. Gasgemische aus SO₃ und Luft oder Inertgasen, beispielsweise Stickstoff, in denen der SO₃-Gehalt zwischen 1 und 10 Vol.-% liegt, werden als Sulfonierungsmittel besonders bevorzugt. Das molare Verhältnis der im Edukt enthaltenen Doppelbindungsäquivalente zu einzusetzendem SO₃ liegt vorzugsweise zwischen 20 und 0,5, besonders bevorzugt zwischen 10 und 0,6.The sulfonation of the phosphoric acid esters of the general formula I are carried out analogously to the processes described in DE-OS 38 02 815 and DE-OS 38 12 718, preferably at temperatures between 20 and 120 ° C, particularly preferably at temperatures between 30 and 100 ° C, for example performed with sulfuric acid, oleum, chlorosulfonic acid or SO₃-containing gas mixtures. Gas mixtures of SO₃ and air or inert gases, for example nitrogen, in which the SO₃ content is between 1 and 10 vol .-%, are particularly preferred as sulfonating agents. The molar ratio of the double bond equivalents contained in the starting material to be used SO₃ is preferably between 20 and 0.5, particularly preferably between 10 and 0.6.
Die Sulfonierungen werden in üblichen, für die Sulfatierung von Fettalkoholen oder die Sulfonierung von Fettsäureestern, Alkylbenzolen oder Olefinen geeigneten und gebräuchlichen Reaktoren, beispielsweise vom Typ des Fallfilmreaktors, kontinuierlich oder diskontinuierlich durchgeführt (Kirk-Othmer: "Encyclopedia of Chemical Technology" 22, 28 ff (1983)).The sulfonations are carried out continuously or batchwise in conventional reactors suitable and customary for the sulfation of fatty alcohols or the sulfonation of fatty acid esters, alkylbenzenes or olefins, for example of the falling film reactor type (Kirk-Othmer: “Encyclopedia of Chemical Technology” 22 , 28 ff (1983)).
Nach beendeter Sulfonierung kann es zweckmäßig sein, das Reaktionsgemisch einem Alterungsprozeß zu unterwerfen. Zu diesem Zweck wird das Reaktionsgemisch in größer 0 bis 240 Minuten, besonders bevorzugt innerhalb von 1 bis 30 Minuten, vorzugsweise bei 10 bis 120 °C, besonders bevorzugt bei 60 bis 100 °C, stehen gelassen oder gerührt. Anschließend wird mit einer wäßrigen Lösung aus Alkalihydroxiden, Ammoniumhydroxid und/oder Aminen oder mit wasserfreien Aminen hydrolysiert, in dem das Reaktionsgemisch zu der wäßrigen Lösung oder den wasserfreien Aminen gegeben wird oder die wäßrige Lösung oder die wasserfreien Amine zu dem Reaktionsgemisch. Vorzugsweise wird das gegebenenfalls gealterte Sulfonierungsprodukt zu einer wäßrigen Lösung aus Alkalihydroxiden, Ammoniumhydroxid und/oder Aminen gegeben, wobei pro Mol angelagertem Schwefeltrioxid 1 bis 1,5 Mol Hydroxide und/oder Amine eingesetzt werden. Natriumhydroxid, Kaliumhydroxid, Ammoniumhydroxid, Diethanolamin, Triethanolamin und/oder Pyridin werden bevorzugt zur Neutralisation eingesetzt. Besonders bevorzugt wird mit wäßrigen Lösungen von Natrium- und/oder Kaliumhydroxid hydrolysiert. Die Konzentration der Hydroxide und/oder Amine in den wäßrigen Lösungen wird vorzugsweise so gewählt, daß das Endprodukt eine noch fließfähige oder pumpbare wäßrige Lösung bildet.After sulfonation has ended, it may be expedient to subject the reaction mixture to an aging process. For this purpose, the reaction mixture is left to stand or stirred for more than 0 to 240 minutes, particularly preferably within 1 to 30 minutes, preferably at 10 to 120 ° C., particularly preferably at 60 to 100 ° C. It is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines or with anhydrous amines by adding the reaction mixture to the aqueous solution or the anhydrous amines or the aqueous solution or the anhydrous amines to the reaction mixture. The optionally aged sulfonation product is preferably added to an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, 1 to 1.5 moles of hydroxides and / or amines being used per mole of sulfur trioxide added. Sodium hydroxide, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine and / or pyridine are preferably used for neutralization. It is particularly preferred to hydrolyze with aqueous solutions of sodium and / or potassium hydroxide. The concentration of the hydroxides and / or amines in the aqueous solutions is preferably chosen so that the end product forms a still flowable or pumpable aqueous solution.
