EP4112748A1 - Tanning agent, use of a tanning agent, process for the tanning of animal skins and furs and leather obtained thereof - Google Patents
Tanning agent, use of a tanning agent, process for the tanning of animal skins and furs and leather obtained thereof Download PDFInfo
- Publication number
- EP4112748A1 EP4112748A1 EP21183144.1A EP21183144A EP4112748A1 EP 4112748 A1 EP4112748 A1 EP 4112748A1 EP 21183144 A EP21183144 A EP 21183144A EP 4112748 A1 EP4112748 A1 EP 4112748A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tanning
- weight
- tanning agent
- reaction solution
- leather
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000010985 leather Substances 0.000 title claims abstract description 46
- 241001465754 Metazoa Species 0.000 title claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims abstract description 16
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000001241 acetals Chemical class 0.000 claims abstract description 10
- 150000002009 diols Chemical group 0.000 claims abstract description 10
- 150000002373 hemiacetals Chemical class 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 96
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 46
- 206010000496 acne Diseases 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 150000004676 glycans Chemical class 0.000 claims description 8
- 239000005017 polysaccharide Substances 0.000 claims description 8
- 150000002772 monosaccharides Chemical class 0.000 claims description 7
- 229920001282 polysaccharide Polymers 0.000 claims description 7
- 235000013311 vegetables Nutrition 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 229920001542 oligosaccharide Polymers 0.000 claims description 6
- 150000002482 oligosaccharides Chemical class 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 35
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- 230000035515 penetration Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 229960000587 glutaral Drugs 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 241000209140 Triticum Species 0.000 description 6
- 235000021307 Triticum Nutrition 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 102000008186 Collagen Human genes 0.000 description 5
- 108010035532 Collagen Proteins 0.000 description 5
- 229920001436 collagen Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 235000000346 sugar Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229940120503 dihydroxyacetone Drugs 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- -1 formaldehyde, hydrogen Chemical class 0.000 description 3
- 229940074076 glycerol formal Drugs 0.000 description 3
- 229960004275 glycolic acid Drugs 0.000 description 3
- 229960004903 invert sugar Drugs 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 235000020374 simple syrup Nutrition 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 240000005852 Mimosa quadrivalvis Species 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001231 Polysaccharide peptide Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 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
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical class [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 108010022457 polysaccharide peptide Proteins 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 231100000828 respiratory toxicity Toxicity 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent 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
- 238000001149 thermolysis Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
Definitions
- the invention relates to a tanning agent and the use of such a tanning agent for tanning animal hides and skins, a process for tanning animal hides and skins to produce leather, and a leather obtained therefrom.
- animal collagen in skins is modified in such a way that the leather resulting from the tanning is resistant to heat, environmental influences and microorganisms, and the suppleness of the tanned skin is retained after the leather has dried.
- mineral tanning especially chrome tanning
- vegetable tanning for example with tara, mimosa, quebracho or chestnut
- synthetic tanning especially with glutardialdehyde, which are based on different strategies.
- Chrome tanning has the greatest economic importance. Hydrated chromium complexes sandwiched between the carboxyl groups of glutamic acid and aspartic acid in the skin's collagen peptide framework result in resilient and soft leather. In addition to the good leather quality to be achieved, a fast and cost-effective process control was established with chrome tanning material. Other mineral tanning agents, such as those based on aluminum or zirconium, also work according to the same principle.
- (heavy) metals has a number of disadvantages. It is known, for example, that chromium(VI) can trigger allergic reactions when it comes into contact with the skin. Usually, chromium(III) sulfates are used in the tanning process. However, chromium(VI) can be formed by oxidation of chromium(III) or enters the tanning process via tanning agent impurities. Other disadvantages of (heavy) metal-loaded tanning are the time-consuming process Treatment of the waste water via a plant for the recovery of chromium and other heavy metals as well as the expensive disposal of leather residues such as shavings using landfill methods or incineration.
- Vegetable tanning uses tannins extracted from plants. However, vegetable tanning requires long and complex tanning processes, which is why vegetable tanning has largely been replaced by chrome tanning.
- Another widespread tanning method is synthetic tanning with glutaraldehyde, in which the bifunctionality of glutaraldehyde serves to cross-link the peptide fibers of the hide.
- the mode of action is mainly due to the reactivity at the nitrogen functionalities of the underlying amino acids.
- the glutaraldehyde reacts on two different fibers and thus permanently connects them by forming a covalent bond.
- composition for tanning leather which comprises a zeolite which has been treated with a concentrated monocarboxylic acid.
- the composition is intended to provide an alternative to chrome tanning.
- the time-consuming production and post-treatment of the zeolite is still necessary, which has a negative effect on the overall ecological balance of the composition.
- the WO 2012/163823 describes graft copolymers obtained by means of free radical polymerization, with a first monomer A), which is a (meth)acrylic acid or a mixture of a (meth)acrylic acid and mono and/or polyethylenically unsaturated monomers, and a second Monomer B) are used, which is generated by degradation of a polysaccharide or polypeptide.
- a first monomer A which is a (meth)acrylic acid or a mixture of a (meth)acrylic acid and mono and/or polyethylenically unsaturated monomers
- a second Monomer B which is generated by degradation of a polysaccharide or polypeptide.
- the production of such graft copolymers is expensive and requires a high use of chemicals.
- adequate crosslinking of the collagen fibers cannot be achieved with the graft copolymers described.
- the graft copolymers are therefore only suitable for retanning and require the additional
- tanning agents should be able to be produced from compounds that are available worldwide, are biodegradable and/or can be obtained from renewable raw materials.
- a tanning agent comprising a reaction solution which contains a tanning component selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof, the reaction solution being obtained by partial Oxidation and/or pyrolysis of an organic substance having a vicinal diol group.
- the tanning-active component is, in particular, biodegradable and environmentally compatible. This enables environmentally friendly and resource-saving tanning.
- classic tanning processes such as chrome tanning
- the effort required to dispose of waste generated during the use of the tanning agent is significantly reduced, which means that a more cost-effective tanning process is made possible.
- organic substances can be used as the starting product, which occur naturally and/or can be produced from renewable raw materials.
- fossil raw materials for example starting materials based on petroleum and/or natural gas, can be avoided or at least reduced in the production of tanning agents.
- the tanning-active component is also hydrophilic and quickly penetrates the skin layers to be tanned. As a result, the exposure time of the tanning liquor can be reduced compared to conventional tanning agents. In addition, a uniform distribution of the tanning-active component in the skin layers is achieved, so that a uniformly through-tanned leather can be obtained with a shrinkage temperature that remains the same across all skin layers.
- the organic substance having a vicinal diol group is an aliphatic substance having a vicinal diol group.
- the organic substance having a vicinal diol group is selected from the group consisting of glycerol, ethylene glycol, monosaccharides, oligosaccharides, polysaccharides, and combinations thereof.
- organic substances occur, for example, as a by-product in large-scale processes, such as in the production of biodiesel or in natural soap production, and/or can be obtained from renewable raw materials.
- the organic substance having a vicinal diol group is glycerol and/or ethylene glycol.
- the organic substance is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides and combinations thereof,
- Monosaccharides according to the invention are in particular monosaccharides with four to seven carbon atoms and oligosaccharides and polysaccharides according to the invention are in particular oligosaccharides or polysaccharides of these monosaccharides.
- the reaction solution is obtained by partial oxidation.
- the partial oxidation produces in particular a reaction solution which contains glyceraldehyde, an acetal of glyceraldehyde and/or a hemiacetal of glyceraldehyde as the tanning-active component.
- the partial oxidation takes place according to the in the WO 2009/100068 A1 described method, with adjustments in the reaction to optimize the composition of the reaction solution are possible.
- This process uses glycerine as the starting product, with the glycerine used preferably being produced as a by-product of large-scale processes such as the production of biodiesel and natural soap production, in which renewable raw materials are used.
- the partial oxidation takes place in particular using hydrogen peroxide as the oxidizing agent in combination with a suitable catalyst, for example an iron catalyst such as iron(II) sulfate.
- a suitable catalyst for example an iron catalyst such as iron(II) sulfate.
- the catalyst in particular the iron catalyst, can be used in a proportion of up to 10 percent by weight, preferably up to 5 percent by weight, based on the total weight of the reaction solution. Good results can be achieved with 750 to 5000 ppm iron are achieved, based on the total weight of the reaction solution, preferably from 1500 to 5000 ppm, particularly preferably from 3500 to 5000 ppm.
- the partial oxidation takes place in particular at a temperature of from 35 to 90.degree. C., preferably from 40 to 70.degree. C., particularly preferably from 45 to 50.degree.
- Purified or unpurified glycerol can be used as the starting product, with a proportion of 10% by weight to 99.5% by weight of glycerol in the starting product used. Preference is given to using purified glycerol with a purity of 90% by weight to 99.5% glycerol.
- the proportion of glycerol in the reaction solution at the beginning of the oxidation is preferably from 80% by weight to 90% by weight based on the weight of the reaction solution.
- the reaction solution is obtained in particular by pyrolysis.
- the pyrolysis takes place as an aqueous thermolysis as in WO 02/40436 A1 described.
- a finely divided aqueous solution of the organic substance is sprayed into a reactor which has a temperature in the range from 500 to 600 °C.
- the pyrolysis product formed in the reactor, which is still in the form of finely divided droplets, is then condensed out to obtain the reaction solution.
- the pyrolysis as in the WO 2018/104508 A1 be carried out as described.
- the tanning-active component is obtained from the organic substance by means of thermal fragmentation, a low content of 200 ppm or less of salts in the reaction solution being set in particular in order to increase the yield of tanning-active component.
- the thermal fragmentation takes place in particular at a temperature of 300°C or higher, for example at a temperature in the range from 350 to 800°C, preferably from 400 to 600°C, particularly preferably from 500 to 600°C.
- reaction solution which were obtained using different methods, can also be mixed to form the reaction solution to obtain a desired composition, each of the partial reaction solutions being obtained as described above.
- a more flexible process control can be realized depending on the available organic substances and a flexible adaptation of the chemical and physical properties of the reaction solution can take place.
- the reaction solution can contain at least one further tanning-promoting component in addition to the tanning-active component.
- the tanning-promoting component like the tanning-active component, also has a penetration effect into a pelt to be tanned or a substrate to be tanned, but in contrast to the tanning-active component itself does not carry out any tanning.
- the tanning-promoting component promotes the penetration effect of the tanning-active component into the pelt to be tanned or into the substrate to be tanned, or increases the proportion of the tanning-active component remaining in the pelt.
- the tanning-promoting component serves in particular to reduce the additional consumption of chemicals, since a comparable tanning result can be achieved with a lower use of tanning-active components.
- the tanning-promoting component can have a positive effect on the biodegradability of a leather obtained and on the tanning and/or process liquors used in the production of the leather, on the coloring of the leather and/or the durability of pretanned material.
- the tanning-promoting substance is preferably selected from the group consisting of (poly)hydroxycarboxylic acids, carboxylic acids, ketones, acetals, hemiacetals and ketals, each having 1 to 8 carbon atoms, and mixtures thereof.
- the tanning substance is preferably also biodegradable and environmentally friendly.
- the tanning-promoting substance is preferably produced as a by-product in the reaction solution from the organic substance, so that no additional addition of tanning-promoting substance is necessary and the production process of the tanning agent is further simplified.
- the tanning substance can be added to the tanning agent in addition to the reaction solution.
- the reaction solution can contain a solvent, preferably water and glycols such as polyethylene glycol and mixtures thereof.
