EP1904658B1 - Method for producing leather - Google Patents
Method for producing leather Download PDFInfo
- Publication number
- EP1904658B1 EP1904658B1 EP06777608A EP06777608A EP1904658B1 EP 1904658 B1 EP1904658 B1 EP 1904658B1 EP 06777608 A EP06777608 A EP 06777608A EP 06777608 A EP06777608 A EP 06777608A EP 1904658 B1 EP1904658 B1 EP 1904658B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- dialdehydes
- leather
- mixture
- 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.)
- Active
Links
- 239000010985 leather Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000009472 formulation Methods 0.000 claims description 28
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 16
- 150000007513 acids Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011265 semifinished product Substances 0.000 claims description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 13
- 241001465754 Metazoa Species 0.000 claims description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000001361 adipic acid Substances 0.000 claims description 10
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 4
- 235000021110 pickles Nutrition 0.000 claims 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- -1 for example Substances 0.000 description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 17
- 150000001991 dicarboxylic acids Chemical class 0.000 description 16
- 206010000496 acne Diseases 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 229960000587 glutaral Drugs 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 241000283690 Bos taurus Species 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000013011 aqueous formulation Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- 239000008233 hard water Substances 0.000 description 5
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 108010019160 Pancreatin Proteins 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229940055695 pancreatin Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- SKCQDFLBBMGDPT-UHFFFAOYSA-L 4-((2,4-dihydroxy-5-((2-hydroxy-3,5-dinitrophenyl)azo)-3-((4-nitrophenyl)azo)phenyl)azo)-5-hydroxy-2,7-naphthalenedisulfonic acid disodium salt Chemical compound [Na+].[Na+].OC1=C(N=NC=2C(=C(C=C(C=2)[N+]([O-])=O)[N+]([O-])=O)O)C=C(N=NC=2C3=C(O)C=C(C=C3C=C(C=2)S([O-])(=O)=O)S([O-])(=O)=O)C(O)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 SKCQDFLBBMGDPT-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000991 leather dye Substances 0.000 description 2
- 125000003136 n-heptyl 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])* 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 241001296405 Tiso Species 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000008063 acylals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001049 brown dye Substances 0.000 description 1
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- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
Definitions
- the present invention relates to leather produced according to the invention.
- chrome tanning In tanning, a distinction is made between chrome tanning and chromium-free tanning, which leads to wet-blue or wet-white semi-finished products.
- the chromium-free tanning offers certain ecological advantages: there are no chrome-containing wastewaters, and the folded waste is also chromium-free and does not need to be specially disposed of.
- Important tanning agents for chromium-free tanning are, for example, polymers and aldehydes, in particular dialdehydes, such as, for example, glutaraldehyde.
- dialdehydes such as glutaraldehyde
- the resulting semi-finished products are poorly withered or poorly folded, and these problems are especially noticeable when using hard water, for example at 20 ° dH or more
- deliming is understood within the scope of the present invention Invention, the step of removing the used liming basic substances from the pelt, in particular of CaO / Ca (OH) 2.
- DD 255 360 relates to a process for the delimitation of pelts.
- Specially disclosed DD 255 360 a suitable formulation containing formaldehyde and an organic acid mixture of maleic acid, acetic acid, acrylic acid and propionic acid in certain proportions.
- the waste water load with salts, and in particular with ammonium can be reduced during the liming.
- a special waste product of the chemical industry was used.
- WO 03/95681 Numerous organic compounds are disclosed which are useful as tanning agents and as preservatives and which can release one or more aldehydes or dialdehydes at acidic pH. A tanning of cattle pelts is revealed. The pH is adjusted by the acidic pores.
- pretanned or tanned animal skins which still require retanning, are referred to as semifinished products.
- semifinished products In the context of the present invention, retanned semifinished products and finished tanned animal skins, in which retreading is no longer required, are referred to as leather.
- the method according to the invention is based on animal skins, which may be obtained from any dead animals, in particular bovine skins, calf skins, goat skins, deer skins or pig skins.
- the method according to the invention is based on animal skins which are limed and deliquesced by any desired method, ie freed from excess CaO and Ca (OH) 2 or other basic substances, such as, for example, NaOH.
- Animal hides used for carrying out the method according to the invention may further be pickled, ie pretreated after the deliming with formic acid or acetic acid.
- one starts from animal skins that are decolored using boric acid for example using mixtures of boric acid and C 1 -C 3 carboxylic acid or using mixtures of boric acid and C 1 -C 3 carboxylic acid and alkali metal sulfite.
- animal hides are deliquesced, in particular using CO 2 or one or more organic compounds which can cleave CO 2 in an aqueous medium, in particular using one or more organic carbonates Use of mixtures of ethylene carbonate and propylene carbonate.
- Suitable compounds which can cleave dialdehydes at acidic pH are bis-oxazolidinones derived, for example, from OHC- (CH 2 ) x -CHO.
- Suitable compounds which can cleave formaldehyde or acetaldehyde at acidic pH are tetrakishydroxymethylphosphonium salts and tetrakishydroxyethylphosphonium salts, especially tetrakishydroxymethylphosphonium chloride.
- C 3 -C 12 dicarboxylic acids (b1) and / or further acidic compound (b2) selected from C 3 -C 12 dicarboxylic acids and C 1 -C 3 monocarboxylic acids, in each case as the free acid or in the form of their salts be used.
- salts which may be mentioned are alkali metal salts, such as sodium or potassium salts.
- salts of amines such as, for example, H 1-y N (R 2 ) y are also suitable.
- R 2 is in each case identical or different and is independently selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl and most preferably methyl or ethyl, and ⁇ -hydroxy-C 2 -C 4 -alkylene such as 3-hydroxypropyl, 4-hydroxybutyl and especially 2-hydroxyethyl.
- C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl and most preferably methyl or ethyl
- ⁇ -hydroxy-C 2 -C 4 -alkylene such as 3-hydroxypropyl, 4-hydroxybutyl and especially 2-hydroxyethyl.
- C 3 -C 12 -dicarboxylic acids (b1) and / or further acidic compound (b2) selected from C 3 -C 12 -dicarboxylic acids and C 1 -C 3 -monocarboxylic acids are partially neutralized.
- the mixture is treated with a mixture containing two different C 3 -C 12 dicarboxylic acids and a C 1 -C 3 monocarboxylic acid.
- C 3 -C 12 dicarboxylic acid (b1) adipic acid and two further acidic compounds (b2) are selected, namely a C 3 -C 12 dicarboxylic acid and a C 1 -C 3 monocarboxylic acid.
- adipic acid and two further acidic compounds are selected as C 3 -C 12 -dicarboxylic acid (b1), namely two C 3 -C 12 dicarboxylic acids, preferably glutaric acid and succinic acid.
- the process according to the invention is preferably carried out in an aqueous liquor.
- suitable devices are drums, preferably rotatable drums and, in particular, rotatable drums with flow-breaking internals.
- organic tanning agent (a) and mixture (b) are used in a weight ratio of 100: 1 to 1: 1, preferably 5: 1 to 1.5: 1.
- animal skin is treated with 0.1 to 10% by weight of tanning agent (a), based on the shaved weight, preferably 1.5 to 5% by weight.
- the process according to the invention is carried out at a temperature in the range from 15 to 50.degree. C., preferably from 20 to 35.degree.
- a pH in the range from 2.0 to 6.5, preferably from 2.8 to 5.0, is used to carry out the process according to the invention.
- the process according to the invention can be carried out over a period of 5 minutes to 24 hours, preferably 60 minutes to 6 hours.
- the process according to the invention can be carried out using soft water, for example water at 0 to 7 ° dH (German hardness).
- the process according to the invention is carried out using medium-hard water, for example water at 7 to 19 ° dH, preferably with hard water of at least 20 to 200 ° dH.
- one or more leather dyes are added while the process according to the invention is being carried out. In another embodiment, the process according to the invention is carried out without the addition of leather dyes.
- one or more other chrome-free tanning agent to, for example, mineral tanning agents such as aluminum compounds, particularly aluminum sulphate or alum, zirconium compounds such as Zr (SO 4) 2 or ZrSO 4 (OH) 2 or titanium compounds such as Ti (SO 4 ) 2 or TiSO 4 (OH) 2 , resin tanning agents, vegetable tanning or enzymatic tanning agents or synthetic tanning agents such as condensation products of carbonyl compounds such as formaldehyde with one or more aromatic sulfonic acids. It is also possible to add one or more dispersants, in particular one or more nonionic surfactants, for example polyethoxylated aliphatic C 6 -C 20 -alcohols, branched or unbranched.
- mineral tanning agents such as aluminum compounds, particularly aluminum sulphate or alum
- zirconium compounds such as Zr (SO 4) 2 or ZrSO 4 (OH) 2
- titanium compounds such as Ti (SO 4 ) 2 or TiSO 4 (OH) 2
- the process according to the invention is carried out as a pretanning or as tanning.
- organic tanning agent (a) and mixture (b) can be separated or preferably metered together.
- the process according to the invention is carried out as a retanning, for example at a pH in the range from 3 to 6 and a temperature in the range from 20 to 65 ° C.
- alkali metal halides in particular sodium chloride, for example 1 to 10% by weight, based on pelt, preferably 4 to 7% by weight.
- alkali metal halide can be completely or partially replaced by ionic polymers.
- the residence time of the pimples in the latter variant of the present invention is for example 10 minutes to 24 hours, preferably 15 minutes to 2 hours and more preferably 15 to 45 minutes.
- Pimpling in the latter variant of the present invention proceeds under otherwise tanning conditions, the temperature is 10 to 35 ° C and the pressure 1 to 10 bar, is particularly useful normal pressure.
- Semi-finished products and leather produced by the process according to the invention are also distinguished by particularly good whiteness, good body and softness and a particularly low tendency to yellowing when using hard water and are particularly well suited for the production of clothing such as coats, jackets, belts , Shoes, gloves, furniture and car parts. Furthermore, semi-finished products produced by the process according to the invention show good to very good hemmability and a good to very good wilting behavior and can be processed very well to leather.