Alkali-, Amin- und/oder Ammoniumsalze von sulfonierten Phosphorsäureestern liegen in Form dunkler bis hellgelber Lösungen vor. Gewünschtenfalls können diese Lösungen mit Wasserstoffperoxidlösung oder Alkalihypochloritlösung (Chlorlauge) in an sich bekannter Weise bei 40 bis 55 °C gebleicht werden.Alkali, amine and / or ammonium salts of sulfonated phosphoric acid esters are in the form of dark to light yellow solutions. If desired, these solutions can be bleached with hydrogen peroxide solution or alkali hypochlorite solution (chlorine solution) in a manner known per se at 40 to 55 ° C.
Die zur Herstellung sulfonierter Phosphorsäureestersalze benötigten Phosphorsäureester der allgemeinen Formel I sind nach literaturbekannten Verfahren zugänglich. Ihre Herstellung geht von Alkyl- und/oder Alkenylalkoholen mit 8 bis 22 C-Atomen, beispielsweise Octyl-, Decyl-, Lauryl-, Myristyl-, Cetyl-, Palmitoleyl-, Stearyl-, Oleyl- und/oder Behenylalkohol, aus. Vorzugsweise werden Alkyl- und/oder Alkenylalkohole mit 12 bis 18 C-Atomen eingesetzt.The phosphoric esters of the general formula I required for the preparation of sulfonated phosphoric acid ester salts are obtainable by processes known from the literature. Their production is based on alkyl and / or alkenyl alcohols with 8 to 22 carbon atoms, for example octyl, decyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl and / or behenyl alcohol. Alkyl and / or alkenyl alcohols having 12 to 18 carbon atoms are preferably used.
Die Alkoxylierungen gesättigter und/oder ungesättigter Alkohole mit Ethylenoxid, Propylenoxid und/oder Butylenoxid, vorzugsweise mit Ethylenoxid werden nach bekannten großtechnischen Verfahren durchgeführt ("Chemische Technologie", Band 7, Seite 131 bis 132, Carl-Hanser-Verlag, München-Wien (1986)). Der mittlere Alkoxylierungsgrad x, y oder z der erhaltenen Gemische homologer Alkoxylate entspricht der molaren Menge der angelagerten Alkylenoxide und liegt vorzugsweise zwischen 0 und 10.The alkoxylations of saturated and / or unsaturated alcohols with ethylene oxide, propylene oxide and / or butylene oxide, preferably with ethylene oxide, are carried out by known industrial processes ("Chemical Technology", Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Munich-Vienna ( 1986)). The average degree of alkoxylation x, y or z of the mixtures of homologous alkoxylates obtained corresponds to the molar amount of the alkylene oxides attached and is preferably between 0 and 10.
Die Phosphatierung gegebenenfalls alkoxylierter Alkyl- und/oder Alkenylalkohole erfolgt in an sich bekannter Weise ("Chemische Technologie", Band 7, Seite 123 ff, Carl-Hanser-Verlag, München-Wien (1986)), in dem die Alkohole mit Phosphorpentoxid oder Polyphosphorsäure umgesetzt werden. Bei diesen Verfahren werden Gemische aus Phosphorsäuremono-, -di- und -triestern gebildet. Unter Einsatz von Wasserschleppmitteln lassen sich solche Estergemische auch direkt unter Verwendung von Orthophosphorsäure erhalten. Bei Reaktionsbedingungen oberhalb von 160 °C findet hierbei jedoch keine klassische Veresterung, sondern primär die Bildung von Di- und Polyphosphorsäure statt, die in bekannter Weise mit Alkoholen und/oder Alkoholpolyoxyalkylenethern reagieren. Zur Herstellung von hochreinen Phosphorsäuremono-, -di- und -triestern können die gegebenenfalls alkoxylierten Alkohole mit Phosphoroxychlorid umgesetzt werden.The phosphating of optionally alkoxylated alkyl and / or alkenyl alcohols is carried out in a manner known per se ("Chemische Technologie", Volume 7, page 123 ff, Carl-Hanser-Verlag, Munich-Vienna (1986)), in which the alcohols contain phosphorus pentoxide or Polyphosphoric acid are implemented. In these processes, mixtures of phosphoric acid mono-, di- and triesters are formed. When using water entraining agents, such ester mixtures can also be obtained directly using orthophosphoric acid. At reaction conditions above 160 ° C however, this does not involve conventional esterification, but primarily the formation of di- and polyphosphoric acid, which react in a known manner with alcohols and / or alcohol polyoxyalkylene ethers. The optionally alkoxylated alcohols can be reacted with phosphorus oxychloride to produce high-purity phosphoric acid mono-, di- and triesters.