- the proportion of the solvent in the reaction solution is preferably at most 80% by weight, more preferably at most 65% by weight, particularly preferably 20 to 50% by weight.
- the tanning agent consists of the reaction solution.
- the reaction solution only substances that are obtained directly from the partial oxidation and/or the pyrolysis are used in this variant.
- the organic substance used is naturally occurring and/or was made from a renewable raw material, it can be ensured in this way that the production of the tanning agent avoids the use of fossil raw materials as far as possible and that the greatest possible environmental compatibility and has biodegradability.
- the tanning agent may comprise a first tanning component and a second tanning component, the first tanning component being the tanning component of the reaction solution and the second tanning component being selected from the group consisting of synthetic tanning agents, vegetable tanning agents and mineral tanning agents , in particular glutardialdehyde and/or chromium salts.
- mixtures of conventional tanning agents and the tanning-active component from the reaction solution can also be used according to the invention.
- the disadvantages of conventional tanning agents can at least be minimized.
- the tanning agent can be optimized in terms of environmental compatibility and consumption of fossil raw materials, while at the same time the physical and chemical properties of the tanning agent can be adjusted with regard to specific requirements of the envisaged tanning process.
- the first tanning component is preferably present in the tanning agent in a higher proportion (w/w) than the second tanning component.
- the first tanning-active component is preferably the tanning-active main component.
- the second tanning-active component is, for example, a syntan (synthetic auxiliary tanning agent), a vegetable tanning agent such as hydrolyzable tanning agents (pyrogallol tanning agents), a condensable tanning agent (pyrocatechin tanning agents), a phenolic or non-phenolic tanning agent, a polycondensation or polymerization compound, or a combination from that.
- a syntan synthetic auxiliary tanning agent
- a vegetable tanning agent such as hydrolyzable tanning agents (pyrogallol tanning agents), a condensable tanning agent (pyrocatechin tanning agents), a phenolic or non-phenolic tanning agent, a polycondensation or polymerization compound, or a combination from that.
- Suitable synthetic auxiliary tanning agents can be produced by sulfonation and condensation of aromatic products.
- compounds of mostly polynuclear hydrocarbons naphthalene, anthracene, phenanthrene
- quinoid substances quine, anthraquinone
- amino compounds aniline, naphthylamine, carbazole.
- the second tanning-active component can also be a chemically treated lignin sulfonic acid or a chemically treated lignin extract. Natural resins, bitumen and petroleum fractions of any kind can also be used.
- the second tanning-active component can also be or comprise a synthetically produced component which is selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof.
- the structurally identical substances as for the first tanning component can be used as the second tanning component, but they do not come from a reaction solution that was obtained by partial oxidation and/or pyrolysis of the organic substance with a vicinal diol group.
- glycolaldehyde can be produced synthetically from formaldehyde, hydrogen, carbon monoxide and a suitable catalyst and added to the tanning agent as the second tanning-active component.
- the synthetic production of the glycol aldehyde can be carried out in accordance with the WO 2005/058788 A1 process described, in which a rhodium catalyst and a phosphine ligand is used.
- tanning-active components which do not occur naturally, cannot be produced from renewable raw materials and/or are not biodegradable, but are minimized in the tanning agent according to the invention.
- the object of the invention is further achieved by using a tanning agent as described above for tanning animal skins and skins to produce leather.
- reaction solution as obtained from the partial oxidation and/or pyrolysis, is directly suitable for use as or in the tanning agent and an excellent tanning effect can be achieved, while at the same time preferably environmentally friendly substances are used.
- the object of the invention is achieved by a method for tanning animal hides and skins to produce leather, comprising the following steps: First, a pelt is produced. In addition, a tanning liquor is provided which comprises the tanning agent as described above. The pelt is then treated with the tanning liquor to obtain a leather.
- the pelt can be delimed, that is, lime absorbed into the pelt can be converted into easily soluble salts and removed in this form.
- acids such as mineral acids, sulfonic acids, aliphatic and aromatic acids, polybasic aliphatic and aromatic acids, salts of the acids mentioned, and one or more ammonium salts.
- ammonium salt or salts are, for example, ammonium chloride and/or ammonium sulfate.
- the pelt can be stained. This is based on animal skins, which using pancreatic proteases or other enzymes in a slightly alkaline pH range from 7.0 up to 10.0, preferably from 8.0 to 9.0.
- the pelt Before the tanning agent is used, and if necessary after deliming and/or pickling, the pelt can be pickled, ie the pH value of the pelt can be lowered in a targeted manner in order to subsequently improve the action of the tanning agent.
- Pickling can be done using a mixture of formic acid and sulfuric acid.
- the tanning agent described above because of the use of the tanning agent described above, in particular because of the good penetration properties of the tanning agent, pickling of the pelt can be dispensed with and a leather with outstanding properties can nevertheless be obtained.
- the tanning liquor can thus be used on a pelt without pimples.
- the shrinkage temperature remains constant over all skin layers of the leather obtained after tanning, even if the pelt is not pickled.
- the tanning liquor can have an active tanning substance content in the range from 1 to 10 percent, preferably from 2 to 4 percent, based on the reference weight of the pelt.
- the weight of the pelt or the weight of the pimple serves as a reference weight. Adequate tanning is not to be expected with lower levels of tanning-active substance, while higher levels would result in a higher use of chemicals.
- the tanning agent comprises a first tanning-active component and a second tanning-active component
- the aforementioned contents apply to the total content of the first and second tanning-active components.
- the pH of the tanning liquor can be adjusted to a pH in the range from 2.0 to 10.0, preferably from 3.0 to 8.0.
- the treatment of the pelt with the tanning liquor is carried out in particular at a temperature in the range from 10 to 60.degree. It can also be several temperature levels are used, for example, initially at Room temperature are treated to then fix at an elevated temperature, for example at 40 ° C.
- the treatment of the pelt with the tanning liquor is carried out in a tanning vessel.
- the pelt can be moved in the tanning vessel.
- the exposure time of the tanning liquor to the pelt can be reduced to 15 to 60 minutes, preferably 15 to 30 minutes, compared to an exposure time of up to about two hours when tanning with glutardialdehyde.
- the tanning agent can be fixed by increasing the pH value in order to crosslink the skin fibers.
- the pH of the tanning liquor is increased by adding one or more alkalis, for example by adding sodium carbonate and/or sodium bicarbonate.
- the pH of the tanning liquor is adjusted in particular to a pH in the range from 5.0 to 7.0, preferably from 5.5 to 6.5.
- the leather is moved in the tanning vessel over its entire cross-section, in particular for at least 60 minutes, to equalize the pH.
- Suitable temperatures are in the range from 20 to 50° C., temperatures between 30 and 45° C. being preferred.
- a leather having a shrinkage temperature of 70°C or more is preferably obtained.
- glyceraldehyde When glyceraldehyde is used as the tanning-active component, a leather with a shrinkage temperature in the range from 72 to 76° C. is obtained in particular.
- glycolaldehyde is used as the tanning-active component, a leather with a shrinkage temperature in the range from 75 to 80° C. is obtained in particular.
- the subject matter of the invention is therefore also a leather obtainable by the process described above using the tanning agent according to the invention.
- Example 1 Tanning with partially oxidized glycerin (with pimples)
- a reaction solution obtained by partial oxidation of glycerine is used as the tanning agent.
- the tanning agent consists of 50% by weight water, 30% by weight glyceraldehyde, 9% by weight dihydroxyacetone, 5% by weight formic acid, 3% by weight glyceric acid, 2% by weight hydroxyacetic acid and 1% by weight % glycerol formal, in each case based on the total weight of the tanning agent.
- the tanning agent is used on a pickled pelt in an aqueous liquor.
- the drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
- a tanning vessel 50% to 100% water and 10% of the tanning agent, corresponding to 3% by weight of glyceraldehyde, in each case based on the reference weight, are added to the split or unsplit pimple pelt.
- the tanning vessel is moved throughout the process.
- the tanning liquor is left to work for 120 minutes to guarantee even and complete penetration.
- the pH is gradually raised to a pH in the range of 6.0 to 6.5.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature is gradually increased over a period of 2 hours, first to 30°C, then to 35°C and finally to 40°C in order to fix the tanning agent.
- the tanning liquor is drained off and 100% water is added to the pretanned material.
- 3% of a naphthalenesulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 hours.
- the percentages relate in each case to the reference weight.
- the leather After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
- Example 2 Tanning with partially oxidized glycerin (without pimples)
- a reaction solution obtained by partial oxidation of glycerine is used as the tanning agent.
- the tanning agent consists of 50% by weight water, 30% by weight glyceraldehyde, 9% by weight dihydroxyacetone, 5% by weight formic acid, 3% by weight glyceric acid, 2% by weight hydroxyacetic acid and 1% by weight % glycerol formal, in each case based on the total weight of the tanning agent.
- the tanning agent is used on a delimed and bated pelt in an aqueous liquor.
- the pelt is weighed, the reference weight in this case referring to the weight obtained after splitting, i.e. the pelt weight.
- the pH is measured and if necessary adjusted to a pH below 8 with formic acid or dilute sulfuric acid.
- the pH value is lowered by the acid contained in the tanning agent.
- the tanning vessel is moved throughout the process.
- the tanning liquor is left to work for 120 minutes to guarantee even and complete penetration.
- the pH is gradually raised to pH 6.0.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature is gradually raised to 40 °C over a period of 2 hours in order to fix the tanning agent.
- the tanning liquor is drained off and 100% water is added to the pretanned material.
- 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 hours.
- the percentages relate in each case to the reference weight.
- the leather After washing again, the leather can be processed further to produce glutaraldehyde wet white.
- Example 3 Tanning with pyrolysis products of sugars (with pimples)
- a reaction solution obtained through sugar pyrolysis is used as the tanning agent.
- the tanning agent consists of 40% by weight glycolaldehyde, 30% by weight water, 20% by weight invert sugar syrup and 10% by weight organic short-chain acids having 1 to 8 carbon atoms.
- the tanning agent is used on a pickled pelt in an aqueous liquor.
- the drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
- the reference weight then refers to the split or unsplit pelt.
- the tanning vessel is moved throughout the process.
- the product is left on for 120 minutes to guarantee uniform and complete penetration.
- the pH is gradually raised to a pH of 6.0.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature starting from room temperature (25 °C), is gradually increased over 2 hours to a temperature of 40 °C in order to fix the tanning agent.
- the tanning liquor is drained off and 100% water is added to the pretanned material.
- 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours.
- the percentages relate in each case to the reference weight.
- the leather After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
- Example 4 Tanning with a mixture of pyrolysis products of sugars and partial glycerol oxidation products (with pimples)
- a mixture of a reaction solution obtained by partial oxidation of glycerol and a reaction solution obtained by pyrolysis of sugar is used as the tanning agent.
- two partial reaction solutions are used in the tanning agent.
- the tanning agent consists of 40% by weight water, 20% by weight glycolaldehyde, 15% by weight glyceraldehyde, 8% by weight invert sugar syrup, 5% by weight dihydroxyacetone, 5% by weight formic acid, 2% by weight % glyceric acid, 2% by weight hydroxyacetic acid, 2% by weight acetic acid and 1% by weight glycerol formal.
- the tanning agent is used on a pickled pelt in an aqueous liquor.
- the drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
- the reference weight then refers to the split or unsplit pelt.
- the tanning vessel is moved throughout the process.