- organic tanning agent (a) selected from dialdehydes and compounds which can cleave dialdehydes at acidic pH, and mixture (b) are as defined above.
- tannin (a) glutaric dialdehyde very particular preference is given to using tannin (a) glutaric dialdehyde.
- mixture (b) comprises at least two C 3 -C 12 dicarboxylic acids selected from adipic acid, glutaric acid, maleic acid and succinic acid, or salts thereof.
- Formulations according to the invention may contain, for example, in the range from 30 to 80% by weight of water.
- Formulations according to the invention may preferably have a pH in the range from 2.5 to 6.5, more preferably in the range from 3.0 to 5.0.
- formulations according to the invention may contain in total from 10 to 70% by weight of organic tanning agent (a), preferably from 15 to 40% by weight,
- mixture (b) in the range from 2.5 to 50% by weight of mixture (b), preferably from 5 to 25% by weight, wherein in wt .-% are based on total formulation of the invention, the remainder is for example water.
- mixture (b) contained in the formulation of the invention may contain in the range of 30 to 99% by weight of C 3 -C 12 -dicarboxylic acid (b1), in total in the range from 1 to 70% by weight of further acidic compound (b2), where in wt .-% on mixture (b) are related.
- Formulations according to the invention are particularly well suited for carrying out the process according to the invention described above.
- Another object of the present invention is the use of formulations according to the invention for the production of leather, for example, for pretanning, tanning, retanning or pimples.
- Another object of the present invention is a process for the production of leather, for example a method for pretanning, tanning, retanning or pimpling, using formulation according to the invention.
- the pre-tanning and the tanning are particularly preferred.
- Another object of the present invention are semi-finished products and leather, prepared by the novel process.
- Leathers according to the invention are also distinguished by good whiteness, good body and softness and a particularly low tendency to yellowing when using hard water and are particularly well suited for the production of clothing such as coats, jackets, belts, shoes, especially lining and upper leather , Gloves, furniture and car parts.
- semi-finished products produced by the process according to the invention show good to very good hemmability and a good to very good wilting behavior and can be processed very well to leather.
- a further subject of the present invention is a process for the preparation of formulations according to the invention, also referred to below as preparation process according to the invention.
- preparation process for carrying out the preparation process according to the invention, it is possible, for example, to initially prepare a mixture (b) of at least one C 3 -C 12 -dicarboxylic acid (b1) and at least one further acidic compound (b2) selected from C 1 -C 3 - mono- or di-C 3 -C 12 dicarboxylic acids, prepared in water, optionally partially or completely neutralized with base such as basic alkali metal salt, for example potassium or sodium salts, such as carbonates or bicarbonates, in particular sodium hydroxide, or with ammonia or organic amine, and thereafter at least an organic tanning agent (a) admixed.
- base such as basic alkali metal salt, for example potassium or sodium salts, such as carbonates or bicarbonates, in particular sodium hydroxide, or with ammonia or organic amine
- Aqueous formulation F-1 according to the invention was obtained.
- Aqueous formulation F-1 according to the invention had a pH of from 3 to 4.
- Aqueous formulation F-2 according to the invention was obtained.
- Aqueous formulation F-2 according to the invention had a pH of from 3 to 4.
- Comparative Formulation V-F-3 a 50% by weight aqueous solution of glutaric dialdehyde was used, pH 3 to 4.
- LVE Löhlein-Volhard units, determinable, for example, by methods based on the degradation of casein by an enzyme to be tested and the subsequent titration of the liberated carboxyl groups with 0.1 N NaOH.
- One LVE corresponds to 0.00575 ml of 0.1 N NaOH.
- bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
- bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
- bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
- the pimples PF-1 to PF-4 were prepared by mixing the substances according to Table 1 and filling with water.
- Table 1 Composition of pimples used PF-1 to PF-4 H 2 SO 4 HCOOH NaCl MgCl 2 CaCl 2 [° dH] [G / l] [G / l] [° Be] [Mmol / l] [Mmol / l] [Mmol / l] PF-1 15 8th 7.0 - - 0 PF-2 15 8th 7.0 0.54 3 20 PF-3 15 8th 7.0 1.1 6.1 40 PF-4 15 8th 7.0 2.7 15.3 100 MgCl 2 was used as the hexahydrate.
- the macerated pelts from BI-1 to BI-3 were each halved and treated in separate barrels over a period of 90 minutes with 150 wt .-% of one of the pimples PF-1 to PF-4 (see Table 2).
- the pimples PB-1 to PB-12 were obtained.
- Each PB-1 to PB-12 was cut into three equal pieces of 1.5 kg pelt weight each.
- the reaction was carried out for a further 90 minutes and then dulled with a mixture (weight ratio 1: 2) of sodium formate and naphthalenesulfonic acid-formaldehyde condensation product, prepared according to US 5,186,846 Example "Dispersant 1", to a pH of 4 from.
- the semifinished product obtained in this way was washed twice with water, wiped off and folded to a thickness of 1.8 mm. They evaluated the Abwelk , the folding and the degree of whiteness. Furthermore, one determined the shrinkage temperature.
- Example II.4 For the evaluation of the finished leather, the product was tanned according to the instructions given in Example II.4.
- the leathers thus obtained were washed twice with 100 wt .-% water, stored moist overnight and dried after Abwalken on tenter at 50 ° C.
- the leathers L-1 to L-24 according to the invention and comparative leathers V-L-25 to V-L-36 were obtained. After the tunnel, the leathers were judged as below.
- the rating was based on a grading system from 1 (very good) to 5 (poor). The evaluation of whiteness and levelness was done visually. The Abwelk was judged at an identical Abwelk réelle of 100 bar on the quality of drainage and the fiber structure on the meat side (isolated fibers with low fiber bonds represent the ideal state). The folding ability was based the levelness of the folding result over the surface, the shavings (isolated fibers, loose structure), the morphology of the meat side (due to the temperature development, it may unintentionally come to irreversible hardening) and the whereabouts of (interfering) shavings on the meat side judged.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Leder, dadurch gekennzeichnet, dass man Tierhäute im Anschluss an das Äschern, Entkälken und ggf. Pickeln oder beim Pickeln behandelt mit
- (a) mindestens einem organischen Gerbstoff, gewählt aus Aldehyden, Dialdehyden und Verbindungen, die bei saurem pH-Wert in Gegenwart von Wasser Formaldehyd, Acetaldehyd oder Dialdehyde abspalten können,
und - (b) einem Gemisch von
- (b1) mindestens einer C3-C12-Dicarbonsäure
- (b2) und mindestens einer weiteren sauren Verbindung, gewählt aus C1-C3-Mono- oder C3-C12-Dicarbonsäuren, oder deren Salzen, die jeweils ungleich C3-C12-Dicarbonsäuren (b1) sind.
- (a) at least one organic tanning agent selected from aldehydes, dialdehydes and compounds which can split off formaldehyde, acetaldehyde or dialdehydes at acidic pH in the presence of water,
and - (b) a mixture of
- (b1) at least one C 3 -C 12 dicarboxylic acid
- (b2) and at least one further acidic compound selected from C 1 -C 3 mono- or C 3 -C 12 dicarboxylic acids, or their salts, which are each different than C 3 -C 12 dicarboxylic acids (b1).
Weiterhin betrifft die vorliegende Erfindung Formulierungen, enthaltend
- (a) mindestens einen organischen Gerbstoff, gewählt aus Dialdehyden und Verbindungen, die bei saurem pH-Wert Dialdehyde abspalten können, und
- (b) ein Gemisch von
- (b1) mindestens einer C3-C12-Dicarbonsäure,
- (b2) und mindestens einer weiteren sauren Verbindung, gewählt aus C1-C3-Mono- oder C3-C12-Dicarbonsäuren, oder deren Salzen, die jeweils ungleich C3-C12-Dicarbonsäure (b1) sind.
- (A) at least one organic tanning agent selected from dialdehydes and compounds which can cleave dialdehydes at acidic pH, and
- (b) a mixture of
- (b1) at least one C 3 -C 12 -dicarboxylic acid,
- (b2) and at least one further acidic compound selected from C 1 -C 3 mono- or C 3 -C 12 dicarboxylic acids, or their salts, each of which is not equal to C 3 -C 12 dicarboxylic acid (b1).
Weiterhin betrifft die vorliegende Erfindung erfindungsgemäß hergestellte Leder.Furthermore, the present invention relates to leather produced according to the invention.
Beim Gerben unterscheidet man die Chrom-Gerbung und die chromfreie Gerbung, die zu Wet-blue bzw. Wet-white-Halbzeugen führt. Dabei bietet die chromfreie Gerbung gewisse ökologische Vorteile: es entstehen keine chromhaltigen Abwässer, und die Falzabfälle sind ebenfalls chromfrei und müssen nicht speziell entsorgt werden.In tanning, a distinction is made between chrome tanning and chromium-free tanning, which leads to wet-blue or wet-white semi-finished products. The chromium-free tanning offers certain ecological advantages: there are no chrome-containing wastewaters, and the folded waste is also chromium-free and does not need to be specially disposed of.
Wichtige Gerbstoffe für die chromfreie Gerbung sind beispielsweise Polymere und Aldehyde, insbesondere Dialdehyde wie beispielsweise Glutardialdehyd. Wenn man Wet-white-Halbzeuge herzustellen wünscht, beobachtet man in vielen Fällen, dass man bei der Verwendung von Aldehyden, insbesondere Dialdehyden wie beispielsweise Glutardialdehyd nicht die erwünschten weißen Halbzeuge erhält, sondern gelbstichige Produkte, siehe beispielsweise
Es ist möglich, das zum Gerben eingesetzte Wasser vorzubehandeln, beispielsweise mit Hilfe eines lonenaustauschers, und damit die Härte zu reduzieren. Eine derartige Vorgehensweise ist jedoch aufwändig und nicht praktikabel.It is possible to pretreat the water used for tanning, for example by means of an ion exchanger, and thus to reduce the hardness. However, such a procedure is laborious and impractical.
