EP0245205B1 - Aqueous composition comprising a sulfonated phenol, an amine and a tanning salt, its manufacture and its use as a tanning agent - Google Patents
Aqueous composition comprising a sulfonated phenol, an amine and a tanning salt, its manufacture and its use as a tanning agent Download PDFInfo
- Publication number
- EP0245205B1 EP0245205B1 EP87810273A EP87810273A EP0245205B1 EP 0245205 B1 EP0245205 B1 EP 0245205B1 EP 87810273 A EP87810273 A EP 87810273A EP 87810273 A EP87810273 A EP 87810273A EP 0245205 B1 EP0245205 B1 EP 0245205B1
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- European Patent Office
- Prior art keywords
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- composition
- phenol
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- 239000000203 mixture Substances 0.000 title claims description 58
- 150000003839 salts Chemical class 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000002989 phenols Chemical class 0.000 title description 2
- 150000001412 amines Chemical class 0.000 title 1
- 229940061610 sulfonated phenol Drugs 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011651 chromium Substances 0.000 claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000010985 leather Substances 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002566 KAl(SO4)2·12H2O Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 235000007831 chromium(III) chloride Nutrition 0.000 claims description 2
- 239000011636 chromium(III) chloride Substances 0.000 claims description 2
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229940048084 pyrophosphate Drugs 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 229910018626 Al(OH) Inorganic materials 0.000 claims 2
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 235000011128 aluminium sulphate Nutrition 0.000 claims 1
- QRTRRDMHGTZPBF-UHFFFAOYSA-L oxygen(2-);zirconium(4+);sulfate Chemical compound [O-2].[Zr+4].[O-]S([O-])(=O)=O QRTRRDMHGTZPBF-UHFFFAOYSA-L 0.000 claims 1
- 239000011369 resultant mixture Substances 0.000 claims 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 244000309466 calf Species 0.000 description 2
- 235000019820 disodium diphosphate Nutrition 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- OOFAEFCMEHZNGP-UHFFFAOYSA-N 1-n',1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(N)N(C)C OOFAEFCMEHZNGP-UHFFFAOYSA-N 0.000 description 1
- CYXGZZFAAUDHQL-UHFFFAOYSA-N 1-n,1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(NC)NC CYXGZZFAAUDHQL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- 229940038485 disodium pyrophosphate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000991 leather dye Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
Definitions
- component (A) of the composition of the invention SO3 or especially oleum.
- reaction products of phenol and oleum are particularly suitable for component (A), the molar ratio (phenol) :( SO3) especially (1) :( 1.4-1.8).
- Component (A) is known per se.
- British Patent 683,084 the production of reaction products from phenol and oleum, which, however, with e.g. Formaldehyde and urea or thiourea are further implemented and also used as tanning agents.
- FR-A-2,263,304 describes tanning agents which are obtained by sulfonation of a phenolic compound and a non-phenolic aromatic compound and subsequent condensation. These tanning agents are used together with a chrome or zirconium salt.
- Component (A) used according to the invention is a mixture of polyhydroxy-polyphenylsulfonic sulfonic acids, which presumably contains a 3,3'-dihydroxydiphenylsulfonic disulfonic acid as the main component.
- component (B) Preferably come for component (B) as primary, secondary or tertiary C1-C4-alkylamine, C2-C3-alkanolamine or C2-C6-alkylenediamine, especially mono-, di- or triethanolamine, dimethylethanolamine, ethylenediamine and N-hydroxyethyl-ethylenediamine , as poly-C2-C3-alkylene-polyamine with 3 to 5 nitrogen atoms N, N-dimethylpropylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene tetramine, and tetraethylene pentamine and especially as a heterocyclic amine, for example morpholine obtainable from diethanolamine and sulfuric acid.
- diethanolamine is the focus of interest.
- the ready-to-use tanning salts suitable for component (c) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chromium and aluminum salts mentioned are also well suited for use as component (C).