Sulfonierte Phosphorsäureestersalze können alleine oder in Kombination mit anderen Fettungsmitteln, beispielsweise Mineralölen, Paraffinen und/oder Silikonen, vorzugsweise in emulgierter Form, mit mehrwertigen Metallionen seifenbildenden Emulgatoren, wie Fettsäuresarkosiden, Partialestern mehrbasischer Carbonsäuren, wie Monooleylzitronensäureestern, Alkenylbernsteinsäureestern und/oder sulfitierten Fetten und/oder Ölen eingesetzt werden. Das Gewichtsverhältnis von sulfonierten Phosphorsäureestersalzen zu anderen Fettungsmitteln liegt vorzugsweise zwischen 0,1 und 9. Die erfindungsgemäßen Fettungsmittel werden in Mengen von vorzugsweise 1 bis 20 Gew.-%, besonders bevorzugt von 2 bis 14 Gew.-% - jeweils bezogen auf Falzgewicht der Leder - eingesetzt.Sulfonated Phosphorsäureestersalze can be used alone or in combination with other oiling agents, for example mineral oils, paraffins and / or silicones, preferably soap-forming in emulsified form, with polyvalent metal ions emulsifiers, such as fatty acid sarcosides, partial esters of polybasic carboxylic acids such as Monooleylzitronensäureestern, Alkenylbernsteinsäureestern and / or sulfited fats and / or Oils are used. The weight ratio of sulfonated phosphoric acid ester salts to other fatliquoring agents is preferably between 0.1 and 9. The fatliquoring agents according to the invention are used in amounts of preferably 1 to 20% by weight, particularly preferably 2 to 14% by weight, in each case based on the shaved weight of the leather - used.
Das erfindungsgemäße Verfahren zur Herstellung von Ledern mit günstigem Wasserverhalten wird in der Weise durchgeführt, daß die sulfonierten Phosphorsäureestersalze gegebenenfalls in Kombination mit anderen Fettungsmitteln im Anschluß an die Gerbung oder Nachgerbung und gegebenenfalls Färbung und nach der Entfernung von überschüssigen Gerbmitteln durch Waschen, als Licker angewendet werden. Die Temperaturen während der Fettung liegen typischerweise zwischen 30 und 50 °C. Gegen Ende der Fettung wird der pH-Wert der Lickerflotte mit Säuren, vorzugsweise mit Ameisensäure, Essigsäure und/oder Schwefelsäure, auf 3,5 bis 4,1, vorzugsweise auf 3,8 bis 4,0 eingestellt. Anschließend werden der Flotte, bezogen auf Falzgewicht, 2 bis 6 Gew.-% Chrom- und/oder Aluminiumgerbstoffe zugesetzt, um die Salze der sulfonierten Phosphorsäureester durch Bildung der entsprechenden Chrom- und/oder Aluminiumseifen zu fixieren. Danach wird in an sich bekannter Weise weiter gearbeitet.The process according to the invention for the production of leathers with favorable water behavior is carried out in such a way that the sulfonated phosphoric acid ester salts are used as a licker, if appropriate in combination with other fatliquoring agents following tanning or retanning and optionally coloring and after removal of excess tanning agents by washing . The temperatures during the greasing are typically between 30 and 50 ° C. Towards the end of the lubrication, the pH of the liquor liquor is adjusted to 3.5 to 4.1, preferably to 3.8 to 4.0, using acids, preferably formic acid, acetic acid and / or sulfuric acid. Then the liquor, based on the shaved weight, is 2 to 6% by weight of chromium and / or aluminum tanning agents added to fix the salts of the sulfonated phosphoric acid esters by forming the appropriate chromium and / or aluminum soaps. Then work continues in a manner known per se.