In
Es bestand also die Aufgabe, ein Verfahren zur Herstellung von Leder bereit zu stellen, durch das man bei der chromfreien Gerbung und insbesondere bei der Gerbung mit Aldehyden, ganz besonders Dialdehyden wie beispielsweise Glutardialdehyd, unabhängig von der Wahl des Entkälkungsverfahrens und der Güte (Vollständigkeit) der Entkälkung, weiße Halbzeuge erhält, die keinen Gelbstich zeigen. Es bestand weiterhin die Aufgabe, Formulierungen bereit zu stellen, die zur chromfreien Herstellung von Leder, insbesondere zur Gerbung mit Aldehyden geeignet sind und die oben genannten Nachteile vermeiden. Es bestand weiterhin die Aufgabe, Leder mit geringer Neigung zum Gelbstich zur Verfügung zu stellen.It was therefore the object to provide a process for the production of leather, by which in chromium-free tanning and especially in the tanning with aldehydes, especially dialdehydes such as glutaric dialdehyde, regardless of the choice of Entkälkungsverfahrens and the quality (completeness) of the deliming, receives white semi-finished products that show no yellowing. A further object was to provide formulations which are suitable for the chromium-free production of leather, in particular for tanning with aldehydes, and which avoid the abovementioned disadvantages. It was still the task to provide leather with a low tendency to yellowish available.
Demgemäß wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.
Im Rahmen der vorliegenden Erfindung werden vorgegerbte oder gegerbte Tierhäute, bei denen noch eine Nachgerbung erforderlich ist, als Halbfabrikate bezeichnet. Im Rahmen der vorliegenden Erfindung werden nachgegerbte Halbfabrikate und fertig gegerbte Tierhäute, bei denen keine Nachgerbung mehr erforderlich ist, als Leder bezeichnen.In the context of the present invention, pretanned or tanned animal skins, which still require retanning, are referred to as semifinished products. In the context of the present invention, retanned semifinished products and finished tanned animal skins, in which retreading is no longer required, are referred to as leather.
Das erfindungsgemäße Verfahren geht aus von Tierhäuten, die von beliebigen toten Tieren erhalten sein können, insbesondere von Rinderhäuten, Kalbshäuten, Ziegenhäuten, Hirschhäuten oder Schweinehäuten.The method according to the invention is based on animal skins, which may be obtained from any dead animals, in particular bovine skins, calf skins, goat skins, deer skins or pig skins.
Das erfindungsgemäße Verfahren geht aus von Tierhäuten, die nach beliebigen Verfahren geäschert und entkälkt, d.h. von überschüssigem CaO und Ca(OH)2 oder anderen basischen Substanzen wie beispielsweise NaOH befreit sind. Zur Durchführung des erfindungsgemäßen Verfahren eingesetzte Tierhäute können weiterhin gepickelt, d.h. nach der Entkälkung mit Ameisensäure oder Essigsäure vorbehandelt sein.The method according to the invention is based on animal skins which are limed and deliquesced by any desired method, ie freed from excess CaO and Ca (OH) 2 or other basic substances, such as, for example, NaOH. Animal hides used for carrying out the method according to the invention may further be pickled, ie pretreated after the deliming with formic acid or acetic acid.
In einer Ausführungsform der vorliegenden Erfindung geht man aus von Tierhäuten, die unter Verwendung von Borsäure entkält sind, beispielsweise unter Verwendung von Mischungen aus Borsäure und C1-C3-Carbonsäure oder unter Verwendung von Mischungen von Borsäure und C1-C3-Carbonsäure und Alkalimetallsulfit. In einer anderen Ausführungsform der vorliegenden Erfindung geht man aus von Tierhäuten, die unter Verwendung von einem oder mehreren Ammoniumsalzen entkälkt sind, insbesondere unter Verwendung von Mischungen von Ammoniumschlorid und Ammoniumsulfat. In einer anderen Ausführungsform der vorliegenden Erfindung geht man aus von Tierhäuten, die unter Verwendung von CO2 oder von einer oder mehreren organischen Verbindungen, die in wässrigem Milieu CO2 abspalten können, insbesondere unter Verwendung von einem oder mehreren organischen Carbonaten entkälkt sind, insbesondere unter Verwendung von Mischungen von Ethylencarbonat und Propylencarbonat.In one embodiment of the present invention, one starts from animal skins that are decolored using boric acid, for example using mixtures of boric acid and C 1 -C 3 carboxylic acid or using mixtures of boric acid and C 1 -C 3 carboxylic acid and alkali metal sulfite. In another embodiment of the present invention, one starts from animal skins delimbed using one or more ammonium salts, in particular using mixtures of ammonium chloride and ammonium sulfate. In another embodiment of the present invention, it is assumed that animal hides are deliquesced, in particular using CO 2 or one or more organic compounds which can cleave CO 2 in an aqueous medium, in particular using one or more organic carbonates Use of mixtures of ethylene carbonate and propylene carbonate.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man ein:
- (a) mindestens einen organischen Gerbstoff, der gewählt wird aus Aldehyden, Dialdehyden und Verbindungen, die bei saurem pH-Wert Formaldehyd, Acetaldehyd oder Dialdehyde abspalten können, insbesondere im wässrigen Milieu bei pH-Werten im Bereich von 1,5 bis 6,5. Bevorzugte Aldehyde sind Formaldehyd, Acetaldehyd und Glyoxalsäure. Bevorzugte Dialdehyde sind Glyoxal und Verbindungen der allgemeinen Formel OHC-(CH2)x-CHO, bei denen x eine ganze Zahl im Bereich von 1 bis 10 sein kann, bevorzugt 2 bis 7 und ganz besonders bevorzugt 3 oder 4. Die Verbindung der Formel OHC-(CH2)3-CHO entspricht dem Glutardialdehyd. Bevorzugte Verbindungen, die bei saurem pH-Wert, insbesondere im wässrigen Milieu bei pH-Werten im Bereich von 1,5 bis 6,5 Formaldehyd oder Dialdehyde abspalten können, sind beispielsweise Dimere, Trimere, Polymere, Hydrate, Dihydrate, Acetale, Halbacetale, Acylale von Formaldehyd, Acetaldehyd oder Dialdehyden. Als Beispiele seien genannt:
C1-C3-Acyl, beispielsweise Formyl, Acetyl, Propionyl,
und insbesondere Wasserstoff.To carry out the process according to the invention, use is made of:
- (A) at least one organic tanning agent which is selected from aldehydes, dialdehydes and compounds which can cleave formaldehyde, acetaldehyde or dialdehydes at acidic pH, in particular in an aqueous medium at pH values in the range from 1.5 to 6.5 , Preferred aldehydes are formaldehyde, acetaldehyde and glyoxylic acid. Preferred dialdehydes are glyoxal and compounds of the general formula OHC- (CH 2 ) x -CHO, in which x can be an integer in the range from 1 to 10, preferably 2 to 7 and very particularly preferably 3 or 4. The compound of the formula OHC- (CH 2 ) 3 -CHO corresponds to the glutaric dialdehyde. Preferred compounds which can cleave off formaldehyde or dialdehydes at an acidic pH, in particular in an aqueous medium, at pH values in the range from 1.5 to 6.5 are, for example, dimers, trimers, polymers, hydrates, dihydrates, acetals, hemiacetals, Acylals of formaldehyde, acetaldehyde or dialdehydes. Examples include:
C 1 -C 3 acyl, for example formyl, acetyl, propionyl,
and especially hydrogen.
Weitere geeignete Verbindungen, die bei saurem pH-Wert Dialdehyde abspalten können, sind beispielsweise in
Weitere geeignete Verbindungen, die bei saurem pH-Wert Dialdehyde abspalten können, sind von beispielsweise OHC-(CH2)x-CHO abgeleitete bis-Oxazolidinone.Other suitable compounds which can cleave dialdehydes at acidic pH are bis-oxazolidinones derived, for example, from OHC- (CH 2 ) x -CHO.
Weitere geeignete Verbindungen, die bei saurem pH-Wert Formaldehyd oder Acetaldehyd abspalten können, sind Tetrakishydroxymethylphosphoniumsalze und Tetrakishydroxyethylphosphoniumsalze, insbesondere Tetrakishydroxymethylphosphoniumchlorid.Other suitable compounds which can cleave formaldehyde or acetaldehyde at acidic pH are tetrakishydroxymethylphosphonium salts and tetrakishydroxyethylphosphonium salts, especially tetrakishydroxymethylphosphonium chloride.
Ganz besonders bevorzugt wählt man organischen Gerbstoff (a) aus Glutardialdehyd, beispielsweise als cyclisches Dihydrat
Weiterhin behandelt man Tierhäute mit einem Gemisch (b) von
- (b1) mindestens einer C3-C12-Dicarbonsäure, bevorzugt mindestens einer olefinisch ungesättigten C4-C12-Dicarbonsäure oder besonders bevorzugt mindestens einer aliphatischen C3-C12-Dicarbonsäure, beispielsweise Malonsäure, Methylmalonsäure, Maleinsäure, Fumarsäure, Bernsteinsäure, Citraconsäure, Metaconsäure, Glutarsäure, Itaconsäure, Adipinsäure, Sebacinsäure, Pimelinsäure, Phthalsäure, Terephthalsäure, Isophthalsäure, insbesondere Bernsteinsäure, Glutarsäure und Adipinsäure,
- (b2) mindestens einer weiteren sauren Verbindung, gewählt aus C1-C3-Monocarbonsäuren wie Ameisensäure, Essigsäure oder Propionsäure, C3-C12-Dicarbonsäuren, beispielsweise Phthalsäure, Terephthalsäure, Isophthalsäure, bevorzugt olefinisch ungesättigten C4-C12-Dicarbonsäuren oder besonders bevorzugt aliphatischen C3-C12-Dicarbonsäuren, beispielsweise Malonsäure, Methylmalonsäure, Maleinsäure, Fumarsäure, Bernsteinsäure, Citraconsäure, Metaconsäure, Glutarsäure, Itaconsäure, Adipinsäure, Sebacinsäure, Pimelinsäure, insbesondere Bernsteinsäure, Glutarsäure und Adipinsäure.