- the product is left on for 120 minutes to guarantee uniform and complete penetration.
- the pH is gradually raised to a pH of 6.0.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature is gradually raised from room temperature (25 °C) to 40 °C over a period of 2 hours in order to fix the tanning agent.
- the tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours.
- the leather After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
- Example 5 Tanning with acetals and hemiacetals of glyceraldehyde (with
- a mixture of a reaction solution obtained by partial oxidation of glycerol and butyl diglycol is used as the tanning agent.
- the tanning agent consists of 40% by weight water, 20% by weight glyceraldehyde, 15% by weight glyceraldehyde butyldiglycol acetal, 15% by weight butyldiglycol and 10% by weight dihydroxyacetone and its ketal with butyldiglycol.
- the tanning agent is used on a pickled pelt in an aqueous liquor.
- the drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
- the reference weight then refers to the split or unsplit pelt.
- the tanning vessel is moved throughout the process.
- the product is left on for 120 minutes to guarantee uniform and complete penetration.
- the pH is gradually raised to a pH of 7.0.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature is gradually raised from room temperature (25 °C) to 40 °C over 4 hours in order to fix the tanning agent.
- a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrink temperature is above about 70°C to 75°C, the process can proceed.
- the tanning liquor is drained off and 100% water is added to the pretanned material.
- 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours.
- the percentages relate in each case to the reference weight.
- the leather After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
- Example 6 Tanning with acetals and hemiacetals of glycolaldehyde (with pick)
- a mixture of a reaction solution obtained by pyrolysis of sugar and butyl diglycol is used as the tanning agent.
- the tanning agent consists of 30% by weight water, 15% by weight glycolaldehyde, 20% by weight glycolaldehyde butyldiglycol acetal, 15% by weight butyldiglycol and 20% by weight invert sugar syrup.
- the tanning agent is used on a pickled pelt in an aqueous liquor.
- the drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
- the reference weight then refers to the split or unsplit pelt.
- the tanning vessel is moved throughout the process.
- the product is left on for 120 minutes to guarantee uniform and complete penetration.
- the pH is gradually raised to a pH of 7.0.
- Sodium bicarbonate is used for this.
- the amount added depends on the acid capacity of the tanning liquor.
- the temperature is gradually raised from room temperature (25 °C) to 40 °C over 4 hours in order to fix the tanning agent.
- the tanning liquor is drained off and 100% water is added to the pretanned material.
- 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours.
- the percentages relate in each case to the reference weight.
- the leather After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
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Abstract
Ein Gerbmittel umfasst eine Reaktionslösung, welche eine gerbaktive Komponente enthält, die ausgewählt ist aus der Gruppe bestehend aus Glycerinaldehyd, Glycolaldehyd, Acetalen dieser Verbindungen, Hemiacetalen dieser Verbindungen und Kombinationen davon, wobei die Reaktionslösung erhalten ist durch partielle Oxidation und/oder Pyrolyse einer organischen Substanz mit einer vicinalen Diolgruppe.Ferner wird die Verwendung eines solchen Gerbmittels zum Gerben von Tierhäuten und Fellen, ein Verfahren zum Gerben von Tierhäuten und Fellen zur Herstellung von Leder und ein daraus erhaltenes Leder angegeben.A tanning agent comprises a reaction solution which contains a tanning component selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof, the reaction solution being obtained by partial oxidation and/or pyrolysis of an organic substance with a vicinal diol group.Furthermore, the use of such a tanning agent for tanning animal skins and skins, a process for tanning animal skins and skins to produce leather and a leather obtained therefrom is specified.
Description
Die Erfindung betrifft ein Gerbmittel und die Verwendung eines solchen Gerbmittels zum Gerben von Tierhäuten und Fellen, ein Verfahren zum Gerben von Tierhäuten und Fellen zur Herstellung von Leder sowie ein daraus erhaltenes Leder.The invention relates to a tanning agent and the use of such a tanning agent for tanning animal hides and skins, a process for tanning animal hides and skins to produce leather, and a leather obtained therefrom.
Beim Gerben wird tierisches Kollagen in Häuten derart verändert, dass das aus der Gerbung entstandene Leder Widerstandsfähigkeit gegenüber Hitze, Umwelteinflüssen und Mikroorganismen besitzt sowie nach Trocknung des entstandenen Leders die Geschmeidigkeit der gegerbten Haut erhalten bleibt.During tanning, animal collagen in skins is modified in such a way that the leather resulting from the tanning is resistant to heat, environmental influences and microorganisms, and the suppleness of the tanned skin is retained after the leather has dried.
Im Wesentlichen werden drei Gerbverfahren angewandt: die mineralische Gerbung, insbesondere die Chromgerbung, die vegetabile Gerbung, beispielsweise mit Tara, Mimosa, Quebracho oder Kastanie, und die synthetische Gerbung, insbesondere mit Glutardialdehyd, die auf unterschiedlichen Strategien beruhen.Essentially, three tanning processes are used: mineral tanning, especially chrome tanning, vegetable tanning, for example with tara, mimosa, quebracho or chestnut, and synthetic tanning, especially with glutardialdehyde, which are based on different strategies.
Die Chromgerbung weist die größte wirtschaftliche Bedeutung auf. Hydratisierte Chromkomplexe, die sich zwischen die Carboxylgruppen von Glutaminsäure und Asparaginsäure des Kollagenpeptidgerüstes der Haut lagern, führen zu einem widerstandsfähigen und weichen Leder. Neben der zu erreichenden guten Lederqualität wurde mit Chromgerbstoff eine schnelle und kostengünstige Prozessführung etabliert. Nach demselben Wirkprinzip wirken auch andere Mineralgerbstoffe, die beispielsweise auf Basis von Aluminium oder Zirkonium arbeiten.Chrome tanning has the greatest economic importance. Hydrated chromium complexes sandwiched between the carboxyl groups of glutamic acid and aspartic acid in the skin's collagen peptide framework result in resilient and soft leather. In addition to the good leather quality to be achieved, a fast and cost-effective process control was established with chrome tanning material. Other mineral tanning agents, such as those based on aluminum or zirconium, also work according to the same principle.
Die Verwendung von (Schwer-)Metallen weist eine Reihe von Nachteilen auf. Es ist zum Beispiel bekannt, dass Chrom(VI) bei Hautkontakt allergische Reaktionen auslösen kann. Üblicherweise werden im Gerbprozess Chrom(III)-Sulfate eingesetzt. Chrom(VI) kann jedoch durch Oxidation aus Chrom (III) entstehen, oder gelangt über Gerbstoffverunreinigungen in den Gerbprozess. Weitere Nachteile einer (schwer-)metallbelasteten Gerbung sind die aufwändige Behandlung der Abwässer über eine Anlage zur Rückgewinnung von Chrom und anderen Schwermetallen sowie die teure Entsorgung von Lederresten wie Falzspänen mittels Deponieverfahren oder Verbrennung.The use of (heavy) metals has a number of disadvantages. It is known, for example, that chromium(VI) can trigger allergic reactions when it comes into contact with the skin. Usually, chromium(III) sulfates are used in the tanning process. However, chromium(VI) can be formed by oxidation of chromium(III) or enters the tanning process via tanning agent impurities. Other disadvantages of (heavy) metal-loaded tanning are the time-consuming process Treatment of the waste water via a plant for the recovery of chromium and other heavy metals as well as the expensive disposal of leather residues such as shavings using landfill methods or incineration.
Die vegetabile Gerbung setzt Tannine ein, welche aus Pflanzen extrahiert werden. Jedoch benötigt die vegetabile Gerbung lange und aufwendige Gerbprozesse, weswegen die vegetabile Gerbung größtenteils von der Chromgerbung abgelöst wurde.Vegetable tanning uses tannins extracted from plants. However, vegetable tanning requires long and complex tanning processes, which is why vegetable tanning has largely been replaced by chrome tanning.
Eine weitere weit verbreitete Gerbmethode ist die synthetische Gerbung mit Glutardialdehyd, bei der die Bifunktionalität des Glutardialdehyds dazu dient, die Peptidfasern der Haut zu vernetzen. Die Wirkungsweise ist hauptsächlich auf die Reaktivität an den Stickstofffunktionalitäten der zu Grunde liegenden Aminosäuren zurückzuführen. Das Glutardialdehyd reagiert an zwei verschiedenen Fasern und verbindet diese so permanent durch die Ausbildung einer kovalenten Bindung.Another widespread tanning method is synthetic tanning with glutaraldehyde, in which the bifunctionality of glutaraldehyde serves to cross-link the peptide fibers of the hide. The mode of action is mainly due to the reactivity at the nitrogen functionalities of the underlying amino acids. The glutaraldehyde reacts on two different fibers and thus permanently connects them by forming a covalent bond.
Nachteile dieses Verfahrens sind die ungünstigen toxikologischen Eigenschaften des Glutardialdehyds, insbesondere dessen Umwelttoxizität und die nicht vorhandene biologische Abbaubarkeit, sowie die energieaufwändige und klimagefährdende Erzeugung aus petrochemischen Grundstoffen. Ferner ist aufgrund der Respirationstoxizität und Mutagenität von Glutardialdehyd nach der REACH-Verordnung eine Einstufung als SVHC-Stoff zu erwarten. Mit Glutardialdehyd gegerbte Leder weisen ferner eine über die Hautschichten variierende Schrumpfungstemperatur auf.Disadvantages of this process are the unfavorable toxicological properties of glutaric dialdehyde, in particular its environmental toxicity and the lack of biodegradability, as well as the energy-intensive and climate-damaging production from petrochemical raw materials. Furthermore, due to the respiratory toxicity and mutagenicity of glutardialdehyde, classification as an SVHC substance is to be expected according to the REACH regulation. Leather tanned with glutardialdehyde also has a shrinkage temperature that varies across the skin layers.
Erstrebenswerter sind umweltverträgliche Gerbverfahren, die insbesondere Verbindungen einsetzen, die aus nachwachsenden Rohstoffen gewonnen werden können.More desirable are environmentally friendly tanning processes that use compounds that can be obtained from renewable raw materials.
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Es ist Aufgabe der Erfindung, eine umweltverträgliche und leistungsfähige Möglichkeit zum Gerben bereitzustellen, welche einen geringen Energieverbrauch und/oder einen geringen Chemikalienverbrauch ermöglicht. Insbesondere sollen die Gerbmittel aus weltweit verfügbaren, biologisch abbaubaren und/oder aus nachwachsenden Rohstoffen erhältlichen Verbindungen hergestellt werden können.It is the object of the invention to provide an environmentally friendly and efficient option for tanning which enables low energy consumption and/or low chemical consumption. In particular, the tanning agents should be able to be produced from compounds that are available worldwide, are biodegradable and/or can be obtained from renewable raw materials.
Die Aufgabe der Erfindung wird gelöst durch ein Gerbmittel, umfassend eine Reaktionslösung, welche eine gerbaktive Komponente enthält, die ausgewählt ist aus der Gruppe bestehend aus Glycerinaldehyd, Glycolaldehyd, Acetalen dieser Verbindungen, Hemiacetalen dieser Verbindungen und Kombinationen davon, wobei die Reaktionslösung erhalten ist durch partielle Oxidation und/oder Pyrolyse einer organischen Substanz mit einer vicinalen Diolgruppe.The object of the invention is achieved by a tanning agent comprising a reaction solution which contains a tanning component selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof, the reaction solution being obtained by partial Oxidation and/or pyrolysis of an organic substance having a vicinal diol group.