- the optional component (D) is used in the composition according to the invention, preference is given to the tetrasodium salt of ethylenediaminetetraacetic acid or the neutral or acidic sodium pyrophosphate (Na4P2O7 or Na2H2P2O7).
- the optional component (D) acts as a complexing agent and is preferably used in the composition in the case of an iron-free tanning agent, provided the iron content of the oleum used in the production of component (A) is relatively high.
- the weights of component (C) in the weight ratio of component (A) to component (C) are advantageously based on the metal atom of the corresponding tanning salts.
- chrome tanning salts as component (C)
- a maximum of 0.375 parts of chromium per part of component (A) can be used. Higher amounts of chromium would no longer be soluble in the composition and would lead to inhomogeneous compositions.
- preferred compositions contain components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.03 to 0.5), based on the metal atom of component (C), at most 0.375 parts of chrome are present.
- compositions which have the highest possible levels of tanning salts are desirable, since the tanning salts as component (c) are cheaper in comparison with the reaction products of phenol and oleum as component (A), the tanning effect of the composition on both component (A) and also on the component (C) is due.
- compositions are particularly preferred which contain the components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.3 to 0.375).
- the compositions contain components (A) and (D) in a weight ratio (A) :( D) of (1) :( 0 to 0.04).
- compositions according to the invention have a water content of 40 to 80, preferably 45 to 62 percent by weight.
- the procedure is generally such that an aqueous solution of component (A) and, if appropriate, component (D) are first mixed with component (B) and then with component (C), which may be present as an aqueous solution .
- component (A) should first be diluted with water for safety reasons, giving about 50 to 70 percent by weight solutions of component (A).
- component (B) alone or in admixture with the optional component (D)
- component (A) and optionally component (D) with component (B) can be carried out in an aqueous medium with moderate external cooling at preferably 60 to 90 ° C.
- component (C) Only at the end is component (C) added to the mixture of components (A), (B) and optionally (D).
- Component (D) can be added as a solid with vigorous stirring. This is particularly true when using e.g. Aluminum tanning salts as component (C).
- component (C) When using chrome tanning salts, it has proven to be particularly advantageous to use component (C) as an aqueous solution, the aqueous solution of component (C) before mixing with components (A), (B) and optionally (D) is usually heated to 60 to 90 ° C. After all the components have been mixed, the composition is generally diluted with water to the preferred water content of 40 to 80 percent by weight.
- compositions according to the invention obtained in this way are liquid and are particularly suitable for tanning raw materials or for retanning leather of all kinds.
- the conventional method is used to treat pale or pretanned leather with an aqueous solution which contains the aqueous composition according to the invention, and then the material which has been tanned in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done.
- 100 to 200, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of leather or leather.
- 100 parts by weight, preferably descaled, of tanned material is tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the composition according to the invention, or 100 parts by weight in the usual manner with chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight Retanned water and 5 to 15 parts of the composition according to the invention.
- the tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
- the composition according to the invention has the essential advantage of being particularly stable in storage thanks to the presence of component (B). Even after several months of storage, no clouding or flocculation can be found in the composition.
- composition comprising 166.5 parts of the reaction product from phenol and oleum, 15 parts of diethanolamine, 198 parts of Cr (OH) SO4 (corresponds to 62.3 parts of chromium), 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and 616.5 parts Contains water. After 3 months of storage, the composition remains homogeneous, i.e. shows no cloudiness or flocculation. A 1% solution of this composition has a pH of 2.9.
- a filtered solution of 139 parts Cr (OH) SO4 (corresponding to 43.8 parts chromium) and 45.78 parts Al2 (OH) 4SO4 (corresponding to 11.3 parts aluminum) in 484 is now added to the reaction solution, preheated to 70 ° C, Given 72 parts of water.
- the reaction solution is then kept under stirring at 70 ° C. for 20 minutes and then cooled to 20 ° C. 1000 parts of a composition are obtained which are stable on storage.