- (b1) at least one C 3 -C 12 -dicarboxylic acid, preferably at least one olefinically unsaturated C 4 -C 12 -dicarboxylic acid or more preferably at least one aliphatic C 3 -C 12 -dicarboxylic acid, for example malonic acid, methylmalonic acid, maleic acid, fumaric acid, succinic acid, Citraconic, metaconic, glutaric, itaconic, adipic, sebacic, pimelic, phthalic, terephthalic, isophthalic, especially succinic, glutaric and adipic acid,
- (b2) at least one further acidic compound selected from C 1 -C 3 monocarboxylic acids such as formic acid, acetic acid or propionic acid, C 3 -C 12 dicarboxylic acids, for example phthalic acid, terephthalic acid, isophthalic acid, preferably olefinically unsaturated C 4 -C 12 dicarboxylic acids or more preferably aliphatic C 3 -C 12 dicarboxylic acids, for example malonic acid, methylmalonic acid, maleic acid, fumaric acid, succinic acid, citraconic acid, metaconic acid, glutaric acid, itaconic acid, adipic acid, sebacic acid, pimelic acid, in particular succinic acid, glutaric acid and adipic acid.
Dabei ist für den Fall, dass man weitere saure Verbindung (b2) aus C3-C12-Dicarbonsäuren wählt, natürlich die C3-C12-Dicarbonsäure (b2) ungleich der C3-C12-Dicarbonsäure (b1).In this case, if one chooses further acidic compound (b2) from C 3 -C 12 dicarboxylic acids, of course, the C 3 -C 12 dicarboxylic acid (b2) is not equal to the C 3 -C 12 dicarboxylic acid (b1).
Dabei können C3-C12-Dicarbonsäuren (b1) und/oder weitere saure Verbindung (b2), gewählt aus C3-C12-Dicarbonsäuren und C1-C3-Monocarbonsäuren, jeweils als freie Säure oder in Form von deren Salzen eingesetzt werden. Als Salze sind beispielsweise Alkalimetallsalze wie Natrium- oder Kaliumsalze zu nennen. Prinzipiell sind weiterhin auch Salze von Aminen wie beispielsweise H1-yN(R2)y geeignet.In this case, C 3 -C 12 dicarboxylic acids (b1) and / or further acidic compound (b2), selected from C 3 -C 12 dicarboxylic acids and C 1 -C 3 monocarboxylic acids, in each case as the free acid or in the form of their salts be used. Examples of salts which may be mentioned are alkali metal salts, such as sodium or potassium salts. In principle, salts of amines such as, for example, H 1-y N (R 2 ) y are also suitable.
Dabei ist R2 jeweils gleich oder verschieden und unabhängig voneinander gewählt aus C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl und ganz besonders bevorzugt Methyl oder Ethyl,
und ω-Hydroxy-C2-C4-Alkylen wie beispielsweise 3-Hydroxypropyl, 4-Hydroxybutyl und insbesondere 2-Hydroxyethyl.In this case, R 2 is in each case identical or different and is independently selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl and most preferably methyl or ethyl,
and ω-hydroxy-C 2 -C 4 -alkylene such as 3-hydroxypropyl, 4-hydroxybutyl and especially 2-hydroxyethyl.
In einer Ausführungsform der vorliegenden Erfindung sind eingesetzte C3-C12-Dicarbonsäuren (b1) und/oder weitere saure Verbindung (b2), gewählt aus C3-C12-Dicarbonsäuren und C1-C3-Monocarbonsäuren, partiell neutralisiert.In one embodiment of the present invention, C 3 -C 12 -dicarboxylic acids (b1) and / or further acidic compound (b2) selected from C 3 -C 12 -dicarboxylic acids and C 1 -C 3 -monocarboxylic acids are partially neutralized.
In einer Ausführungsform der vorliegenden Erfindung behandelt man mit einem Gemisch, enthaltend zwei verschiedene C3-C12-Dicarbonsäuren und eine C1-C3-Monocarbonsäure.In one embodiment of the present invention, the mixture is treated with a mixture containing two different C 3 -C 12 dicarboxylic acids and a C 1 -C 3 monocarboxylic acid.
In einer Ausführungsform der vorliegenden Erfindung wählt man als C3-C12-Dicarbonsäure (b1) Adipinsäure und zwei weitere saure Verbindungen (b2), und zwar eine C3-C12-Dicarbonsäure und eine C1-C3-Monocarbonsäure.In one embodiment of the present invention, as C 3 -C 12 dicarboxylic acid (b1), adipic acid and two further acidic compounds (b2) are selected, namely a C 3 -C 12 dicarboxylic acid and a C 1 -C 3 monocarboxylic acid.
In einer Ausführungsform der vorliegenden Erfindung wählt man als C3-C12-Dicarbonsäure (b1) Adipinsäure und zwei weitere saure Verbindungen (b2), und zwar zwei C3-C12-Dicarbonsäuren, bevorzugt Glutarsäure und Bernsteinsäure.In one embodiment of the present invention adipic acid and two further acidic compounds (b2) are selected as C 3 -C 12 -dicarboxylic acid (b1), namely two C 3 -C 12 dicarboxylic acids, preferably glutaric acid and succinic acid.
Bevorzugt führt man das erfindungsgemäße Verfahren in wässriger Flotte durch. Als geeignete Geräte sind beispielsweise Fässer, bevorzugt drehbare Fässer und insbesondere drehbare Fässer mit strömungsbrechenden Einbauten zu nennen.The process according to the invention is preferably carried out in an aqueous liquor. Examples of suitable devices are drums, preferably rotatable drums and, in particular, rotatable drums with flow-breaking internals.
In einer Ausführungsform der vorliegenden Erfindung setzt man organischen Gerbstoff (a) und Gemisch (b) in einem Gewichtsverhältnis von 100 : 1 bis 1 : 1 ein, bevorzugt 5 : 1 bis 1,5 : 1.In one embodiment of the present invention, organic tanning agent (a) and mixture (b) are used in a weight ratio of 100: 1 to 1: 1, preferably 5: 1 to 1.5: 1.
In einer Ausführungsform der vorliegenden Erfindung behandelt man Tierhaut mit 0,1 bis 10 Gew.-% Gerbstoff (a), bezogen auf das Falzgewicht, bevorzugt 1,5 bis 5 Gew.-%.In one embodiment of the present invention, animal skin is treated with 0.1 to 10% by weight of tanning agent (a), based on the shaved weight, preferably 1.5 to 5% by weight.
In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren bei einer Temperatur im Bereich von 15 bis 50°C durch, bevorzugt 20 bis 35°C.In one embodiment of the present invention, the process according to the invention is carried out at a temperature in the range from 15 to 50.degree. C., preferably from 20 to 35.degree.
In einer Ausführungsform der vorliegenden Erfindung stellt man zur Durchführung des erfindungsgemäßen Verfahrens einen pH-Wert im Bereich von 2,0 bis 6,5, bevorzugt 2,8 bis 5,0 ein.In one embodiment of the present invention, a pH in the range from 2.0 to 6.5, preferably from 2.8 to 5.0, is used to carry out the process according to the invention.
In einer Ausführungsform der vorliegenden Erfindung kann man das erfindungsgemäße Verfahren über einen Zeitraum von 5 Minuten bis 24 Stunden ausführen, bevorzugt 60 Minuten bis 6 Stunden.In one embodiment of the present invention, the process according to the invention can be carried out over a period of 5 minutes to 24 hours, preferably 60 minutes to 6 hours.
Das erfindungsgemäße Verfahren lässt sich unter Verwendung von weichem Wasser durchführen, beispielsweise Wasser mit 0 bis 7 °dH (Deutscher Härte). In einer besonderen Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren unter Verwendung von mittelhartem Wasser durch, beispielsweise Wasser mit 7 bis 19 °dH, bevorzugt mit hartem Wasser von mindestens 20 bis 200 °dH.The process according to the invention can be carried out using soft water, for example water at 0 to 7 ° dH (German hardness). In a particular embodiment of the present invention, the process according to the invention is carried out using medium-hard water, for example water at 7 to 19 ° dH, preferably with hard water of at least 20 to 200 ° dH.
In einer Ausführungsform der vorliegenden Erfindung setzt man während der Durchführung des erfindungsgemäßen Verfahrens einen oder mehrere Lederfarbstoffe zu. In einer anderen Ausführungsform führt man das erfindungsgemäße Verfahren ohne Zusatz von Lederfarbstoffen durch.In one embodiment of the present invention, one or more leather dyes are added while the process according to the invention is being carried out. In another embodiment, the process according to the invention is carried out without the addition of leather dyes.
In einer Ausführungsform der vorliegenden Erfindung setzt man während der Durchführung des erfindungsgemäßen Verfahrens einen oder mehrere weitere chromfreie Gerbmittel zu, beispielsweise mineralische Gerbmittel wie beispielsweise Aluminiumverbindungen, insbesondere Aluminiumsulfat oder Alaun, Zirkonverbindungen wie beispielsweise Zr(SO4)2 oder ZrSO4(OH)2 oder Titanverbindungen wie beispielsweise Ti(SO4)2 oder TiSO4(OH)2, Harzgerbstoffe, Vegetabilgerbstoffe oder enzymatische Gerbmittel oder synthetische Gerbstoffe wie beispielsweise Kondensationsprodukte von Carbonylverbindungen wie beispielsweise Formaldehyd mit einer oder mehreren aromatischen Sulfonsäuren. Weiterhin kann man ein oder mehrere Dispergiermittel zusetzen, insbesondere ein oder mehrere nichtionische Tenside, beispielsweise mehrfach ethoxylierte aliphatische C6-C20-Alkohole, verzweigt oder unverzweigt.In one embodiment of the present invention are employed during the execution of the method according to the invention one or more other chrome-free tanning agent to, for example, mineral tanning agents such as aluminum compounds, particularly aluminum sulphate or alum, zirconium compounds such as Zr (SO 4) 2 or ZrSO 4 (OH) 2 or titanium compounds such as Ti (SO 4 ) 2 or TiSO 4 (OH) 2 , resin tanning agents, vegetable tanning or enzymatic tanning agents or synthetic tanning agents such as condensation products of carbonyl compounds such as formaldehyde with one or more aromatic sulfonic acids. It is also possible to add one or more dispersants, in particular one or more nonionic surfactants, for example polyethoxylated aliphatic C 6 -C 20 -alcohols, branched or unbranched.