Es wurde erkannt, dass ausgehend von organischen Substanzen mit einer vicinalen Diolgruppe eine Reaktionslösung erhalten werden kann, welche sich aufgrund der durch die partielle Oxidation und/oder Pyrolyse entstehenden Verbindungen Glycerinaldehyd, auch als 1,2-Dihydroxypropanal bezeichnet, Glycolaldehyd, auch als Hydroxyethanal bezeichnet, Acetalen dieser Verbindungen und/oder Hemiacetalen dieser Verbindungen direkt für den Einsatz in einem Gerbmittel eignet.It was recognized that, starting from organic substances with a vicinal diol group, a reaction solution can be obtained which, due to the compounds glyceraldehyde, also referred to as 1,2-dihydroxypropanal, and glycolaldehyde, also referred to as hydroxyethanal, formed as a result of the partial oxidation and/or pyrolysis , Acetals of these compounds and/or hemiacetals of these compounds are directly suitable for use in a tanning agent.
Erfindungsgemäß ist die gerbaktive Komponente insbesondere biologisch abbaubar und umweltverträglich. Dadurch wird ein umweltverträgliches und ressourcenschonendes Gerben ermöglicht. Zudem sinkt im Vergleich zu klassischen Gerbverfahren, beispielsweise der Chromgerbung, der Aufwand in der Entsorgung von bei der Anwendung des Gerbmittels anfallenden Abfällen erheblich, wodurch ein kostengünstigerer Gerbprozess ermöglicht wird.According to the invention, the tanning-active component is, in particular, biodegradable and environmentally compatible. This enables environmentally friendly and resource-saving tanning. In addition, compared to classic tanning processes, such as chrome tanning, the effort required to dispose of waste generated during the use of the tanning agent is significantly reduced, which means that a more cost-effective tanning process is made possible.
Insbesondere können organische Substanzen als Ausgangsprodukt verwendet werden, welche natürlich vorkommen und/oder aus erneuerbaren Rohstoffen hergestellt werden können. Auf diese Weise kann der Einsatz von fossilen Rohstoffen, beispielsweise erdöl- und/oder erdgasbasierter Ausgangsstoffe, in der Herstellung von Gerbmitteln vermieden oder zumindest reduziert werden.In particular, organic substances can be used as the starting product, which occur naturally and/or can be produced from renewable raw materials. In this way, the use of fossil raw materials, for example starting materials based on petroleum and/or natural gas, can be avoided or at least reduced in the production of tanning agents.
Die gerbaktive Komponente ist ferner hydrophil und dringt schnell in die zu gerbenden Hautschichten ein. Dadurch kann die Einwirkzeit der Gerbflotte im Vergleich zu herkömmlichen Gerbmitteln verkürzt werden. Zusätzlich wird eine gleichmäßige Verteilung der gerbaktiven Komponente in den Hautschichten erreicht, so dass ein gleichmäßig durchgegerbtes Leder mit einer über alle Hautschichten gleichbleibenden Schrumpfungstemperatur erhalten werden kann.The tanning-active component is also hydrophilic and quickly penetrates the skin layers to be tanned. As a result, the exposure time of the tanning liquor can be reduced compared to conventional tanning agents. In addition, a uniform distribution of the tanning-active component in the skin layers is achieved, so that a uniformly through-tanned leather can be obtained with a shrinkage temperature that remains the same across all skin layers.
Die organische Substanz mit einer vicinalen Diolgruppe ist insbesondere eine aliphatische Substanz mit einer vicinalen Diolgruppe.Specifically, the organic substance having a vicinal diol group is an aliphatic substance having a vicinal diol group.
Bevorzugt ist die organische Substanz mit einer vicinalen Diolgruppe ausgewählt aus der Gruppe bestehend aus Glycerin, Ethylenglykol, Monosacchariden, Oligosacchariden, Polysacchariden und Kombinationen davon.Preferably, the organic substance having a vicinal diol group is selected from the group consisting of glycerol, ethylene glycol, monosaccharides, oligosaccharides, polysaccharides, and combinations thereof.
Diese organischen Substanzen fallen beispielsweise als Nebenprodukt in großtechnischen Prozessen an, wie beispielsweise in der Produktion von Biodiesel oder bei der Naturseifenherstellung, und/oder können aus nachwachsenden Rohstoffen gewonnen werden.These organic substances occur, for example, as a by-product in large-scale processes, such as in the production of biodiesel or in natural soap production, and/or can be obtained from renewable raw materials.
In einer Variante ist die organische Substanz mit einer vicinalen Diolgruppe Glycerin und/oder Ethylenglykol.In a variant, the organic substance having a vicinal diol group is glycerol and/or ethylene glycol.
In einer weiteren Variante ist die organische Substanz ausgewählt aus der Gruppe bestehend aus Monosacchariden, Oligosacchariden, Polysacchariden und Kombinationen davon,In a further variant, the organic substance is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides and combinations thereof,
Erfindungsgemäße Monosaccharide sind insbesondere Monosaccharide mit vier bis sieben Kohlenstoffatomen und erfindungsgemäße Oligosaccharide und Polysaccharide sind insbesondere Oligo- beziehungsweise Polysaccharide dieser Monosaccharide.Monosaccharides according to the invention are in particular monosaccharides with four to seven carbon atoms and oligosaccharides and polysaccharides according to the invention are in particular oligosaccharides or polysaccharides of these monosaccharides.
Ist die organische Substanz Glycerin und/oder Ethylenglykol, wird die Reaktionslösung insbesondere durch partielle Oxidation erhalten.In particular, when the organic substance is glycerin and/or ethylene glycol, the reaction solution is obtained by partial oxidation.
Die partielle Oxidation erzeugt insbesondere eine Reaktionslösung, welche als gerbaktive Komponente Glycerinaldehyd, ein Acetal von Glycerinaldehyd und/oder ein Hemiacetal von Glycerinaldehyd enthält.The partial oxidation produces in particular a reaction solution which contains glyceraldehyde, an acetal of glyceraldehyde and/or a hemiacetal of glyceraldehyde as the tanning-active component.
Beispielsweise erfolgt die partielle Oxidation gemäß des in der
Die partielle Oxidation erfolgt insbesondere unter Einsatz von Wasserstoffperoxid als Oxidationsmittel in Kombination mit einem geeigneten Katalysator, beispielweise ein Eisenkatalysator wie Eisen-(II)-sulfat.The partial oxidation takes place in particular using hydrogen peroxide as the oxidizing agent in combination with a suitable catalyst, for example an iron catalyst such as iron(II) sulfate.
Der Katalysator, insbesondere der Eisenkatalysator, kann in Abhängigkeit der weiteren Reaktionsbedingungen in einem Anteil von bis zu 10 Gewichtsprozent, vorzugsweise bis zu 5 Gewichtsprozent eingesetzt werden, bezogen auf das Gesamtgewicht der Reaktionslösung. Gute Ergebnisse können mit 750 bis 5000 ppm Eisen erzielt werden, bezogen auf das Gesamtgewicht der Reaktionslösung, bevorzugt von 1500 bis 5000 ppm, besonders bevorzugt von 3500 bis 5000 ppm.Depending on the further reaction conditions, the catalyst, in particular the iron catalyst, can be used in a proportion of up to 10 percent by weight, preferably up to 5 percent by weight, based on the total weight of the reaction solution. Good results can be achieved with 750 to 5000 ppm iron are achieved, based on the total weight of the reaction solution, preferably from 1500 to 5000 ppm, particularly preferably from 3500 to 5000 ppm.
Die partielle Oxidation erfolgt insbesondere bei einer Temperatur von 35 bis 90 °C, bevorzugt von 40 bis 70 °C, besonders bevorzugt von 45 bis 50°C.The partial oxidation takes place in particular at a temperature of from 35 to 90.degree. C., preferably from 40 to 70.degree. C., particularly preferably from 45 to 50.degree.
Als Ausgangsprodukt kann gereinigtes oder ungereinigtes Glycerin eingesetzt werden, mit einem Anteil von 10 Gew.-% bis 99.5 Gew.-% Glycerin im verwendeten Ausgangsprodukt. Bevorzugt wird gereinigtes Glycerin mit einem Reinheitsgrad von 90 Gew.-% bis 99,5 Glycerin verwendet. Der Anteil von Glycerin in der Reaktionslösung zu Beginn der Oxidation beträgt vorzugsweise von 80 Gew.-% bis 90 Gew.-%, bezogen auf das Gewicht der Reaktionslösung.Purified or unpurified glycerol can be used as the starting product, with a proportion of 10% by weight to 99.5% by weight of glycerol in the starting product used. Preference is given to using purified glycerol with a purity of 90% by weight to 99.5% glycerol. The proportion of glycerol in the reaction solution at the beginning of the oxidation is preferably from 80% by weight to 90% by weight based on the weight of the reaction solution.
Ist die organische Substanz aus der Gruppe bestehend aus Monosacchariden, Oligosacchariden, Polysacchariden und Kombination davon ausgewählt, wird die Reaktionslösung insbesondere durch Pyrolyse erhalten.If the organic substance is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides and combinations thereof, the reaction solution is obtained in particular by pyrolysis.
Beispielsweise erfolgt die Pyrolyse als wässrige Thermolyse wie in der
Alternativ kann die Pyrolyse wie in der
Die thermische Fragmentierung findet insbesondere bei einer Temperatur von 300 °C oder höher statt, beispielweise bei einer Temperatur im Bereich von 350 bis 800 °C, bevorzugt von 400 bis 600 °C, besonders bevorzugt von 500 bis 600 °C.The thermal fragmentation takes place in particular at a temperature of 300°C or higher, for example at a temperature in the range from 350 to 800°C, preferably from 400 to 600°C, particularly preferably from 500 to 600°C.
Grundsätzlich können auch mehrere Teilreaktionslösungen, welche über verschiedene Verfahren gewonnen wurden, zur Reaktionslösung vermischt werden, um eine gewünschte Zusammensetzung zu erhalten, wobei jede der Teilreaktionslösungen wie zuvor beschrieben erhalten sind. Auf diese Weise kann eine flexiblere Prozessführung in Abhängigkeit der verfügbaren organischen Substanzen realisiert werden sowie eine flexible Anpassung der chemischen und physikalischen Eigenschaften der Reaktionslösung erfolgen.In principle, several partial reaction solutions, which were obtained using different methods, can also be mixed to form the reaction solution to obtain a desired composition, each of the partial reaction solutions being obtained as described above. In this way, a more flexible process control can be realized depending on the available organic substances and a flexible adaptation of the chemical and physical properties of the reaction solution can take place.
Um die Gerbwirkung des erfindungsgemäßen Gerbmittels weiter zu steigern, kann die Reaktionslösung neben der gerbaktiven Komponente wenigstens eine weitere gerbfördernde Komponente enthalten.In order to further increase the tanning effect of the tanning agent according to the invention, the reaction solution can contain at least one further tanning-promoting component in addition to the tanning-active component.
Die gerbfördernde Komponente zeigt wie die gerbaktive Komponente ebenfalls eine Penetrationswirkung in eine zu gerbende Blöße bzw. ein zu gerbendes Substrat, führt jedoch im Gegensatz zur gerbaktiven Komponente selbst keine Gerbung durch. Insbesondere fördert die gerbfördernde Komponente die Penetrationswirkung der gerbaktiven Komponente in die zu gerbende Blöße bzw. in das zu gerbende Substrat oder steigert den Anteil der in der Blöße verbleibenden gerbaktiven Komponente.The tanning-promoting component, like the tanning-active component, also has a penetration effect into a pelt to be tanned or a substrate to be tanned, but in contrast to the tanning-active component itself does not carry out any tanning. In particular, the tanning-promoting component promotes the penetration effect of the tanning-active component into the pelt to be tanned or into the substrate to be tanned, or increases the proportion of the tanning-active component remaining in the pelt.