Die erfindungsgemäß einzusetzenden sulfonierten Phosphorsäureestersalze besitzen ein gutes Emulgiervermögen und eine hohe Emulsionsbeständigkeit. Mit den erfindungsgemäßen Fettungsmitteln lassen sich alle Lederarten, beispielsweise Rindsleder, Schweineleder oder Schafsleder, behandeln. Die mit den erfindungsgemäßen Fettungsmitteln behandelten Leder zeigen im Vergleich zu mit Phosphorsäureestern behandelten Ledern bessere ledertechnische Eigenschaften, insbesondere einen besseren Griff und eine bessere Narbenfestigkeit, sowie aufgrund eines verzögerten Wasserdurchtritts und einer geringeren Wasseraufnahme eine deutlich verbesserte Imprägnierwirkung.The sulfonated phosphoric acid ester salts to be used according to the invention have good emulsifying power and high emulsion resistance. All types of leather, for example cowhide leather, pig leather or sheep leather, can be treated with the fatliquoring agents according to the invention. Compared to leathers treated with phosphoric acid esters, the leathers treated with the fatliquoring agents according to the invention show better leather properties, in particular a better grip and better grain resistance, as well as a significantly improved impregnation effect due to a delayed water penetration and a lower water absorption.
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1. Herstellung von sulfoniertem Oleylalkoholphosphat, Kaliumsalz
In einem mit Rührer und Thermometer versehenen 1-l-Dreihalskolben, der 420 g (1,5 Mol) technischen Oleylalkohol (HD-OcenolR 80/85: Jodzahl 89, OH-Zahl 205) enthielt, wurden bei einer Temperatur von 60 bis 70 °C mit Hilfe eines gegen Luftfeuchtigkeit geschützten Pulverdosiergerätes innerhalb von 2 Stunden 71 g (0,5 Mol) Phosphorpentoxid gegeben. Nach einer Reaktionszeit von 2 Stunden wurden bei 70 °C 10 ml Wasser zugegeben und weitere 3 Stunden bei 90 °C gerührt.
Es wurden 490 g eines dunkelfarbigen Öls erhalten, das folgende Kenndaten besaß:
Monoester 43,3 Gew.-%
Diester 38,4 Gew.-%
Triester 3,4 Gew.-%
H₃PO₄ 1,7 Gew.-%
freier Alkohol 13,0 Gew.-%
H₂O (nach Fischer) 0,15 Gew.-%
Jodzahl 74
mittleres Molekulargewicht 451
Doppelbindungsäquivalente pro Mol Phosphat 1,3
225 g (0,5 Mol) des erhaltenen Oleylphosphates wurden in einen 1-l-Sulfierkolben, versehen mit einem mechanischen Rührer, einem Gaseinleitungsrohr und Mantelkühlung, gegeben und bei 35 °C mit 68 g (0,85 Mol) SO₃, entsprechend einem auf die Doppelbindungsäquivalente bezogenen 30 %igem Überschuß, umgesetzt. SO₃ wurde durch Erhitzen aus einer entsprechenden Menge 65 gew.-%igem Oleum ausgetrieben, mit Stickstoff auf eine Konzentration von 5 Vol.-% verdünnt und bei einer Temperatur von 50 °C innerhalb von 31 Minuten in den Phosphorsäureester eingeleitet. Nach der Sulfonierung wurde das Reaktionsgemisch in eine verdünnte Lösung von 56 g (1 Mol) Kaliumhydroxid in 700 ml Wasser eingerührt und eine Stunde auf dem Dampfbad bei 95 °C erhitzt. Nach dem Abkühlen auf 20 °C wurde der pH-Wert des Reaktionsgemisches durch Zugabe von HCl-Lösung auf 7,5 eingestellt.
Kenndaten des sulfonierten Oleylalkoholphosphates, Kaliumsalz:
Aniontensid (DGF-H-III-10): 16 Gew.-% = 0,28 mEq/g
unsulfierte Anteile (DGF-G-III-6b): 1 Gew.-%
Kaliumsulfat: 1 Gew.-%
Kaliumphosphat: < 1 Gew.-%
Wasser (nach Fischer): 82 Gew.-%
mittleres Molekulargewicht: 560 1. Preparation of sulfonated oleyl alcohol phosphate, potassium salt
In a 1 liter three-necked flask equipped with a stirrer and thermometer and containing 420 g (1.5 mol) of technical oleyl alcohol (HD-Ocenol R 80/85: iodine number 89, OH number 205) were at a temperature of 60 to 70 ° C with the help of a powder dosing device protected against atmospheric humidity within 2 hours 71 g (0.5 mol) of phosphorus pentoxide. After a reaction time of 2 hours, 10 ml of water were added at 70 ° C. and the mixture was stirred at 90 ° C. for a further 3 hours.