In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren als Vorgerbung oder als Gerbung durch.In one embodiment of the present invention, the process according to the invention is carried out as a pretanning or as tanning.
Zur Durchführung des erfindungsgemäßen Verfahrens kann man organischen Gerbstoff (a) und Gemisch (b) getrennt oder vorzugsweise gemeinsam dosieren.For carrying out the process according to the invention, organic tanning agent (a) and mixture (b) can be separated or preferably metered together.
In einer speziellen Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren als Nachgerbung durch, beispielsweise bei einem pH-Wert im Bereich von 3 bis 6 und einer Temperatur im Bereich von 20 bis 65°C.In a specific embodiment of the present invention, the process according to the invention is carried out as a retanning, for example at a pH in the range from 3 to 6 and a temperature in the range from 20 to 65 ° C.
In einer speziellen Variante der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren so durch, dass man beim Pickeln behandelt mit
- (a) mindestens einem organischen Gerbstoff und
- (b) einem Gemisch von
- (b1) mindestens einer C3-C12-Dicarbonsäure
- (b2) und mindestens einer weiteren sauren Verbindung, gewählt aus C1-C3-Mono- oder C3-C12-Dicarbonsäuren, oder deren Salzen, die jeweils ungleich C3-C12-Dicarbonsäure (b1) sind.
- (a) at least one organic tanning agent and
- (b) a mixture of
- (b1) at least one C 3 -C 12 dicarboxylic acid
- (b2) and at least one further acidic compound selected from C 1 -C 3 mono- or C 3 -C 12 dicarboxylic acids, or their salts, each of which is not equal to C 3 -C 12 dicarboxylic acid (b1).
Zur Durchführung der letztgenannten Variante der vorliegenden Erfindung geht man von Blößen aus.To carry out the latter variant of the present invention, one starts from pelts.
Zur Durchführung der letztgenannten Variante der vorliegenden Erfindung kann man ein oder mehrere Alkalimetallhalogenide, insbesondere Kochsalz, zusetzen, beispielsweise 1 bis 10 Gew.-%, bezogen auf Blöße, bevorzugt 4 bis 7 Gew.-%. Man kann jedoch Alkalimetallhalogenid vollständig oder anteilig durch ionische Polymere ersetzen.To carry out the last-mentioned variant of the present invention, it is possible to add one or more alkali metal halides, in particular sodium chloride, for example 1 to 10% by weight, based on pelt, preferably 4 to 7% by weight. However, alkali metal halide can be completely or partially replaced by ionic polymers.
Die Verweilzeit der Blößen im Pickel beträgt bei der letztgenannten Variante der vorliegenden Erfindung beispielsweise 10 Minuten bis 24 Stunden, bevorzugt 15 Minuten bis 2 Stunden und besonders bevorzugt 15 bis 45 Minuten.The residence time of the pimples in the latter variant of the present invention is for example 10 minutes to 24 hours, preferably 15 minutes to 2 hours and more preferably 15 to 45 minutes.
Das Pickeln in der letztgenannten Variante der vorliegenden Erfindung verläuft unter ansonsten gerbereiüblichen Bedingungen, die Temperatur beträgt 10 bis 35°C und der Druck 1 bis 10 bar, besonders zweckmäßig ist Normaldruck.Pimpling in the latter variant of the present invention proceeds under otherwise tanning conditions, the temperature is 10 to 35 ° C and the pressure 1 to 10 bar, is particularly useful normal pressure.
Im Anschluss an die Durchführung von einem oder mehreren der vorstehend beschriebenen Schritte des erfindungsgemäßen Verfahrens kann man nach an sich bekannten Verfahren nachgerben, beispielsweise mit einem oder mehreren synthetischen Gerbstoffen, Harzgerbstoffen oder Vegetabilgerbstoffen oder Mischungen der vorgenannten Nachgerbmittel, weiterhin fetten, hydrophobieren und aufarbeiten.Subsequent to carrying out one or more of the above-described steps of the process according to the invention, it is possible to rethen by processes known per se, for example with one or more synthetic tanning agents, resin tanning or vegetable tanning agents or mixtures of the aforementioned tanning agents, further greasing, hydrophobicizing and working up.
Nach dem erfindungsgemäßen Verfahren hergestellte Halbfabrikate und Leder zeichnen sich auch bei der Verwendung von hartem Wasser durch besonders gute Weißegrade, gute Fülle und Weichheit und eine besonders geringe Tendenz zur Vergilbung aus und sind besonders gut geeignet zur Herstellung von Bekleidungsstücken wie beispielsweise Mäntel, Jacken, Gürteln, Schuhen, Handschuhen, weiterhin Möbeln und Autoinnenteilen. Weiterhin zeigen nach dem erfindungsgemäßen Verfahren hergestellte Halbfabrikate gute bis sehr gute Falzbarkeit und ein gutes bis sehr gutes Abwelkverhalten und lassen sich sehr gut zu Leder verarbeiten.Semi-finished products and leather produced by the process according to the invention are also distinguished by particularly good whiteness, good body and softness and a particularly low tendency to yellowing when using hard water and are particularly well suited for the production of clothing such as coats, jackets, belts , Shoes, gloves, furniture and car parts. Furthermore, semi-finished products produced by the process according to the invention show good to very good hemmability and a good to very good wilting behavior and can be processed very well to leather.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Formulierungen, insbesondere wässrige Formulierungen, enthaltend
- (a) mindestens einen organischen Gerbstoff, gewählt aus Dialdehyden und Verbindungen, die bei saurern pH-Wert Dialdehyde abspalten können, und
- (b) ein Gemisch von
- (b1) mindestens einer C3-C12-Dicarbonsäure
- (b2) und mindestens einer weiteren sauren Verbindung, gewählt aus C1-C3-Mono- oder C3-C12-Dicarbonsäuren, oder deren Salzen, die jeweils ungleich C3-C12-Dicarbonsäure (b1) sind.
- (A) at least one organic tanning agent selected from dialdehydes and compounds which can split dialdehydes at acidic pH, and
- (b) a mixture of
- (b1) at least one C 3 -C 12 dicarboxylic acid
- (b2) and at least one further acidic compound selected from C 1 -C 3 mono- or C 3 -C 12 dicarboxylic acids, or their salts, each of which is not equal to C 3 -C 12 dicarboxylic acid (b1).
Dabei sind organischer Gerbstoff (a), gewählt aus Dialdehyden und Verbindungen, die bei saurem pH-Wert Dialdehyde abspalten können, und Gemisch (b) wie vorstehend definiert.In this case, organic tanning agent (a) selected from dialdehydes and compounds which can cleave dialdehydes at acidic pH, and mixture (b) are as defined above.
Ganz besonders bevorzugt wählt man als Gerbstoff (a) Glutardialdehyd.Very particular preference is given to using tannin (a) glutaric dialdehyde.
In einer Ausführungsform der vorliegenden Erfindung umfasst Gemisch (b) mindestens zwei C3-C12-Dicarbonsäuren, gewählt aus Adipinsäure, Glutarsäure, Maleinsäure und Bernsteinsäure, oder deren Salze.In one embodiment of the present invention, mixture (b) comprises at least two C 3 -C 12 dicarboxylic acids selected from adipic acid, glutaric acid, maleic acid and succinic acid, or salts thereof.
Erfindungsgemäße Formulierungen können beispielsweise im Bereich von 30 bis 80 Gew.-% Wasser enthalten.Formulations according to the invention may contain, for example, in the range from 30 to 80% by weight of water.
Erfindungsgemäße Formulierungen können bevorzugt einen pH-Wert im Bereich von 2,5 bis 6,5, besonders bevorzugt im Bereich von 3,0 bis 5,0 aufweisen.Formulations according to the invention may preferably have a pH in the range from 2.5 to 6.5, more preferably in the range from 3.0 to 5.0.
Erfindungsgemäße Formulierungen können beispielsweise enthalten insgesamt im Bereich von 10 bis 70 Gew.-% organischen Gerbstoff (a), bevorzugt 15 bis 40 Gew.-%,For example, formulations according to the invention may contain in total from 10 to 70% by weight of organic tanning agent (a), preferably from 15 to 40% by weight,
im Bereich von 2,5 bis 50 Gew.-% Gemisch (b), bevorzugt 5 bis 25 Gew.-%,
wobei Angaben in Gew.-% auf gesamte erfindungsgemäße Formulierung bezogen sind, der Rest ist beispielsweise Wasser.in the range from 2.5 to 50% by weight of mixture (b), preferably from 5 to 25% by weight,
wherein in wt .-% are based on total formulation of the invention, the remainder is for example water.
In erfindungsgemäßer Formulierung enthaltenes Gemisch (b) kann beispielsweise enthalten
insgesamt im Bereich von 30 bis 99 Gew.-% C3-C12-Dicarbonsäure (b1),
insgesamt im Bereich von 1 bis 70 Gew.-% weiteren saure Verbindung (b2),
wobei Angaben in Gew.-% auf Gemisch (b) bezogen sind.For example, mixture (b) contained in the formulation of the invention may contain
in the range of 30 to 99% by weight of C 3 -C 12 -dicarboxylic acid (b1),
in total in the range from 1 to 70% by weight of further acidic compound (b2),
where in wt .-% on mixture (b) are related.