Die gerbfördernde Komponente dient insbesondere zum Absenken des zusätzlichen Chemikalienverbrauchs, indem bei einem geringeren Einsatz an gerbaktiver Komponente ein vergleichbares Gerbergebnis erzielt werden kann. Zudem kann sich die gerbfördernde Komponente positiv auf die biologische Abbaubarkeit eines erhaltenen Leders sowie der in der Herstellung des Leders eingesetzten Gerb- und/oder Prozessflotten, auf die Färbung des Leders und/oder die Haltbarkeit von vorgegerbten Material auswirken.The tanning-promoting component serves in particular to reduce the additional consumption of chemicals, since a comparable tanning result can be achieved with a lower use of tanning-active components. In addition, the tanning-promoting component can have a positive effect on the biodegradability of a leather obtained and on the tanning and/or process liquors used in the production of the leather, on the coloring of the leather and/or the durability of pretanned material.
Die gerbfördernde Substanz ist bevorzugt ausgewählt aus der Gruppe bestehend aus (Poly)Hydroxycarbonsäuren, Carbonsäuren, Ketonen, Acetalen, Hemiacetalen und Ketalen, jeweils mit 1 bis 8 Kohlenstoffatomen, sowie Mischungen davon.The tanning-promoting substance is preferably selected from the group consisting of (poly)hydroxycarboxylic acids, carboxylic acids, ketones, acetals, hemiacetals and ketals, each having 1 to 8 carbon atoms, and mixtures thereof.
Die gerbfördernde Substanz ist bevorzugt ebenfalls biologisch abbaubar und umweltverträglich.The tanning substance is preferably also biodegradable and environmentally friendly.
Bevorzugt wird die gerbfördernde Substanz als Nebenprodukt in der Reaktionslösung aus der organischen Substanz erzeugt, sodass keine zusätzliche Zugabe an gerbfördernder Substanz notwendig ist und sich der Herstellungsprozess des Gerbmittels weiter vereinfacht.The tanning-promoting substance is preferably produced as a by-product in the reaction solution from the organic substance, so that no additional addition of tanning-promoting substance is necessary and the production process of the tanning agent is further simplified.
Alternativ oder zusätzlich kann die gerbfördernde Substanz dem Gerbmittel zusätzlich zur Reaktionslösung zugesetzt sein.Alternatively or additionally, the tanning substance can be added to the tanning agent in addition to the reaction solution.
Die Reaktionslösung kann ein Lösungsmittel enthalten, bevorzugt Wasser und Glykole wie Polyethylenglykol sowie Gemische davon.The reaction solution can contain a solvent, preferably water and glycols such as polyethylene glycol and mixtures thereof.
Der Anteil des Lösungsmittels an der Reaktionslösung beträgt vorzugweise höchstens 80 Gewichtsprozent, weiter bevorzugt höchstens 65 Gewichtsprozent, besonders bevorzugt 20 bis 50 Gewichtsprozent.The proportion of the solvent in the reaction solution is preferably at most 80% by weight, more preferably at most 65% by weight, particularly preferably 20 to 50% by weight.
In einer Variante besteht das Gerbmittel aus der Reaktionslösung. Mit anderen Worten kommen in dieser Variante lediglich Substanzen zum Einsatz, welche direkt aus der partiellen Oxidation und/oder der Pyrolyse erhalten werden. Insbesondere im Fall, dass die eingesetzte organische Substanz natürlich vorkommend ist und/oder aus einem erneuerbaren Rohstoff hergestellt wurde, kann auf diese Weise sichergestellt werden, dass die Herstellung des Gerbmittels auf den Einsatz von fossilen Rohstoffen soweit wie möglich verzichtet und eine möglichst umfassende Umweltverträglichkeit und biologische Abbaubarkeit aufweist.In one variant, the tanning agent consists of the reaction solution. In other words, only substances that are obtained directly from the partial oxidation and/or the pyrolysis are used in this variant. Especially in the case that the organic substance used is naturally occurring and/or was made from a renewable raw material, it can be ensured in this way that the production of the tanning agent avoids the use of fossil raw materials as far as possible and that the greatest possible environmental compatibility and has biodegradability.
Es ist auch möglich, dass das Gerbmittel eine erste gerbaktive Komponente und eine zweite gerbaktive Komponente umfasst, wobei die erste gerbaktive Komponente die gerbaktive Komponente der Reaktionslösung ist und die zweite gerbaktive Komponente ausgewählt ist aus der Gruppe bestehend aus synthetischen Gerbstoffen, vegetabilen Gerbstoffen und mineralischen Gerbstoffen, insbesondere Glutardialdehyd und/oder Chromsalze.It is also possible for the tanning agent to comprise a first tanning component and a second tanning component, the first tanning component being the tanning component of the reaction solution and the second tanning component being selected from the group consisting of synthetic tanning agents, vegetable tanning agents and mineral tanning agents , in particular glutardialdehyde and/or chromium salts.
Mit anderen Worten können auch Mischungen aus konventionellen Gerbstoffen und der gerbaktiven Komponente aus der Reaktionslösung erfindungsgemäß zum Einsatz kommen. In dieser Alternative können die Nachteile der konventionellen Gerbstoffe zumindest minimiert werden, insbesondere kann das Gerbmittel hinsichtlich Umweltverträglichkeit und Verbrauch fossiler Rohstoffe optimiert werden, während zugleich die physikalischen und chemischen Eigenschaften des Gerbmittels im Hinblick auf spezifische Anforderungen des angedachten Gerbprozesses angepasst werden können.In other words, mixtures of conventional tanning agents and the tanning-active component from the reaction solution can also be used according to the invention. In this alternative, the disadvantages of conventional tanning agents can at least be minimized. In particular, the tanning agent can be optimized in terms of environmental compatibility and consumption of fossil raw materials, while at the same time the physical and chemical properties of the tanning agent can be adjusted with regard to specific requirements of the envisaged tanning process.
Bevorzugt liegt im Gerbmittel die erste gerbaktive Komponente in einem höheren Anteil (w/w) vor als die zweite gerbaktive Komponente. Mit anderen Worten ist die erste gerbaktive Komponente bevorzugt die gerbaktive Hauptkomponente.The first tanning component is preferably present in the tanning agent in a higher proportion (w/w) than the second tanning component. With others In other words, the first tanning-active component is preferably the tanning-active main component.
Die zweite gerbaktive Komponente ist beispielsweise ein Syntan (synthetischer Hilfsgerbstoff), ein vegetabiler Gerbstoff wie zum Beispiel hydrolysierbare Gerbstoffe (Pyrogallol-Gerbstoffe), ein kondensierbarer Gerbstoff (Pyrokatechin-Gerbstoffe), ein phenolischer oder nichtphenolischer Gerbstoff, eine Polykondensations- oder Polymerisationsverbindung oder eine Kombination davon.The second tanning-active component is, for example, a syntan (synthetic auxiliary tanning agent), a vegetable tanning agent such as hydrolyzable tanning agents (pyrogallol tanning agents), a condensable tanning agent (pyrocatechin tanning agents), a phenolic or non-phenolic tanning agent, a polycondensation or polymerization compound, or a combination from that.
Geeignete synthetische Hilfsgerbstoffe können durch Sulfonierung und Kondensation aromatischer Produkte erzeugt sein. Hierbei werden im Wesentlichen Verbindungen meist mehrkerniger Kohlenwasserstoffe (Naphthalin, Anthracen, Phenantren) eingesetzt oder in Form einwertiger Phenole (Phenol, Naphthol, Kresol u.ä.) als chinoide Substanzen (Chinon, Antrachinon), Aminoverbindungen (Anilin, Naphthylamin, Carbazol) verarbeitet.Suitable synthetic auxiliary tanning agents can be produced by sulfonation and condensation of aromatic products. Essentially, compounds of mostly polynuclear hydrocarbons (naphthalene, anthracene, phenanthrene) are used or processed in the form of monohydric phenols (phenol, naphthol, cresol, etc.) as quinoid substances (quinone, anthraquinone), amino compounds (aniline, naphthylamine, carbazole). .
Auch kann die zweite gerbaktive Komponente eine chemisch behandelte Ligninsulfonsäure bzw. ein chemisch behandeltes Ligninextrakt sein. Ebenso können natürliche Harze, Bitumen und Erdölfraktionen jeglicher Art zum Einsatz kommen.The second tanning-active component can also be a chemically treated lignin sulfonic acid or a chemically treated lignin extract. Natural resins, bitumen and petroleum fractions of any kind can also be used.
Die zweite gerbaktive Komponente kann auch eine synthetisch hergestellte Komponente sein oder umfassen, welche ausgewählt ist aus der Gruppe bestehend aus Glycerinaldehyd, Glycolaldehyd, Acetalen dieser Verbindungen, Hemiacetalen dieser Verbindungen und Kombinationen davon.The second tanning-active component can also be or comprise a synthetically produced component which is selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof.
Mit anderen Worten können als zweite gerbaktive Komponente die strukturell gleichen Substanzen wie für die erste gerbaktive Komponente zum Einsatz kommen, welche jedoch nicht aus einer Reaktionslösung stammen, die durch partielle Oxidation und/oder Pyrolyse der organischen Substanz mit einer vicinalen Diolgruppe erhalten wurde.In other words, the structurally identical substances as for the first tanning component can be used as the second tanning component, but they do not come from a reaction solution that was obtained by partial oxidation and/or pyrolysis of the organic substance with a vicinal diol group.
Beispielsweise kann Glycolaldehyd aus Formaldehyd, Wasserstoff, Kohlenmonoxid und einem geeigneten Katalysator synthetisch hergestellt und als zweite gerbaktive Komponente im Gerbmittel zugesetzt sein. Die synthetische Herstellung des Glycolaldehyds kann gemäß dem in der
Bevorzugt wird der Einsatz von gerbaktiven Komponenten, welche nicht natürlich vorkommen, nicht aus erneuerbaren Rohstoffen herstellbar und/oder nicht biologisch abbaubar sind, im erfindungsgemäßen Gerbmittel jedoch minimiert.Preference is given to using tanning-active components which do not occur naturally, cannot be produced from renewable raw materials and/or are not biodegradable, but are minimized in the tanning agent according to the invention.
Die Aufgabe der Erfindung wird des Weiteren gelöst durch die Verwendung eines Gerbmittels wie zuvor beschrieben zum Gerben von Tierhäuten und Fellen zur Herstellung von Leder.The object of the invention is further achieved by using a tanning agent as described above for tanning animal skins and skins to produce leather.
Insbesondere wurde erkannt, dass sich die Reaktionslösung, wie sie aus der partiellen Oxidation und/oder der Pyrolyse erhalten wird, direkt für den Einsatz als bzw. im Gerbmittel eignet und eine ausgezeichnete Gerbwirkung erzielt werden kann, während zugleich bevorzugt umweltverträgliche Stoffe zum Einsatz kommen.In particular, it was recognized that the reaction solution, as obtained from the partial oxidation and/or pyrolysis, is directly suitable for use as or in the tanning agent and an excellent tanning effect can be achieved, while at the same time preferably environmentally friendly substances are used.