- a 1% solution of this composition has a pH of 3.
- a storage-stable composition is also obtained if instead of the 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and the 10 parts of diethanolamine, 3 parts of trisodium phosphate or 7.5 parts of N, N'-dimethyl-propane-diamine are used.
- Example 2 The procedure is as given in Example 2, but using a filtered solution which has been preheated to 70 ° C. and contains the following parts of tanning salt or water instead of the 45.78 parts of Al2 (OH) 4SO4 and the 484.72 parts of water: example Parts of tannin salt Parts of water 3rd 98.6 AlCl3 ⁇ 6H2O * 431.9 4th 130 Al2 (SO4) 316H2O * 400.5 5 40.3 Al (OH) 2Cl * 490.2 6 47 Al (OH) Cl2 * 483.5 7 195 KAl (SO4) 212H2O * 335.5 8th 76 Fe2 (SO4) 39H2O ** 458.5 * corresponding to 11.03 parts of aluminum ** corresponding to 15 parts of iron
- compositions with good storage stability are also obtained if, instead of the 65.36 parts of Zr (OH) 2SO4, 95.0 parts of ZrOCl2 ⁇ 8H2O or 106 parts of Zr (SO4) 2 ⁇ 4H2O (all corresponding to 26.82 parts of zirconium) are used.
- 100 parts of decalcified veal pellet are treated with 150 parts of water and 15 parts of the composition prepared according to Example 1 for 24 hours at 20 ° C. in a rolling barrel. After neutralizing, washing, greasing, stretching, drying, conditioning, studs and sperm, you get a tanned, lightly covered leather that has a full grain and a soft feel.
- 100 parts of folded chrome grain calf leather are treated with 150 parts of water and 10 parts of the composition prepared according to Example 1 for 2 hours at 50 ° C. in a rolling barrel.
- the leather is neutralized with sodium formate and sodium bicarbonate using customary methods, washed, dyed with 1 part of the leather dye CI Acid Brown 189 and aftertreated with a commercially available fatliquor based on sulfonated fish oil.
- a tanned, brown-colored, brilliant leather is obtained, which also has a full grain and a soft handle.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Coloring (AREA)
Description
Gegenstand der vorliegenden Erfindung ist eine wässrige Zusammensetzung enthaltend als Komponente C ein wassenlösliches Chrom-, Aluminium-, Eisen oder Zirkoniumgerbesalz oder dessen Gemische, die dadurch gekennzeichnet ist, dass sie
- (A) ein Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel, wobei das Molverhältnis (Phenol):(SO₃) (1):(1,1-2,2) beträgt,
- (B) ein wasserlösliches, primäres, sekundäres oder tertiäres C₁-C₄-Alkylamin, C₂-C₃-Alkanolamin oder C₂-C₆-Alkylendiamin, ein Poly-C₂-C₃-alkylen-polyamin mit 3 bis 5 Stickstoffatomen oder ein heterocyclisches Amin, wobei höchstens 0,2 Gewichtsteile der Komponente B pro gewichtsteil der Komponente (A) eingesetzt werden und gegebenenfalls
- (D) ein Alkalimetallsalz der Ethylendiamintetraessigsäure oder eines Pyrophosphates
- (A) a reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO₃) (1) :( being 1.1-2.2),
- (B) a water-soluble, primary, secondary or tertiary C₁-C₄-alkylamine, C₂-C₃-alkanolamine or C₂-C₆-alkylenediamine, a poly-C₂-C₃-alkylene-polyamine with 3 to 5 nitrogen atoms or a heterocyclic amine, where not more than 0.2 part by weight of component B per part by weight of component (A) and, if appropriate
- (D) an alkali metal salt of ethylenediaminetetraacetic acid or a pyrophosphate
Das Herstellungsverfahren und die Verwendung als Gerbstoff der vorstehend angegebenen Zusammensetzung bilden weitere Erfindungsgegenstände.The production process and the use as tanning agent of the composition specified above form further subject matter of the invention.