490 g of a dark-colored oil were obtained, which had the following characteristics:
Monoester 43.3% by weight
Diester 38.4% by weight
Triester 3.4% by weight
H₃PO₄ 1.7% by weight
free alcohol 13.0% by weight
H₂O (according to Fischer) 0.15% by weight
Iodine number 74
average molecular weight 451
Double bond equivalents per mole of phosphate 1.3
225 g (0.5 mol) of the oleyl phosphate obtained were placed in a 1 liter sulfonation flask provided with a mechanical stirrer, a gas inlet tube and jacket cooling and at 35 ° C. with 68 g (0.85 mol) SO₃, corresponding to one based on the double bond equivalents 30% excess. SO₃ was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 5% by volume with nitrogen and introduced into the phosphoric acid ester at a temperature of 50 ° C. within 31 minutes. After sulfonation, the reaction mixture was stirred into a dilute solution of 56 g (1 mol) of potassium hydroxide in 700 ml of water and heated on a steam bath at 95 ° C. for one hour. After cooling to 20 ° C., the pH of the reaction mixture was adjusted to 7.5 by adding HCl solution.
Characteristics of the sulfonated oleyl alcohol phosphate, potassium salt:
Anionic surfactant (DGF-H-III-10): 16% by weight = 0.28 mEq / g
unsulphated components (DGF-G-III-6b): 1% by weight
Potassium sulfate: 1% by weight
Potassium phosphate: <1% by weight
Water (according to Fischer): 82% by weight
average molecular weight: 560 -
2. Herstellung von sulfoniertem Oleylalkohol-0,5 Mol Ethylenoxid-Phosphat, Kaliumsalz
Analog Beispiel 1 wurden 1,5 Mol Oleylalkohol-0,5 Mol Ethylenoxid mit 0,5 Mol Phosphorpentoxid umgesetzt. Der erhaltene Phosphorsäureester hatte ein mittleres Molekulargewicht von 478 und 1,3 Doppelbindungsäquivalente pro Mol Phosphat.
Die Sulfonierung von 240 g (0,5 Mol) Oleyl-0,5 Mol Ethylenoxid-Phosphat wurde analog Beispiel 1 durchgeführt. Das erhaltene sulfonierte Produkt hatte folgende Kenndaten
Aniontensid (DGF-H-III-10): 20 Gew.-% = 0,31 mEq/g
unsulfierte Anteile (DGF-G-III-6b): 5 Gew.-%
Kaliumsulfat: 2 Gew.-%
Kaliumphosphat: 1 Gew.-%
Wasser (nach Fischer): 72 Gew.-%
mittleres Molekulargewicht: 635 2. Preparation of sulfonated oleyl alcohol-0.5 mol ethylene oxide phosphate, potassium salt
Analogously to Example 1, 1.5 mol of oleyl alcohol-0.5 mol of ethylene oxide were reacted with 0.5 mol of phosphorus pentoxide. The phosphoric acid ester obtained had an average molecular weight of 478 and 1.3 double bond equivalents per mole of phosphate.
The sulfonation of 240 g (0.5 mol) of oleyl-0.5 mol of ethylene oxide phosphate was carried out analogously to Example 1. The sulfonated product obtained had the following characteristics
Anionic surfactant (DGF-H-III-10): 20% by weight = 0.31 mEq / g
unsulphated components (DGF-G-III-6b): 5% by weight
Potassium sulfate: 2% by weight
Potassium phosphate: 1% by weight
Water (according to Fischer): 72% by weight
average molecular weight: 635 -
3. Herstellung von sulfoniertem Oleylalkohol-2 Mol Ethylenoxid-Phosphat, Kaliumsalz
Analog Beispiel 1 wurden 1,5 Mol Oleylalkohol-2 Mol Ethylenoxid mit 0,5 Mol Phosphorpentoxid umgesetzt. Der erhaltene Phosphorsäureester hatte ein mittleres Molekulargewicht von 570 und 1,3 Doppelbindungsäquivalente pro Mol Phosphat.