Ferner wird die Aufgabe der Erfindung gelöst durch ein Verfahren zum Gerben von Tierhäuten und Fellen zur Herstellung von Leder, umfassend folgende Schritte: Zunächst wird eine Blöße erzeugt. Zudem wird eine Gerbflotte bereitgestellt, welche das Gerbmittel wie zuvor beschrieben umfasst. Anschließend wird die Blöße mit der Gerbflotte unter Erhalt eines Leders behandelt.Furthermore, the object of the invention is achieved by a method for tanning animal hides and skins to produce leather, comprising the following steps: First, a pelt is produced. In addition, a tanning liquor is provided which comprises the tanning agent as described above. The pelt is then treated with the tanning liquor to obtain a leather.
Die Blöße kann entkälkt werden, das heißt, in die Blöße aufgenommener Kalk kann in leichtlösliche Salze überführt und in dieser Form entfernt werden. Zu diesem Zweck geht man von Tierhäuten aus, die unter Verwendung von Säuren wie beispielweise Mineralsäuren, Sulfonsäuren, aliphatischen und aromatischen Säuren, mehrwertigen aliphatischen und aromatischen Säuren, Salze der genannten Säuren, sowie durch ein Ammoniumsalz oder mehrere Ammoniumsalze entkälkt sind.The pelt can be delimed, that is, lime absorbed into the pelt can be converted into easily soluble salts and removed in this form. For this purpose one starts from animal skins which have been delimed using acids such as mineral acids, sulfonic acids, aliphatic and aromatic acids, polybasic aliphatic and aromatic acids, salts of the acids mentioned, and one or more ammonium salts.
Das Ammoniumsalz bzw. die Ammoniumsalze sind beispielsweise Ammoniumchlorid und/oder Ammoniumsulfat.The ammonium salt or salts are, for example, ammonium chloride and/or ammonium sulfate.
Die Blöße kann gebeizt werden. Dazu wird von Tierhäuten ausgegangen, welche unter Verwendung von Pankreas-Proteasen oder anderer Enzyme in einem leicht alkalischen pH-Bereich von 7,0 bis zu 10,0, bevorzugt von 8,0 bis 9,0, gebeizt wurden.The pelt can be stained. This is based on animal skins, which using pancreatic proteases or other enzymes in a slightly alkaline pH range from 7.0 up to 10.0, preferably from 8.0 to 9.0.
Vor dem Einsatz des Gerbmittels, und ggf. nach dem Entkälken und/oder Beizen, kann die Blöße gepickelt werden, das heißt der pH-Wert der Blöße kann gezielt abgesenkt werden, um die Einwirkung des Gerbmittels nachfolgend zu verbessern.Before the tanning agent is used, and if necessary after deliming and/or pickling, the pelt can be pickled, ie the pH value of the pelt can be lowered in a targeted manner in order to subsequently improve the action of the tanning agent.
Das Pickeln kann unter Einsatz einer Mischung aus Ameisensäure und Schwefelsäure erfolgen.Pickling can be done using a mixture of formic acid and sulfuric acid.
Im erfindungsgemäßen Verfahren kann aufgrund der Verwendung des zuvor beschriebenen Gerbmittels, insbesondere wegen der guten Penetrationseigenschaften des Gerbmittels, auf das Pickeln der Blöße verzichtet und trotzdem ein Leder mit hervorragenden Eigenschaften erhalten werden. Die Gerbflotte kann somit auf einer Blöße ohne Pickel eingesetzt werden. Insbesondere bleibt die Schrumpfungstemperatur über alle Hautschichten des nach dem Gerben erhaltenen Leders konstant, selbst wenn die Blöße nicht gepickelt wird.In the process according to the invention, because of the use of the tanning agent described above, in particular because of the good penetration properties of the tanning agent, pickling of the pelt can be dispensed with and a leather with outstanding properties can nevertheless be obtained. The tanning liquor can thus be used on a pelt without pimples. In particular, the shrinkage temperature remains constant over all skin layers of the leather obtained after tanning, even if the pelt is not pickled.
Die Gerbflotte kann einen Gehalt an gerbaktiver Substanz im Bereich von 1 bis 10 Prozent aufweisen, bevorzugt von 2 bis 4 Prozent, bezogen auf das Referenzgewicht der Blöße. Als Referenzgewicht dient insbesondere das Blößengewicht oder das Pickelgewicht. Bei niedrigeren Gehalten an gerbaktiver Substanz ist keine ausreichende Gerbung zu erwarten, während höhere Gehalte einen höheren Chemikalieneinsatz zur Folge hätten.The tanning liquor can have an active tanning substance content in the range from 1 to 10 percent, preferably from 2 to 4 percent, based on the reference weight of the pelt. In particular, the weight of the pelt or the weight of the pimple serves as a reference weight. Adequate tanning is not to be expected with lower levels of tanning-active substance, while higher levels would result in a higher use of chemicals.
Umfasst das Gerbmittel eine erste gerbaktive Komponente und eine zweite gerbaktive Komponente, gelten die zuvor genannten Gehalte für den Gesamtgehalt an erster und zweiter gerbaktiver Komponente.If the tanning agent comprises a first tanning-active component and a second tanning-active component, the aforementioned contents apply to the total content of the first and second tanning-active components.
Der pH-Wert der Gerbflotte kann auf einen pH-Wert im Bereich von 2,0 bis 10,0 eingestellt werden, bevorzugt von 3,0 bis 8,0.The pH of the tanning liquor can be adjusted to a pH in the range from 2.0 to 10.0, preferably from 3.0 to 8.0.
Das Behandeln der Blöße mit der Gerbflotte wird insbesondere bei einer Temperatur im Bereich von 10 bis 60 °C durchgeführt. Es können auch mehrere Temperaturstufen zum Einsatz kommen, beispielsweise kann zunächst bei Raumtemperatur behandelt werden, um anschließend bei einer erhöhten Temperatur zu fixieren, beispielsweise bei 40 °C.The treatment of the pelt with the tanning liquor is carried out in particular at a temperature in the range from 10 to 60.degree. It can also be several temperature levels are used, for example, initially at Room temperature are treated to then fix at an elevated temperature, for example at 40 ° C.
Das Behandeln der Blöße mit der Gerbflotte wird in einem Gerbgefäß durchgeführt. Um eine gleichmäßige und vollständige Penetration der Blöße zu gewährleisten, kann die Blöße im Gerbgefäß bewegt werden.The treatment of the pelt with the tanning liquor is carried out in a tanning vessel. In order to ensure an even and complete penetration of the pelt, the pelt can be moved in the tanning vessel.
Wegen der guten Penetrationswirkung des erfindungsgemäßen Gerbmittels kann die Einwirkzeit der Gerbflotte auf die Blöße auf 15 bis 60 min, bevorzugt 15 bis 30 min, verkürzt werden, im Vergleich zu einer Einwirkzeit von bis zu etwa zwei Stunden beim Gerben mit Glutardialdehyd.Due to the good penetration effect of the tanning agent according to the invention, the exposure time of the tanning liquor to the pelt can be reduced to 15 to 60 minutes, preferably 15 to 30 minutes, compared to an exposure time of up to about two hours when tanning with glutardialdehyde.
Nachdem das aus der Blöße erhaltene Leder im gesamten Querschnitt mit dem Gerbmittel penetriert wurde, kann das Gerbmittel durch Erhöhung des pH-Wertes fixiert werden, um die Hautfasern zu vernetzen. Dabei wird der pH-Wert der Gerbflotte durch Zugabe einer oder mehrerer Alkalien erhöht, beispielsweise durch Zugabe von Natriumcarbonat und/oder Natriumhydrogencarbonat.After the leather obtained from the pelt has been penetrated with the tanning agent over its entire cross section, the tanning agent can be fixed by increasing the pH value in order to crosslink the skin fibers. The pH of the tanning liquor is increased by adding one or more alkalis, for example by adding sodium carbonate and/or sodium bicarbonate.
Der pH-Wert der Gerbflotte wird insbesondere auf einen pH-Wert im Bereich von 5,0 bis 7,0 eingestellt, bevorzugt von 5,5 bis 6,5.The pH of the tanning liquor is adjusted in particular to a pH in the range from 5.0 to 7.0, preferably from 5.5 to 6.5.
Nachdem der pH-Wert eingestellt wurde, wird das Leder zum pH-Ausgleich über dessen gesamten Querschnitt insbesondere noch mindestens 60 Minuten im Gerbgefäß bewegt.After the pH has been adjusted, the leather is moved in the tanning vessel over its entire cross-section, in particular for at least 60 minutes, to equalize the pH.
Durch eine Temperaturerhöhung kann dieser Vorgang beschleunigt werden. Geeignete Temperaturen liegen im Bereich von 20 bis 50 °C, wobei Temperaturen zwischen 30 und 45 °C bevorzugt hervorzuheben sind.This process can be accelerated by increasing the temperature. Suitable temperatures are in the range from 20 to 50° C., temperatures between 30 and 45° C. being preferred.
Bevorzugt wird ein Leder mit einer Schrumpfungstemperatur von 70 °C oder mehr erhalten.A leather having a shrinkage temperature of 70°C or more is preferably obtained.
Bei Einsatz von Glycerinaldehyd als gerbaktiver Komponente wird insbesondere ein Leder mit einer Schrumpfungstemperatur im Bereich von 72 bis 76 °C erhalten.When glyceraldehyde is used as the tanning-active component, a leather with a shrinkage temperature in the range from 72 to 76° C. is obtained in particular.
Bei Einsatz von Glycolaldehyd als gerbaktive Komponente wird insbesondere ein Leder mit einer Schrumpfungstemperatur im Bereich von 75 bis 80 °C erhalten.If glycolaldehyde is used as the tanning-active component, a leather with a shrinkage temperature in the range from 75 to 80° C. is obtained in particular.
Gegenstand der Erfindung ist somit auch ein nach dem oben beschriebenen Verfahren unter Verwendung des erfindungsgemäßen Gerbmittels erhältliches Leder.The subject matter of the invention is therefore also a leather obtainable by the process described above using the tanning agent according to the invention.
Weitere Vorteile und Eigenschaften ergeben sich aus der nachfolgenden Beschreibung bevorzugter Ausführungsbeispiele, die jedoch nicht in einem einschränkenden Sinne verstanden werden sollen.Further advantages and properties emerge from the following description of preferred exemplary embodiments, which, however, should not be understood in a restrictive sense.
Als Gerbmittel wird eine Reaktionslösung eingesetzt, welche durch partielle Oxidation von Glycerin gewonnen wurde.A reaction solution obtained by partial oxidation of glycerine is used as the tanning agent.
Das Gerbmittel besteht aus 50 Gew.-% Wasser, 30 Gew.-% Glycerinaldehyd, 9 Gew.-% Dihydroxyaceton, 5 Gew.-% Ameisensäure, 3 Gew.-% Glycerinsäure, 2 Gew.-% Hydroxyessigsäure und 1 Gew.-% Glycerinformal, jeweils bezogen auf das Gesamtgewicht des Gerbmittels.The tanning agent consists of 50% by weight water, 30% by weight glyceraldehyde, 9% by weight dihydroxyacetone, 5% by weight formic acid, 3% by weight glyceric acid, 2% by weight hydroxyacetic acid and 1% by weight % glycerol formal, in each case based on the total weight of the tanning agent.
Das Gerbmittel wird auf einer Pickelblöße in wässriger Flotte eingesetzt.The tanning agent is used on a pickled pelt in an aqueous liquor.