Erfindungsgemäße Formulierungen sind zur Durchführung des vorstehend beschriebenen erfindungsgemäßen Verfahrens besonders gut geeignet.Formulations according to the invention are particularly well suited for carrying out the process according to the invention described above.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Formulierungen zur Herstellung von Leder, beispielsweise zur Vorgerbung, Gerbung, Nachgerbung oder im Pickel. Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Leder, beispielsweise ein Verfahren zur Vorgerbung, Gerbung, Nachgerbung oder zum Pickeln, unter Verwendung von erfindungsgemäßer Formulierung. Dabei sind die Vorgerbung und die Gerbung besonders bevorzugt. Man kann jedoch auch speziell im Pickel eine erfindungsgemäße Formulierung einsetzen.Another object of the present invention is the use of formulations according to the invention for the production of leather, for example, for pretanning, tanning, retanning or pimples. Another object of the present invention is a process for the production of leather, for example a method for pretanning, tanning, retanning or pimpling, using formulation according to the invention. In this case, the pre-tanning and the tanning are particularly preferred. However, it is also possible to use a formulation according to the invention especially in the pimple.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Halbfabrikate und Leder, hergestellt nach dem erfindungsgemäßen Verfahren. Erfindungsgemäße Leder zeichnen sich auch bei der Verwendung von hartem Wasser durch gute Weißegrade, gute Fülle und Weichheit und eine besonders geringe Tendenz zur Vergilbung aus und sind besonders gut geeignet zur Herstellung von Bekleidungsstücken wie beispielsweise Mäntel, Jacken, Gürteln, Schuhen, insbesondere Futter und Oberleder, Handschuhen, weiterhin Möbeln und Autoinnenteilen. Weiterhin zeigen nach dem erfindungsgemäßen Verfahren hergestellte Halbfabrikate gute bis sehr gute Falzbarkeit und ein gutes bis sehr gutes Abwelkverhalten und lassen sich sehr gut zu Leder verarbeiten.Another object of the present invention are semi-finished products and leather, prepared by the novel process. Leathers according to the invention are also distinguished by good whiteness, good body and softness and a particularly low tendency to yellowing when using hard water and are particularly well suited for the production of clothing such as coats, jackets, belts, shoes, especially lining and upper leather , Gloves, furniture and car parts. Furthermore, semi-finished products produced by the process according to the invention show good to very good hemmability and a good to very good wilting behavior and can be processed very well to leather.
Ein weiterer Gegenstand der vorliegende Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen, im Folgenden auch erfindungsgemäßes Herstellverfahren genannt. Zur Durchführung des erfindungsgemäßen Herstellverfahrens kann man beispielsweise so vorgehen, dass man zunächst ein Gemisch (b) von mindestens einer C3-C12-Dicarbonsäure (b1) und mindestens einer weiteren sauren Verbindung (b2), gewählt aus C1-C3-Mono- oder C3-C12-Dicarbonsäuren, in Wasser herstellt, gegebenenfalls partiell oder vollständig mit Base wie beispielsweise basischem Alkalimetallsalz, beispielsweise Kalium- oder Natriumsalzen wie Carbonaten oder Hydrogencarbonaten, insbesondere Natriumhydroxid, oder mit Ammoniak oder organischem Amin neutralisiert, und danach mindestens einen organischen Gerbstoff (a) zumischt.A further subject of the present invention is a process for the preparation of formulations according to the invention, also referred to below as preparation process according to the invention. For carrying out the preparation process according to the invention, it is possible, for example, to initially prepare a mixture (b) of at least one C 3 -C 12 -dicarboxylic acid (b1) and at least one further acidic compound (b2) selected from C 1 -C 3 - mono- or di-C 3 -C 12 dicarboxylic acids, prepared in water, optionally partially or completely neutralized with base such as basic alkali metal salt, for example potassium or sodium salts, such as carbonates or bicarbonates, in particular sodium hydroxide, or with ammonia or organic amine, and thereafter at least an organic tanning agent (a) admixed.
Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention will be explained by working examples.
In einem Rührgefäß wurden 18 g (123 mmol) Adipinsäure (b1-1), 12 g (102 mmol) Bernsteinsäure (b2-1) und 3 g (65 mmol) konzentrierte Ameisensäure (b2-2) und 210 ml destilliertes Wasser miteinander vermischt. Man setzte 8 g einer 50 Gew.-% wässrigen Natronlauge zu (entsprechend 100 mmol NaOH). Anschließend dosierte man unter Rühren 240 g einer 50 Gew.-% wässrigen Lösung von Glutardialdehyd (a-1) zu. Man erhielt erfindungsgemäße wässrige Formulierung F-1. Erfindungsgemäße wässrige Formulierung F-1 wies einen pH-Wert von 3 bis 4 auf.In a stirred vessel, 18 g (123 mmol) of adipic acid (b1-1), 12 g (102 mmol) of succinic acid (b2-1) and 3 g (65 mmol) of concentrated formic acid (b2-2) and 210 ml of distilled water were mixed together , 8 g of a 50% by weight aqueous sodium hydroxide solution (corresponding to 100 mmol NaOH) were added. 240 g of a 50% strength by weight aqueous solution of glutaric dialdehyde (a-1) were then added while stirring. Aqueous formulation F-1 according to the invention was obtained. Aqueous formulation F-1 according to the invention had a pH of from 3 to 4.
In einem Rührgefäß wurden 22 g (151 mmol) Adipinsäure (b1-1), 8 g (69 mmol) Maleinsäure (b2-3) und 2,5 g (26 mmol) Natriumpropionat (b2-4) und 210 ml destilliertes Wasser miteinander vermischt. Man setzte 8 g einer 50 Gew.-% wässrigen Natronlauge zu (entsprechend 100 mmol NaOH). Anschließend dosierte man unter Rühren 240 g einer 50 Gew.-% wässrigen Lösung von Glutardialdehyd (a-1) zu. Man erhielt erfindungsgemäße wässrige Formulierung F-2. Erfindungsgemäße wässrige Formulierung F-2 wies einen pH-Wert von 3 bis 4 auf.In a stirred vessel 22 g (151 mmol) of adipic acid (b1-1), 8 g (69 mmol) of maleic acid (b2-3) and 2.5 g (26 mmol) of sodium propionate (b2-4) and 210 ml of distilled water with each other mixed. 8 g of a 50% by weight aqueous sodium hydroxide solution (corresponding to 100 mmol NaOH) were added. 240 g of a 50% strength by weight aqueous solution of glutaric dialdehyde (a-1) were then added while stirring. Aqueous formulation F-2 according to the invention was obtained. Aqueous formulation F-2 according to the invention had a pH of from 3 to 4.
Als Vergleichsformulierung V-F-3 wurde eine 50 Gew.-% wässrige Lösung von Glutardialdehyd verwendet, pH-Wert 3 bis 4.As Comparative Formulation V-F-3, a 50% by weight aqueous solution of glutaric dialdehyde was used, pH 3 to 4.
Im Folgenden beziehen sich Angaben in Gew.-% auf im jeweiligen Schritt eingesetzte Ausgangsmaterial (Spalt, Blöße, Haut), wenn nicht ausdrücklich anders angegeben. Behandlungsschritte erfolgten bei Zimmertemperatur, wenn nicht ausdrücklich anders angegeben.In the following, data in% by weight refer to starting material (gap, pelt, skin) used in each step, unless expressly stated otherwise. Treatment steps were carried out at room temperature, unless expressly stated otherwise.
Es wurde Wasser mit 24 °dH verwendet, wenn nicht ausdrücklich anders angegeben. LVE: Löhlein-Volhard-Einheiten, bestimmbar beispielsweise durch Methoden, die auf dem Abbau von Kasein durch ein zu untersuchendes Enzym und der anschließenden Titration der freigesetzten Carboxylgruppen mit 0,1 N NaOH beruht. Eine LVE entspricht 0,00575 ml 0,1 N NaOH.Water at 24 ° dH was used unless expressly stated otherwise. LVE: Löhlein-Volhard units, determinable, for example, by methods based on the degradation of casein by an enzyme to be tested and the subsequent titration of the liberated carboxyl groups with 0.1 N NaOH. One LVE corresponds to 0.00575 ml of 0.1 N NaOH.
40 kg Rinderhäute (süddeutsche Ware) wurden geweicht und mit 3 Gew.-% Kalk, 1,5 Gew.-% Natriumsulfid und 0,7 Gew.-% Natriumhydrogensulfid bei einer Flottenlänge von 150% über 16 Stunden geäschert. Anschließend wurde mit Wasser gewaschen, entfleischt und auf eine Spaltstärke von 2,5 mm gespalten. Man erhielt Spalte, die man in zwei Hälften pro Rind aufschnitt.40 kg of bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
In einem drehbaren Fass mit strömungsbrechenden Einbauten versetzte man den Spalt eines Rinds mit 100 Gew.-% Wasser, 0,4 Gew.-% Borsäure und 0,1 Gew.-% Ameisensäure und 0,1 Gew.-% Na2SO3. Man walkte über einen Zeitraum von 30 Minuten. Danach ließ man die Flotte ab und versetzte mit 50 Gew.-% Wasser, 1,0 Gew.-% Borsäure und 0,2 Gew.-% Ameisensäure und 0,1 Gew.-% Na2SO3. Man walkte weitere 45 Minuten und gab weitere 100 Gew.-% Wasser zu, weiterhin 0,5 Gew.-% kommerziell erhältliches Pankreatin mit 1000 LVE/g und 0,1 Gew.-% eines Tensids (mit 6 Äquivalenten Ethylenoxid ethoxyliertes 2-Ethylhexanol). Man walkte weitere 30 Minuten bei 32°C. Danach ließ man die Flotte ab und wusch die entkälkten Blößen BI-1 zweimal mit je 150 Gew.-% Wasser.In a rotary drum with flow-breaking internals, the gap of a cow with 100% by weight of water, 0.4% by weight of boric acid and 0.1% by weight of formic acid and 0.1% by weight of Na 2 SO 3 was added , One walked over a period of 30 minutes. Thereafter, the liquor was drained off and mixed with 50% by weight of water, 1.0% by weight of boric acid and 0.2% by weight of formic acid and 0.1% by weight of Na 2 SO 3 . A further 45 minutes were passed and an additional 100% by weight of water were added, furthermore 0.5% by weight of commercially available pancreatin with 1000 LVE / g and 0.1% by weight of a surfactant (ethoxylated with 6 equivalents of ethylene oxide). ethylhexanol). One walked another 30 minutes at 32 ° C. Thereafter, the liquor was drained off and washed the entblälkten pelts BI-1 twice with 150 wt .-% water.