Die Sulfonierung von 284 g (0,5 Mol) Oleyl-2 Mol Ethylenoxid-Phosphat, Kaliumsalz wurde analog Beispiel 1 durchgeführt. Das erhaltene sulfonierte Produkt hatte folgende Kenndaten:
Aniontensid (DGF-H-III-10): 18 Gew.-% = 0,25 mEq/g
unsulfierte Anteile (DGF-G-III-6b): 6 Gew.-%
Kaliumsulfat: 3 Gew.-%
Kaliumphosphat: 1 Gew.-%
Wasser (nach Fischer): 72 Gew.-%
mittleres Molekulargewicht: 722 3. Preparation of sulfonated oleyl alcohol-2 moles of ethylene oxide phosphate, potassium salt
Analogously to Example 1, 1.5 mol of oleyl alcohol-2 mol of ethylene oxide were reacted with 0.5 mol of phosphorus pentoxide. The phosphoric acid ester obtained had an average molecular weight of 570 and 1.3 double bond equivalents per mole of phosphate.
The sulfonation of 284 g (0.5 mol) of oleyl-2 mol of ethylene oxide phosphate, potassium salt was carried out analogously to Example 1. The sulfonated product obtained had the following characteristics:
Anionic surfactant (DGF-H-III-10): 18% by weight = 0.25 mEq / g
unsulphated components (DGF-G-III-6b): 6% by weight
Potassium sulfate: 3% by weight
Potassium phosphate: 1% by weight
Water (according to Fischer): 72% by weight
average molecular weight: 722
Alle %-Angaben sind Gew.-% und beziehen sich auf das Falzgewicht der Leder.All percentages are% by weight and relate to the fold weight of the leather.
Chromoberleder, 1,8 mm Dicke, wurden nach folgender Rezeptur nachgegerbt und nach der Entfernung von überschüssigen Gerbstoffen durch Waschen mit Kaliumsalzen von sulfonierten Phosphorsäureestern gefettet:
Die Fettung wurde mit einem der folgenden Fettungsmittel durchgeführt:The greasing was carried out with one of the following greasing agents:
oder
or
oder
or
oder
or
oder
or
Nach der Fettung wurde wie folgt weitergearbeitet:
Die nachfolgende Tabelle enthält die an den mit den oben angegebenen verschiedenen Fettungsmitteln behandelten Ledern durchgeführten Prüfungen sowie die Prüfergebnisse.
Claims (8)
- A process for the production of leathers having favourable water behaviour, characterized in that, after tanning, retanning or dyeing, the leather is oiled with alkali metal, amine and/or ammonium salts of sulfonated phosphoric acid esters obtainable by reaction of phosphoric acid esters corresponding to general formula I:
R¹ is an alkyl or alkenyl group containing 8 to 22 carbon atoms,
R² and R³ may be the same or different and represent H or an alkyl or alkenyl group containing 8 to 22 carbon atoms,
the indices m, n and p may be the same or different and each represent a number of 2 to 4 and
the indices x, y and z may be the same or different and each represent a number of 0 to 30,
with sulfonating agents and subsequent hydrolysis of the products obtained with alkali metal hydroxides, ammonium hydroxide and/or amines,
the treatment liquid containing the oiling agents is then adjusted with acids to a pH value of 3.5 to 4.1 in known manner and the sulfonated phosphoric acid ester salts are fixed on and in the leather by addition of chrome and/or aluminium tanning agents. - A process as claimed in claim 4, characterized in that the treatment liquor is adjusted to a pH value of 3.8 to 4.0 with formic acid, acetic acid and/or sulfuric acid.
- A process as claimed in one or both of claims 1 and 2, characterized in that salts of sulfonated phosphoric acid esters are used on their own or in combination with other oiling agents in quantities - based on the pared weight - of 1 to 20% by weight and preferably 2 to 14% by weight.
- A process as claimed in one or more of claims 1 to 3, characterized in that alkali metal salts of sulfonated phosphoric acid esters are used.
- A process as claimed in one or more of claims 1 to 4, characterized in that salts of sulfonated phosphoric acid esters obtainable from phosphoric acid esters of general formula I, in which R¹ is an alkyl or alkenyl group containing 12 to 18 carbon atoms, R² and R³ may be the same or different and each represent H or an alkyl or alkenyl group containing 12 to 18 carbon atoms, the indices m, n and p stand for the number 2 and the indices x, y and z may be the same or different and each represent a number of 0 to 10, are used.