Bevorzugt wird als Sulfonierungsmittel zur Darstellung der Komponente (A) der erfindungsgemässen Zusammensetzung SO₃ oder vor allem Oleum eingesetzt. Somit kommen für die Komponente (A) insbesondere Umsetzungsprodukte aus Phenol und Oleum in Frage, wobei das Molverhältnis (Phenol):(SO₃) vor allem (1):(1,4-1,8) beträgt.Is preferably used as a sulfonating agent for the preparation of component (A) of the composition of the invention SO₃ or especially oleum. Thus, reaction products of phenol and oleum are particularly suitable for component (A), the molar ratio (phenol) :( SO₃) especially (1) :( 1.4-1.8).
Die Komponente (A) ist an sich bekannt. So beschreibt z.B. die britische Patentschrift 683 084 die Herstellung von Umsetzungsprodukten aus Phenol und Oleum, die jedoch mit z.B. Formaldehyd und Harnstoff oder Thioharnstoff weiter umgesetzt werden und ebenfalls als Gerbstoffe Verwendung finden. Die FR-A-2,263,304 beschreibt Gerbstoffe, die durch Sulfonierung einer phenolischen Verbindung und einer nichtphenolischen aromatischen Verbindung und anschliessender Kondensation erhalten werden. Diese Gerbstoffe werden zusammen mit einem Chrom- oder Zirkoniumsalz eingesetzt. Die erfindungsgemäss eingesetzte Komponente (A) stellt ein Gemisch aus Polyhydroxy-polyphenylsulfon-sulfonsäuren dar, das vermutlich eine 3,3'-Dihydroxydiphenylsulfon-disulfonsäure als Hauptbestandteil enthält.Component (A) is known per se. For example, British Patent 683,084, the production of reaction products from phenol and oleum, which, however, with e.g. Formaldehyde and urea or thiourea are further implemented and also used as tanning agents. FR-A-2,263,304 describes tanning agents which are obtained by sulfonation of a phenolic compound and a non-phenolic aromatic compound and subsequent condensation. These tanning agents are used together with a chrome or zirconium salt. Component (A) used according to the invention is a mixture of polyhydroxy-polyphenylsulfonic sulfonic acids, which presumably contains a 3,3'-dihydroxydiphenylsulfonic disulfonic acid as the main component.
Bevorzugt kommen für die Komponente (B) als primäres, sekundäres oder tertiäres C₁-C₄-Alkylamin, C₂-C₃-Alkanolamin oder C₂-C₆-Alkylendiamin vor allem Mono-, Di- oder Triethanolamin, Dimethylethanolamin, Ethylendiamin und N-Hydroxyethyl-ethylendiamin, als Poly-C₂-C₃-alkylen-polyamin mit 3 bis 5 Stickstoffatomen N,N-Dimethylpropylendiamin, Pentamethylendiamin, Hexamethylendiamin, Triethylentetramin, und Tetraethylenpentamin und als heterocyclisches Amin vor allem das z.B. aus Diethanolamin und Schwefelsäure erhältliche Morpholin in Betracht. Hierbei steht indessen Diethanolamin im Vordergrund des Interesses.Preferably come for component (B) as primary, secondary or tertiary C₁-C₄-alkylamine, C₂-C₃-alkanolamine or C₂-C₆-alkylenediamine, especially mono-, di- or triethanolamine, dimethylethanolamine, ethylenediamine and N-hydroxyethyl-ethylenediamine , as poly-C₂-C₃-alkylene-polyamine with 3 to 5 nitrogen atoms N, N-dimethylpropylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene tetramine, and tetraethylene pentamine and especially as a heterocyclic amine, for example morpholine obtainable from diethanolamine and sulfuric acid. Here, however, diethanolamine is the focus of interest.