Die abgetropfte Pickelblöße wird zum Ermitteln des Pickelgewichts gewogen, um auf Basis des Pickelgewichts die Einsatzmengen der Chemikalien zu berechnen, das heißt das Pickelgewicht wird als Referenzgewicht verwendet.The drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
Zu der gespaltenen oder ungespaltenen Pickelblöße wird in einem Gerbgefäß 50 % bis 100 % Wasser und 10 % des Gerbmittels hinzugefügt, entsprechend 3 Gew.-% Glycerinaldehyd, jeweils bezogen auf das Referenzgewicht.In a tanning vessel, 50% to 100% water and 10% of the tanning agent, corresponding to 3% by weight of glyceraldehyde, in each case based on the reference weight, are added to the split or unsplit pimple pelt.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Die Gerbflotte wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The tanning liquor is left to work for 120 minutes to guarantee even and complete penetration.
Danach wird der pH-Wert graduell auf einen pH-Wert im Bereich von 6,0 bis 6,5 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur graduell innerhalb von 2 Stunden zunächst auf 30 °C, dann auf 35 °C und schließlich auf 40 °C angehoben, um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to a pH in the range of 6.0 to 6.5. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature is gradually increased over a period of 2 hours, first to 30°C, then to 35°C and finally to 40°C in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials entnommen und die Schrumpfungstemperatur überprüft. Sofern die Schrumpfungstemperatur über etwa 70 - 75 °C liegt, kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is taken and the shrinkage temperature is checked. If the shrinkage temperature is above about 70 - 75 °C, the process can be continued.
Nach einem anschließenden Waschgang, insbesondere mit Wasser und wahlweise unter Zusatz von Tensiden, wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent washing cycle, in particular with water and optionally with the addition of surfactants, work continues as follows or the folding begins directly, ie the thickness of the hide substance is reduced, possibly already to the thickness of the end product.
Auch ist es möglich, die Prozessschritte zu erweitern sowie von den im Stand der Technik bekannten Standardprozessen abzuweichen in Form von zusätzlicher mechanischer Bearbeitung, zum Beispiel durch sogenanntes Nassstollen (Weichmachen) des Leders.It is also possible to expand the process steps and to deviate from the standard processes known in the prior art in the form of additional mechanical processing, for example by so-called wet staking (softening) of the leather.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100 % Wasser versetzt. Zu dieser Flotte wird 3 % eines Naphthalensulfon-Formaldehyd-Harnstoff-Kondensats sowie 3 % Weizendunst zugesetzt und 2 Stunden auf das Leder einwirken gelassen. Die Prozentangaben beziehen sich jeweils auf das Referenzgewicht.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalenesulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 hours. The percentages relate in each case to the reference weight.
Nach erneutem Waschen mit Wasser kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
Als Gerbmittel wird eine Reaktionslösung eingesetzt, welche durch partielle Oxidation von Glycerin gewonnen wurde.A reaction solution obtained by partial oxidation of glycerine is used as the tanning agent.
Das Gerbmittel besteht aus 50 Gew.-% Wasser, 30 Gew.-% Glycerinaldehyd, 9 Gew.-% Dihydroxyaceton, 5 Gew.-% Ameisensäure, 3 Gew.-% Glycerinsäure, 2 Gew.-% Hydroxyessigsäure und 1 Gew.-% Glycerinformal, jeweils bezogen auf das Gesamtgewicht des Gerbmittels.The tanning agent consists of 50% by weight water, 30% by weight glyceraldehyde, 9% by weight dihydroxyacetone, 5% by weight formic acid, 3% by weight glyceric acid, 2% by weight hydroxyacetic acid and 1% by weight % glycerol formal, in each case based on the total weight of the tanning agent.
Das Gerbmittel wird auf einer entkälkten und gebeizten Blöße in wässriger Flotte eingesetzt.The tanning agent is used on a delimed and bated pelt in an aqueous liquor.
Die Blöße wird gewogen, wobei sich das Referenzgewicht in diesem Fall auf das Gewicht bezieht, welches nach dem Spalten erhalten wird, also auf das Blößengewicht.The pelt is weighed, the reference weight in this case referring to the weight obtained after splitting, i.e. the pelt weight.
Zu der vollständig entkälkten und gebeizten Blöße werden in einem Gerbgefäß 100 % Wasser zugesetzt, bezogen auf das Referenzgewicht.100% water, based on the reference weight, is added to the completely delimed and bated pelt in a tanning vessel.
Der pH-Wert wird gemessen und falls nötig auf einen pH-Wert unter 8 mit Ameisensäure oder verdünnter Schwefelsäure angepasst.The pH is measured and if necessary adjusted to a pH below 8 with formic acid or dilute sulfuric acid.
Zu dieser Flotte werden dann 10 % des Gerbmittels zugegeben, bezogen auf das Referenzgewicht.10% of the tanning agent, based on the reference weight, is then added to this liquor.
Durch die enthaltene Säure im Gerbmittel wird der pH-Wert abgesenkt.The pH value is lowered by the acid contained in the tanning agent.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Die Gerbflotte wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The tanning liquor is left to work for 120 minutes to guarantee even and complete penetration.
Danach wird der pH-Wert graduell auf pH 6,0 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur graduell innerhalb von 2 Stunden auf 40 °C angehoben, um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to pH 6.0. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature is gradually raised to 40 °C over a period of 2 hours in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials abgeschnitten und die Schrumpfungstemperatur überprüft. Sofern die Schrumpfungstemperatur über etwa 70 °C bis 75 °C, liegt kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is cut off and the shrinkage temperature is checked. Provided the shrinkage temperature is above about 70°C to 75°C, the process can continue.
Nach einem anschließenden Waschgang wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent washing cycle, work is continued as follows or folding can be started directly, i.e. reducing the thickness of the skin substance, possibly already to the thickness of the end product.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100% Wasser versetzt. Zu dieser Flotte wird 3 % eines Naphtalensulfon-Formaldehyd-Harnstoff-Kondensat sowie 3 % Weizendunst zugesetzt und 2 Stunden auf das Leder einwirken gelassen. Die Prozentangaben beziehen sich jeweils auf das Referenzgewicht.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 hours. The percentages relate in each case to the reference weight.
Nach erneutem Waschen kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again, the leather can be processed further to produce glutaraldehyde wet white.
Als Gerbmittel wird eine Reaktionslösung eingesetzt, welche durch Zuckerpyrolyse gewonnen wurde.A reaction solution obtained through sugar pyrolysis is used as the tanning agent.
Das Gerbmittel besteht aus 40 Gew.-% Glycolaldehyd, 30 Gew.-% Wasser, 20 Gew.-% Invertzuckersirup und 10 Gew.-% organischen kurzkettigen Säuren mit 1 bis 8 Kohlenstoffatomen.The tanning agent consists of 40% by weight glycolaldehyde, 30% by weight water, 20% by weight invert sugar syrup and 10% by weight organic short-chain acids having 1 to 8 carbon atoms.
Das Gerbmittel wird auf einer Pickelblöße in wässriger Flotte eingesetzt.The tanning agent is used on a pickled pelt in an aqueous liquor.
Die abgetropfte Pickelblöße wird zum Ermitteln des Pickelgewichts gewogen, um auf Basis des Pickelgewichts die Einsatzmengen der Chemikalien zu berechnen, das heißt das Pickelgewicht wird als Referenzgewicht verwendet.The drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
Das Referenzgewicht bezieht sich dann auf die gespaltene bzw. ungespaltene Blöße.The reference weight then refers to the split or unsplit pelt.
Zu der gespaltenen oder ungespaltenen Pickelblöße in einem Gerbgefäß wird 50% Wasser und 10% des Gerbmittels hinzugefügt, entsprechend etwa 4 Gew.-% Glycolaldehyd, bezogen auf das Referenzgewicht.To the split or unsplit pickled pelt in a tanning vessel is added 50% water and 10% of the tanning agent, corresponding to about 4% by weight glycolaldehyde based on the reference weight.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Das Produkt wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The product is left on for 120 minutes to guarantee uniform and complete penetration.
Danach wird der pH-Wert graduell auf einen pH-Wert von 6,0 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur ausgehend von Raumtemperatur (25 °C) graduell über 2 Stunden auf eine Temperatur von 40 °C angehoben um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to a pH of 6.0. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature, starting from room temperature (25 °C), is gradually increased over 2 hours to a temperature of 40 °C in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials abgeschnitten und die Schrumpfungstemperatur überprüft. Wenn die Schrumpfungstemperatur über etwa 70 °C bis 80 °C liegt, kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrinkage temperature is above about 70°C to 80°C, the process can proceed.
Nach einem anschließenden Waschgang mit Wasser wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent washing cycle with water, work continues as follows or the folding can be started directly, i.e. reducing the thickness of the hide substance, possibly already to the thickness of the end product.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100% Wasser versetzt. Zu dieser Flotte wird 3% eines Naphtalensulfon-Formaldehyd-Harnstoff-Kondensats sowie 3 % Weizendunst zugesetzt und 2 bis 4 Stunden auf das Leder einwirken gelassen. Die Prozentangaben beziehen sich jeweils auf das Referenzgewicht.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours. The percentages relate in each case to the reference weight.
Nach erneutem Waschen mit Wasser kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
Als Gerbmittel wird eine Mischung einer Reaktionslösung, welche durch partielle Oxidation von Glycerin gewonnen wurde, und einer Reaktionslösung, welche durch Zuckerpyrolyse gewonnen wurde, eingesetzt. Mit anderen Worten werden zwei Teilreaktionslösungen im Gerbmittel eingesetzt.A mixture of a reaction solution obtained by partial oxidation of glycerol and a reaction solution obtained by pyrolysis of sugar is used as the tanning agent. In other words, two partial reaction solutions are used in the tanning agent.
Das Gerbmittel besteht aus 40 Gew.-% Wasser, 20 Gew.-% Glycolaldehyd, 15 Gew.-% Glycerinaldehyd, 8 Gew.-% Invertzuckersirup, 5 Gew.-% Dihydroxyaceton, 5 Gew.-% Ameisensäure, 2 Gew.-% Glycerinsäure, 2 Gew.-% Hydroxyessigsäure, 2 Gew.-% Essigsäure und 1 Gew.-% Glycerinformal.The tanning agent consists of 40% by weight water, 20% by weight glycolaldehyde, 15% by weight glyceraldehyde, 8% by weight invert sugar syrup, 5% by weight dihydroxyacetone, 5% by weight formic acid, 2% by weight % glyceric acid, 2% by weight hydroxyacetic acid, 2% by weight acetic acid and 1% by weight glycerol formal.
Das Gerbmittel wird auf einer Pickelblöße in wässriger Flotte eingesetzt.The tanning agent is used on a pickled pelt in an aqueous liquor.
Die abgetropfte Pickelblöße wird zum Ermitteln des Pickelgewichts gewogen, um auf Basis des Pickelgewichts die Einsatzmengen der Chemikalien zu berechnen, das heißt das Pickelgewicht wird als Referenzgewicht verwendet.The drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
Das Referenzgewicht bezieht sich dann auf die gespaltene bzw. ungespaltene Blöße.The reference weight then refers to the split or unsplit pelt.
Zu der gespaltenen oder ungespaltenen Pickelblöße in einem Gerbgefäß wird 50 % Wasser und 10 % des Gerbmittels hinzugefügt, bezogen auf das Referenzgewicht.50% water and 10% of the tanning agent, based on the reference weight, are added to the split or unsplit pelt in a tanning vessel.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Das Produkt wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The product is left on for 120 minutes to guarantee uniform and complete penetration.