- The use of sulfonated phosphoric acid esters obtainable by reaction of phosphoric acid esters corresponding to general formula I:
R¹ is an alkyl or alkenyl group containing 8 to 22 carbon atoms,
R² and R³ may be the same or different and represent H or an alkyl or alkenyl group containing 8 to 22 carbon atoms,
the indices m, n and p may be the same or different and each represent a number of 2 to 4 and
the indices x, y and z may be the same or different and each represent a number of 0 to 30,
with sulfonating agents and subsequent hydrolysis of the products obtained with alkali metal hydroxides, ammonium hydroxide and/or amines,
for the production of leathers having favourable water behaviour. - The use claimed in claim 6, characterized in that alkali metal salts of sulfonated phosphoric acid esters are used.
- The use claimed in one or both of claims 6 and 7, characterized in that salts of sulfonated phosphoric acid esters obtainable from phosphoric acid esters of general formula I, in which R¹ is an alkyl or alkenyl group containing 12 to 18 carbon atoms, R² and R³ may be the same or different and each represent H or an alkyl or alkenyl group containing 12 to 18 carbon atoms, the indices m, n and p stand for the number 2 and the indices x, y and z may be the same or different and each represent a number of 0 to 10, are used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4004293A DE4004293A1 (en) | 1990-02-13 | 1990-02-13 | Dubbing agent for leather |
| DE4004293 | 1990-02-20 | ||
| PCT/EP1991/000206 WO1991012344A2 (en) | 1990-02-13 | 1991-02-04 | Salts of sulphonated phosphoric acid esters for use as leather-oiling agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0515426A1 EP0515426A1 (en) | 1992-12-02 |
| EP0515426B1 true EP0515426B1 (en) | 1994-08-31 |
Family
ID=6399982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91903401A Expired - Lifetime EP0515426B1 (en) | 1990-02-13 | 1991-02-04 | Method of preparing salts of sulphonated phosphoric acid esters and their use as leather-oiling agents |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0515426B1 (en) |
| JP (1) | JPH05504161A (en) |
| AT (1) | ATE110792T1 (en) |
| BR (1) | BR9106036A (en) |
| DE (2) | DE4004293A1 (en) |
| ES (1) | ES2060363T3 (en) |
| WO (1) | WO1991012344A2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4435399A1 (en) * | 1994-10-04 | 1996-04-11 | Henkel Kgaa | Leather and fur lubricants |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3504308A1 (en) * | 1984-02-22 | 1985-08-22 | Sandoz-Patent-GmbH, 7850 Lörrach | Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather |
| GB2198452B (en) * | 1986-12-04 | 1990-05-02 | Sandoz Ltd | Phosphoric acid partial ester compositions and method of fatting leather therewith |
| DE3812718A1 (en) * | 1988-04-16 | 1989-10-26 | Henkel Kgaa | SURFACE ACTIVE, SULFOPHOSPHORIC ACID (PARTIAL) ALKYLESTER |
-
1990
- 1990-02-13 DE DE4004293A patent/DE4004293A1/en not_active Withdrawn
-
1991
- 1991-02-04 EP EP91903401A patent/EP0515426B1/en not_active Expired - Lifetime
- 1991-02-04 DE DE59102749T patent/DE59102749D1/en not_active Expired - Fee Related
- 1991-02-04 JP JP3503702A patent/JPH05504161A/en active Pending
- 1991-02-04 BR BR919106036A patent/BR9106036A/en not_active Application Discontinuation
- 1991-02-04 ES ES91903401T patent/ES2060363T3/en not_active Expired - Lifetime
- 1991-02-04 AT AT91903401T patent/ATE110792T1/en active
- 1991-02-04 WO PCT/EP1991/000206 patent/WO1991012344A2/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE4004293A1 (en) | 1991-08-14 |
| BR9106036A (en) | 1993-02-02 |
| DE59102749D1 (en) | 1994-10-06 |
| WO1991012344A2 (en) | 1991-08-22 |
| JPH05504161A (en) | 1993-07-01 |
| WO1991012344A3 (en) | 1991-10-03 |
| ATE110792T1 (en) | 1994-09-15 |
| EP0515426A1 (en) | 1992-12-02 |
| ES2060363T3 (en) | 1994-11-16 |
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