40 kg Rinderhäute (süddeutsche Ware) wurden geweicht und mit 3 Gew.-% Kalk, 1,5 Gew.-% Natriumsulfid und 0,7 Gew.-% Natriumhydrogensulfid bei einer Flottenlänge von 150% über 16 Stunden geäschert. Anschließend wurde mit Wasser gewaschen, entfleischt und auf eine Spaltstärke von 2,5 mm gespalten. Man erhielt Spalte, die man in zwei Hälften pro Rind aufschnitt.40 kg of bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
In einem drehbaren Fass mit strömungsbrechenden Einbauten versetzte man den Spalt eines Rinds mit 100 Gew.-% Wasser, 0,35 Gew.-% NH4Cl und 0,15 Gew.-% (NH4)2SO4 und 0,1 Gew.-% Na2SO3. Man walkte über einen Zeitraum von 30 Minuten. Danach ließ man die Flotte ab und versetzte mit 50 Gew.-% Wasser, 0,8 Gew.-% NH4Cl und 0,4 Gew.-% (NH4)2SO4 und 0,1 Gew.-% Na2SO3. Man walkte weitere 45 Minuten und gab weitere 100 Gew.-% Wasser zu, weiterhin 0,5 Gew.-% kommerziell erhältliches Pankreatin mit 1000 LVE/g und 0,1 Gew.-% eines Tensids (mit 6 Äquivalenten Ethylenoxid ethoxyliertes 2-Ethylhexanol). Man walkte weitere 30 Minuten bei 32°C. Danach ließ man die Flotte ab und wusch die entkälkten Blößen BI-2 zweimal mit je 150 Gew.-% Wasser.In a rotary drum with flow-breaking internals, the gap of a cow with 100 wt .-% water, 0.35 wt .-% NH 4 Cl and 0.15 wt .-% (NH 4 ) 2 SO 4 and 0.1 was added Wt% Na 2 SO 3 . One walked over a period of 30 minutes. Thereafter, the liquor was released and added with 50 wt .-% water, 0.8 wt .-% NH 4 Cl and 0.4 wt .-% (NH 4 ) 2 SO 4 and 0.1 wt .-% Na 2 SO 3 . A further 45 minutes were passed and an additional 100% by weight of water were added, furthermore 0.5% by weight of commercially available pancreatin with 1000 LVE / g and 0.1% by weight of a surfactant (ethoxylated with 6 equivalents of ethylene oxide). ethylhexanol). It was allowed to cool for another 30 minutes at 32 ° C. Thereafter, the liquor was drained off and washed the entkälkten pelts BI-2 twice with 150 wt .-% water.
40 kg Rinderhäute (süddeutsche Ware) wurden geweicht und mit 3 Gew.-% Kalk, 1,5 Gew.-% Natriumsulfid und 0,7 Gew.-% Natriumhydrogensulfid bei einer Flottenlänge von 150% über 16 Stunden geäschert. Anschließend wurde mit Wasser gewaschen, entfleischt und auf eine Spaltstärke von 2,5 mm gespalten. Man erhielt Spalte, die man in zwei Hälften pro Rind aufschnitt.40 kg of bovine hides (southern German ware) were softened and cremated with 3% by weight of lime, 1.5% by weight of sodium sulfide and 0.7% by weight of sodium hydrogen sulfide at a liquor length of 150% over 16 hours. It was then washed with water, defiled and split to a gap thickness of 2.5 mm. Columns were obtained, which were cut in half for each beef.
In einem drehbaren Fass mit strömungsbrechenden Einbauten versetzte man den Spalt eines Rinds mit 100 Gew.-% Wasser, 0,15 Gew.-% Ethylencarbonat und 0,15 Gew.-% Propylencarbonat und 0,1 Gew.-% Na2SO3. Man walkte über einen Zeitraum von 30 Minuten. Danach ließ man die Flotte ab und versetzte mit 50 Gew.-% Wasser, 0,6 Gew.-% Ethylencarbonat und 0,6 Gew.-% Propylencarbonat und 0,1 Gew.-% Na2SO3. Man walkte weitere 45 Minuten und gab weitere 100 Gew.-% Wasser zu, weiterhin 0,5 Gew.-% kommerziell erhältliches Pankreatin mit 1000 LVE/g und 0,1 Gew.-% eines Tensids (mit 6 Äquivalenten Ethylenoxid ethoxyliertes 2-Ethylhexanol). Man walkte weitere 30 Minuten bei 32°C. Danach ließ man die Flotte ab und wusch die entkälkten Blößen BI-3 zweimal mit je 150 Gew.-% Wasser.In a rotary drum with flow-breaking internals, the gap of a cow with 100 wt .-% water, 0.15 wt .-% of ethylene carbonate and 0.15 wt .-% propylene carbonate and 0.1 wt .-% Na 2 SO 3 was added , One walked over a period of 30 minutes. Thereafter, the liquor was drained off and mixed with 50% by weight of water, 0.6% by weight of ethylene carbonate and 0.6% by weight of propylene carbonate and 0.1% by weight of Na 2 SO 3 . A further 45 minutes were passed and an additional 100% by weight of water were added, furthermore 0.5% by weight of commercially available pancreatin with 1000 LVE / g and 0.1% by weight of a surfactant (ethoxylated with 6 equivalents of ethylene oxide). ethylhexanol). It was allowed to cool for another 30 minutes at 32 ° C. Thereafter, the liquor was drained off and washed the entkälkten pelts BI-3 twice with 150 wt .-% water.
Man bereitete die Pickelflotten PF-1 bis PF-4 durch Vermischen der Substanzen nach Tabelle 1 und Auffüllen mit Wasser. Die so erhältlichen Pickelflotten PF-1 bis PF-4 hatten einen pH-Wert von 2,8.
Die entkälkten Blößen aus BI-1 bis BI-3 wurden jeweils halbiert und in getrennten Fässern über einen Zeitraum von 90 Minuten mit 150 Gew.-% von einer der Pickelflotten PF-1 bis PF-4 behandelt (s. Tabelle 2). Man erhielt die Pickelblößen PB-1 bis PB-12. Man schnitt PB-1 bis PB-12 jeweils in drei gleich große Stücke zu je 1,5 kg Blößengewicht.The macerated pelts from BI-1 to BI-3 were each halved and treated in separate barrels over a period of 90 minutes with 150 wt .-% of one of the pimples PF-1 to PF-4 (see Table 2). The pimples PB-1 to PB-12 were obtained. Each PB-1 to PB-12 was cut into three equal pieces of 1.5 kg pelt weight each.
In einem drehbaren Fass mit strömungsbrechenden Einbauten versetzte man ein Stück Pickelblöße aus II.2 mit 120 Gew.-% Pickelflotte aus II.2 und danach mit 3 Gew.-% einer erfindungsgemäßen Formulierung F-1 oder F-2 (erfindungsgemäße Beispiele) oder Vergleichsformulierung V-F-3. Man walkte 30 Minuten und setzte anschließend 3 Gew.-% Sulfongerbstoff aus
Die Schrumpftemperaturen wurden gemäß der Vorschrift aus DIN 53 336 (Jahr 1977) bestimmt, wobei die Vorschrift wie folgt modifiziert wurde:
- Punkt 4.1:
- Die Probestücke hatten die Abmessungen 3 cm · 1 cm; die Dicke wurde nicht bestimmt.
- Punkt 4.2:
- es wurde nur eine anstatt 2 Proben pro Ledermuster geprüft.
- Punkt 6:
- entfiel
- Punkt 7:
- die Trocknung im Vakuumexsikkator entfiel.
- Punkt 8:
- bei Rückgang des Zeigers wurde die Schrumpfungstemperatur gemes- sen.
- Point 4.1:
- The specimens had the dimensions 3 cm x 1 cm; the thickness was not determined.
- Point 4.2:
- Only one sample per leather sample was tested instead.
- Point 6:
- accounted
- Point 7:
- the drying in the vacuum desiccator was eliminated.
- Point 8:
- when the pointer dropped, the shrinkage temperature was measured.
Zur Beurteilung der fertigen Leder gerbte man nach der in Beispiel II.4 angegebenen Vorschrift nach.For the evaluation of the finished leather, the product was tanned according to the instructions given in Example II.4.
Die Ergebnisse der anwendungstechnischen Prüfungen sind in Tabelle 2 und 3 aufgeführt.The results of the performance tests are listed in Tables 2 and 3.
Halbfabrikat nach Beispiel II.3 wurde in einem drehbaren Fass mit strömungsbrechenden Einbauten mit 150 Gew.-% Wasser versetzt. Man gab jeweils im Abstand von 15 Minuten zu:
- 2 Gew.-% Fettungsmittel C2 aus
WO 03/70988 - 4 Gew.-% einer 30 Gew.-% wässrigen, mit NaOH teilneutralisierten Lösung eines Methacrylsäure-Homopolymers mit den folgenden analytischen Daten: Mn 10.000 g/mol; K-Wert nach Fikentscher: 12 (bestimmt als 1 Gew.-% wässrige Lösung), Viskosität der 30 Gew.-% Lösung: 65 mPa·s (DIN EN ISO 3219, 23°C), pH-Wert 5,1.
- 5 Gew.-% Sulfongerbstoff aus
EP-B 0 459 168
- 2% by weight of fatliquoring agent C2
WO 03/70988 - 4 wt .-% of a 30 wt .-% aqueous, neutralized with NaOH solution of a methacrylic acid homopolymer having the following analytical data: M n 10,000 g / mol; K value according to Fikentscher: 12 (determined as 1% by weight aqueous solution), viscosity of the 30% by weight solution: 65 mPa · s (DIN EN ISO 3219, 23 ° C.), pH 5.1.