Danach wird der pH-Wert graduell auf einen pH-Wert von 6,0 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur ausgehend von Raumtemperatur (25 °C) graduell über 2 Stunden auf eine Temperatur von 40 °C angehoben, um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to a pH of 6.0. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature is gradually raised from room temperature (25 °C) to 40 °C over a period of 2 hours in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials abgeschnitten und die Schrumpfungstemperatur überprüft. Wenn die Schrumpfungstemperatur über etwa 70 °C bis 80 °C liegt, kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrinkage temperature is above about 70°C to 80°C, the process can proceed.
Nach einem anschließenden Waschgang mit Wasser wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent washing cycle with water, work continues as follows or the folding can be started directly, i.e. reducing the thickness of the hide substance, possibly already to the thickness of the end product.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100% Wasser versetzt. Zu dieser Flotte wird 3 % eines Naphtalensulfon-Formaldehyd-Harnstoff-Kondensats sowie 3 % Weizendunst zugesetzt und 2 bis 4 Stunden auf das Leder einwirken gelassen.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours.
Nach erneutem Waschen mit Wasser kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
Beispiel 5: Gerbung mit Acetalen und Hemiacetalen von Glycerinaldehyd (mitExample 5: Tanning with acetals and hemiacetals of glyceraldehyde (with
Als Gerbmittel wird eine Mischung einer Reaktionslösung, welche durch partielle Oxidation von Glycerin gewonnen wurde, und Butyldiglykol eingesetzt.A mixture of a reaction solution obtained by partial oxidation of glycerol and butyl diglycol is used as the tanning agent.
Das Gerbmittel besteht aus 40 Gew.-% Wasser, 20 Gew.-% Glycerinaldehyd, 15 Gew.-% Glycerinaldehyd-Butyldiglykolacetal, 15 Gew.-% Butyldiglykol und 10 Gew.-% Dihydroxyaceton und dessen Ketal mit Butyldiglykol.The tanning agent consists of 40% by weight water, 20% by weight glyceraldehyde, 15% by weight glyceraldehyde butyldiglycol acetal, 15% by weight butyldiglycol and 10% by weight dihydroxyacetone and its ketal with butyldiglycol.
Das Gerbmittel wird auf einer Pickelblöße in wässriger Flotte eingesetzt.The tanning agent is used on a pickled pelt in an aqueous liquor.
Die abgetropfte Pickelblöße wird zum Ermitteln des Pickelgewichts gewogen, um auf Basis des Pickelgewichts die Einsatzmengen der Chemikalien zu berechnen, das heißt das Pickelgewicht wird als Referenzgewicht verwendet.The drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
Das Referenzgewicht bezieht sich dann auf die gespaltene bzw. ungespaltene Blöße.The reference weight then refers to the split or unsplit pelt.
Zu der gespaltenen oder ungespaltenen Pickelblöße in einem Gerbgefäß wird 50 % Wasser und 10 % des Gerbmittels hinzugefügt, bezogen auf das Referenzgewicht.50% water and 10% of the tanning agent, based on the reference weight, are added to the split or unsplit pelt in a tanning vessel.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Das Produkt wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The product is left on for 120 minutes to guarantee uniform and complete penetration.
Danach wird der pH-Wert graduell auf einen pH-Wert von 7,0 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur ausgehend von Raumtemperatur (25 °C) graduell über 4 Stunden auf eine Temperatur von 40 °C angehoben, um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to a pH of 7.0. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature is gradually raised from room temperature (25 °C) to 40 °C over 4 hours in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials abgeschnitten und die Schrumpfungstemperatur überprüft. Wenn die Schrumpfungstemperatur über etwa 70 °C bis 75 °C liegt, kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrink temperature is above about 70°C to 75°C, the process can proceed.
Nach einem anschließenden Waschgang mit Wasser wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent wash with water, work continues as follows or start folding directly, i.e. with the Reducing the thickness of the skin substance, if necessary already to the thickness of the end product.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100% Wasser versetzt. Zu dieser Flotte wird 3 % eines Naphtalensulfon-Formaldehyd-Harnstoff-Kondensats sowie 3 % Weizendunst zugesetzt und 2 bis 4 Stunden auf das Leder einwirken gelassen. Die Prozentangaben beziehen sich jeweils auf das Referenzgewicht.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours. The percentages relate in each case to the reference weight.
Nach erneutem Waschen mit Wasser kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
Als Gerbmittel wird eine Mischung einer Reaktionslösung, welche durch Zuckerpyrolyse gewonnen wurde, und Butyldiglykol eingesetzt.A mixture of a reaction solution obtained by pyrolysis of sugar and butyl diglycol is used as the tanning agent.
Das Gerbmittel besteht aus 30 Gew.-% Wasser, 15 Gew.-% % Glycolaldehyd, 20 Gew.-% Glycolaldehyd-Butyldiglykolacetal, 15 Gew.-% Butyldiglykol und 20 Gew.-% Invertzuckersirup.The tanning agent consists of 30% by weight water, 15% by weight glycolaldehyde, 20% by weight glycolaldehyde butyldiglycol acetal, 15% by weight butyldiglycol and 20% by weight invert sugar syrup.
Das Gerbmittel wird auf einer Pickelblöße in wässriger Flotte eingesetzt.The tanning agent is used on a pickled pelt in an aqueous liquor.
Die abgetropfte Pickelblöße wird zum Ermitteln des Pickelgewichts gewogen, um auf Basis des Pickelgewichts die Einsatzmengen der Chemikalien zu berechnen, das heißt das Pickelgewicht wird als Referenzgewicht verwendet.The drained pimple pelt is weighed to determine the pimple weight in order to calculate the quantities of chemicals used on the basis of the pimple weight, i.e. the pimple weight is used as a reference weight.
Das Referenzgewicht bezieht sich dann auf die gespaltene bzw. ungespaltene Blöße.The reference weight then refers to the split or unsplit pelt.
Zu der gespaltenen oder ungespaltenen Pickelblöße in einem Gerbgefäß wird 50 % Wasser und 10 % des Gerbmittels hinzugefügt, bezogen auf das Referenzgewicht.50% water and 10% of the tanning agent, based on the reference weight, are added to the split or unsplit pelt in a tanning vessel.
Das Gerbgefäß wird während des gesamten Prozesses bewegt. Das Produkt wird 120 Minuten einwirken gelassen, um eine gleichmäßige und vollständige Penetration zu garantieren.The tanning vessel is moved throughout the process. The product is left on for 120 minutes to guarantee uniform and complete penetration.
Danach wird der pH-Wert graduell auf einen pH-Wert von 7,0 angehoben. Hierzu wird Natriumhydrogencarbonat verwendet. Die zugegebene Menge ist abhängig von der Säurekapazität der Gerbflotte. Nach Erreichen des pH-Wertes wird die Temperatur ausgehend von Raumtemperatur (25 °C) graduell über 4 Stunden auf eine Temperatur von 40 °C angehoben, um den Gerbstoff zu fixieren.Thereafter, the pH is gradually raised to a pH of 7.0. Sodium bicarbonate is used for this. The amount added depends on the acid capacity of the tanning liquor. After the pH value has been reached, the temperature is gradually raised from room temperature (25 °C) to 40 °C over 4 hours in order to fix the tanning agent.
Nach der Fixierung wird eine Probe des gegerbten Materials abgeschnitten und die Schrumpfungstemperatur überprüft. Wenn die Schrumpfungstemperatur über etwa 70 °C bis 80 °C liegt, kann mit dem Prozess fortgefahren werden.After fixing, a sample of the tanned material is cut off and the shrinkage temperature is checked. If the shrinkage temperature is above about 70°C to 80°C, the process can proceed.
Nach einem anschließenden Waschgang mit Wasser wird wie folgt weitergearbeitet oder direkt mit dem Falzen begonnen, das heißt mit dem Verringern der Dicke der Hautsubstanz, ggf. bereits auf die Dicke des Endprodukts.After a subsequent washing cycle with water, work continues as follows or the folding can be started directly, i.e. reducing the thickness of the hide substance, possibly already to the thickness of the end product.
Die Gerbflotte wird abgelassen und das vorgegerbte Material mit 100% Wasser versetzt. Zu dieser Flotte wird 3 % eines Naphtalensulfon-Formaldehyd-Harnstoff-Kondensats sowie 3 % Weizendunst zugesetzt und 2 bis 4 Stunden auf das Leder einwirken gelassen. Die Prozentangaben beziehen sich jeweils auf das Referenzgewicht.The tanning liquor is drained off and 100% water is added to the pretanned material. 3% of a naphthalene sulfone-formaldehyde-urea condensate and 3% of wheat vapor are added to this liquor and the leather is left to act for 2 to 4 hours. The percentages relate in each case to the reference weight.
Nach erneutem Waschen mit Wasser kann das Leder gleichwertig zu Glutaraldehyd-Wetwhite weiterverarbeitet werden.After washing again with water, the leather can be processed further to produce glutaraldehyde wet white.
Claims (13)
wobei die Reaktionslösung erhalten ist durch partielle Oxidation und/oder Pyrolyse einer organischen Substanz mit einer vicinalen Diolgruppe.Tanning agent, comprising a reaction solution which contains a tanning-active component selected from the group consisting of glyceraldehyde, glycolaldehyde, acetals of these compounds, hemiacetals of these compounds and combinations thereof,
wherein the reaction solution is obtained by partial oxidation and/or pyrolysis of an organic substance having a vicinal diol group.
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ES21183144T ES2975566T3 (en) | 2021-07-01 | 2021-07-01 | Tanning agent, use of a tanning agent and procedure for tanning animal skins and the leather obtained from them |
PL21183144.1T PL4112748T3 (en) | 2021-07-01 | 2021-07-01 | Tanning agent, use of a tanning agent, process for the tanning of animal skins and furs and leather obtained thereof |
EP21183144.1A EP4112748B1 (en) | 2021-07-01 | 2021-07-01 | Tanning agent, use of a tanning agent, process for the tanning of animal skins and furs and leather obtained thereof |
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CN116622919A (en) * | 2023-07-06 | 2023-08-22 | 四川大学 | Method for preparing transparent leather by adopting chrome-free tanning blank |
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EP2607500A1 (en) | 2011-12-23 | 2013-06-26 | Hermes Sellier | Leather manufacturing process using a soluble oxidized starch-derived polysaccharide and compositions containing it |
EP2574682B1 (en) | 2011-09-30 | 2013-10-30 | Kemira Oyj | Environmentally friendly composition, suitable for leather tanning, comprising zeolite |
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2021
- 2021-07-01 EP EP21183144.1A patent/EP4112748B1/en active Active
- 2021-07-01 ES ES21183144T patent/ES2975566T3/en active Active
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EP2574682B1 (en) | 2011-09-30 | 2013-10-30 | Kemira Oyj | Environmentally friendly composition, suitable for leather tanning, comprising zeolite |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116622919A (en) * | 2023-07-06 | 2023-08-22 | 四川大学 | Method for preparing transparent leather by adopting chrome-free tanning blank |
CN116622919B (en) * | 2023-07-06 | 2024-05-24 | 四川大学 | Method for preparing transparent leather by adopting chrome-free tanning blank |
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EP4112748C0 (en) | 2024-01-03 |
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PL4112748T3 (en) | 2024-04-08 |
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