- 5% by weight of sulfone tanning agent
EP-B 0 459 168
Danach dosierte man: 4 Gew.-% eines Vegetabilgerbstoffs (Quebracho), 4 Gew.-% Melamin-Formaldehyd-Harz (Harzgerbstoff), weitere 2 Gew.-% Fettungsmittel C2 aus
- 70 Gewichtsteile Farbstoff aus
EP-B 0 970 148 - 30 Gewichtsteile Acid Brown 75 (Eisenkomplex), Color Index 1.7.16.
- 70 parts by weight of dye
EP-B 0 970 148 - 30 parts by weight Acid Brown 75 (iron complex), Color Index 1.7.16.
Man walkte eine Stunde bei 30°C, stellte mit Ameisensäure einen pH-Wert von 3,6 ein und gab weitere 5,5 Gew.-% Fettungsmittel C2 aus
Die so erhältlichen Leder wurden zweimal mit 100 Gew.-% Wasser gewaschen, über Nacht feucht gelagert und nach dem Abwalken auf Spannrahmen bei 50°C getrocknet. Man erhielt die erfindungsgemäßen Leder L-1 bis L-24 und die Vergleichsleder V-L-25 bis V-L-36. Nach dem Stollen wurden die Leder wie unten stehend beurteilt.The leathers thus obtained were washed twice with 100 wt .-% water, stored moist overnight and dried after Abwalken on tenter at 50 ° C. The leathers L-1 to L-24 according to the invention and comparative leathers V-L-25 to V-L-36 were obtained. After the tunnel, the leathers were judged as below.
Die Bewertung erfolgte nach einem Notensystem von 1 (sehr gut) bis 5 (mangelhaft). Die Bewertung des Weißegrads und der Egalität erfolgte visuell. Das Abwelkverhalten wurde bei jeweils identischem Abwelkdruck von 100 bar anhand der Güte der Entwässerung und der Faserstruktur auf der Fleischseite beurteilt (isolierte Fasern mit geringen Faser-Verklebungen stellen den idealen Zustand dar). Die Falzbarkeit wurde anhand der Egalität des Falzergebnisses über die Fläche, den Falzspänen (isolierte Fasern, lockere Struktur), der Morphologie der Fleischseite (durch die Temperaturentwicklung kann es ungewollt zu irreversiblen Verhärtungen kommen) und dem Verbleib von (störenden) Falzspänen auf der Fleischseite beurteilt.The rating was based on a grading system from 1 (very good) to 5 (poor). The evaluation of whiteness and levelness was done visually. The Abwelkverhalten was judged at an identical Abwelkdruck of 100 bar on the quality of drainage and the fiber structure on the meat side (isolated fibers with low fiber bonds represent the ideal state). The folding ability was based the levelness of the folding result over the surface, the shavings (isolated fibers, loose structure), the morphology of the meat side (due to the temperature development, it may unintentionally come to irreversible hardening) and the whereabouts of (interfering) shavings on the meat side judged.
Die Beurteilung der Fülle; Narbenfestigkeit und Weichheit erfolgte jeweils im direkten Vergleich durch entsprechend geschulte Leder-Techniker.
Claims (12)
- A process for the production of leather, wherein, after liming, deliming and, if appropriate, pickling, or during the pickling, animal hides are treated with(a) at least one organic tanning agent selected from aldehydes, dialdehydes and compounds which can eliminate formaldehyde, acetaldehyde or dialdehydes at acidic pH in the presence of water,
and(b) a mixture of(b1) at least one C3-C12-dicarboxylic acid(b2) and at least one further acidic compound selected from C1-C3-mono- or C3-C12-dicarboxylic acids or salts thereof which in each case are not C3-C12-dicarboxylic acid (b1). - The process according to claim 1, wherein the organic tanning agent (a) selected is glutaraldehyde.
- The process according to claim 1 or 2, wherein mixture (b) comprises at least two C3-C12-dicarboxylic acids selected from adipic acid, glutaric acid, maleic acid and succinic acid, or salts thereof.
- The process according to any of claims 1 to 3, wherein the treatment is a pretanning or tanning.
- A formulation comprising(a) at least one organic tanning agent selected from dialdehydes and compounds which can eliminate dialdehydes at acidic pH, and(b) a mixture of(b1) at least one C3-C12-dicarboxylic acid(b2) and at least one further acidic compound selected from C1-C3-mono- or C3-C12-dicarboxylic acids or salts thereof which in each case are not C3-C12-dicarboxylic acid (b1).
- The formulation according to claim 5, wherein the organic tanning agent (a) selected is glutaraldehyde.
- The formulation according to either of claims 5 and 6, wherein mixture (b) comprises at least two C3-C12-dicarboxylic acids selected from adipic acid, glutaric acid, maleic acid and succinic acid, or salts thereof.
- The use of formulations according to any of claims 5 to 7 for the production of leather.
- A process for the production of leather using formulations according to any of claims 5 to 7.
- The process according to claim 9, wherein a formulation according to any of claims 5 to 7 is used in the pickle.
- A semifinished product or leather produced by a process according to any of claims 1 to 4 or 9 and 10.
- A process for the preparation of formulations according to any of claims 5 to 7, wherein first a mixture (b) of at least one C3-C12-dicarboxylic acid (b1) and at least one further acidic compound (b2) selected from C1-C3-mono- or C3-C12-dicarboxylic acids in water is prepared and, if appropriate, partly or completely neutralized and then at least one organic tanning agent (a), selected from dialdehydes and compounds which eliminate dialdehydes at acidic pH, is admixed.
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| DE102005032585A DE102005032585A1 (en) | 2005-07-11 | 2005-07-11 | Process for the production of leather |
| PCT/EP2006/063956 WO2007006718A1 (en) | 2005-07-11 | 2006-07-06 | Method for producing leather |
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| US (2) | US20080207812A1 (en) |
| EP (1) | EP1904658B1 (en) |
| CN (1) | CN101223289B (en) |
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| JP5683793B2 (en) * | 2009-06-03 | 2015-03-11 | ウィンテックポリマー株式会社 | Molded parts for electric car parts |
| US20110237693A1 (en) * | 2010-03-23 | 2011-09-29 | Basf Se | Blends made of polyarylene ethers and of polyarylene sulfides |
| CN101812553B (en) * | 2010-04-23 | 2013-01-09 | 海宁森德皮革有限公司 | Production method for non-chrome-tanned ecological automobile seat cushion leather |
| DE102013014641B4 (en) | 2013-09-04 | 2018-07-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Wood product or natural fiber composite product and use of a formaldehyde-free aminoplast resin for their preparation |
| EP2853605A1 (en) * | 2013-09-30 | 2015-04-01 | Rhodia Poliamida E Especialidades Ltda | Tanning process for obtaining leather |
| EP2853604A1 (en) * | 2013-09-30 | 2015-04-01 | Rhodia Poliamida E Especialidades Ltda | Tanning process |
| CN104561397B (en) * | 2013-10-18 | 2017-12-19 | 罗门哈斯公司 | The tanning again of chromium-free leather |
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| US10280474B2 (en) * | 2015-07-13 | 2019-05-07 | Council Of Scientific & Industrial Research | Dispersing agent composition for tanning of hides/skins and process for the preparation thereof |
| ITUB20152180A1 (en) * | 2015-07-14 | 2017-01-14 | Db Patents Ltd | IMPROVED METHOD TO SKIN ANIMAL SKIN. |
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| DE10132928A1 (en) * | 2001-07-03 | 2003-01-16 | Buehler Ag | Modified post-condensed polyester |
| BR0309772A (en) * | 2002-05-07 | 2005-03-22 | Basf Ag | Tanning agent, processes for preparing the same, for tanning, tanning or shortening animal skins, and for preparing a powdery active ingredient, powdery active ingredient, leather, and uses of a tanning agent and a powdery active ingredient. |
| DE102004050025A1 (en) * | 2004-10-13 | 2006-04-20 | Basf Ag | Flowable thermoplastics with halogen flame protection |
| DE102004051241A1 (en) * | 2004-10-20 | 2006-05-04 | Basf Ag | Flowable polyamides with hyperbranched polyesters / polycarbonates |
-
2005
- 2005-07-11 DE DE102005032585A patent/DE102005032585A1/en not_active Withdrawn
-
2006
- 2006-07-03 AR ARP060102855A patent/AR057429A1/en active IP Right Grant
- 2006-07-06 CN CN2006800254586A patent/CN101223289B/en active Active
- 2006-07-06 DE DE502006006803T patent/DE502006006803D1/en active Active
- 2006-07-06 WO PCT/EP2006/063956 patent/WO2007006718A1/en active Application Filing
- 2006-07-06 AT AT06777608T patent/ATE465277T1/en active
- 2006-07-06 BR BRPI0612827A patent/BRPI0612827B1/en active IP Right Grant
- 2006-07-06 EP EP06777608A patent/EP1904658B1/en active Active
- 2006-07-06 US US11/995,503 patent/US20080207812A1/en not_active Abandoned
- 2006-07-06 US US11/995,511 patent/US20090172890A1/en not_active Abandoned
- 2006-07-06 ES ES06777608T patent/ES2343433T3/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US20080207812A1 (en) | 2008-08-28 |
| US20090172890A1 (en) | 2009-07-09 |
| CN101223289A (en) | 2008-07-16 |
| CN101223289B (en) | 2012-08-22 |
| BRPI0612827B1 (en) | 2016-12-13 |
| AR057429A1 (en) | 2007-12-05 |
| DE102005032585A1 (en) | 2007-01-25 |
| BRPI0612827A2 (en) | 2012-10-09 |
| ES2343433T3 (en) | 2010-07-30 |
| EP1904658A1 (en) | 2008-04-02 |
| ATE465277T1 (en) | 2010-05-15 |
| DE502006006803D1 (en) | 2010-06-02 |
| WO2007006718A1 (en) | 2007-01-18 |
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