Die für die Komponente (c) in Betracht kommenden gebrauchsfertigen Gerbesalze sind in der einschlägigen Fachliteratur beschrieben. Es handelt sich hierbei in der Regel um Chrom-, Aluminium-, Eisen- oder Zirkoniumsalze. Als Beispiele solcher Salze sei basisches Chrom(III)-chlorid oder -sulfat, ein Chromalaun, gegebenenfalls basisches Aluminiumchlorid oder -sulfat, ein Alaun, Eisen(III)-chlorid oder -sulfat, Zirkonoxychlorid und Zirkoniumsulfat genannt. Auch Gemische der genannten Chrom- und Aluminiumsalze eignen sich gut dazu, als Komponente (C) eingesetzt zu werden. Bevorzugt sind indessen [CrCl₂(OH₂)₄]Cl·2 H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄,KCr(SO₄)₂·12 H₂O, AlCl₃·6 H₂O, Al₂(SO₄)₃·16 H₂O, Al₂(OH)₄SO₄, Al(OH)₂Cl, Al(OH)Cl₂, KAl(SO₄)₂·12 H₂O, Fe₂(SO₄)₃·9 H₂O, Zr(OH)₂SO₄, ZrOCl₂·8 H₂O und Zr(SO₄)₂·4 H₂O.The ready-to-use tanning salts suitable for component (c) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chromium and aluminum salts mentioned are also well suited for use as component (C). However, preference is given to [CrCl₂ (OH₂) ₄] Cl · 2 H₂O, [Cr (OH₂) ₆] Cl₃, Cr (OH) SO₄, Cr₂ (OH) ₄SO₄, KCr (SO₄) ₂ · 12 H₂O, AlCl₃ · 6 H₂O, Al₂ (SO₄) ₃ · 16 H₂O, Al₂ (OH) ₄SO₄, Al (OH) ₂Cl, Al (OH) Cl₂, KAl (SO₄ ) ₂ · 12 H₂O, Fe₂ (SO₄) ₃ · 9 H₂O, Zr (OH) ₂SO₄, ZrOCl₂ · 8 H₂O and Zr (SO₄) ₂ · 4 H₂O.
Im Vordergrund des Interesses stehen die basischen Chromsulfate Cr(OH)SO₄ und Cr₂(OH)₄SO₄, die aus Chromalaun und einem Alkali im Aequivalentverhältnis 3:1 und 3:2 erhältlich sind (vgl. z.B. Gerbereichemisches Taschenbuch von A. Küntzel, Steinkopff Verlag, 1955).In the foreground of interest are the basic chromium sulfates Cr (OH) SO₄ and Cr₂ (OH) ₄SO₄, which are available from chromium alum and an alkali in an equivalent ratio of 3: 1 and 3: 2 (see e.g. Gerreichemisches Taschenbuch by A. Küntzel, Steinkopff Verlag , 1955).
Sofern die fakultative Komponente (D) in der erfindungsgemässen Zusammensetzung mitverwendet wird, kommt bevorzugt das Tetranatriumsalz der Ethylendiamintetraessigsäure oder das neutrale oder saure Natriumpyrophosphat (Na₄P₂O₇ oder Na₂H₂P₂O₇) in Betracht. Die fakultative Komponente (D) wirkt als Komplexierungsmittel und wird in der Zusammensetzung vorzugsweise bei eisenfreiem Gerbmittel mitverwendet, sofern der Eisengehalt des bei der Herstellung der Komponente (A) eingesetzten Oleums relativ hoch ist.If the optional component (D) is used in the composition according to the invention, preference is given to the tetrasodium salt of ethylenediaminetetraacetic acid or the neutral or acidic sodium pyrophosphate (Na₄P₂O₇ or Na₂H₂P₂O₇). The optional component (D) acts as a complexing agent and is preferably used in the composition in the case of an iron-free tanning agent, provided the iron content of the oleum used in the production of component (A) is relatively high.
Da die Gerbesalze der angegebenen Art als Komponente (c) sehr unterschiedliche Molgewichte aufweisen, werden im Gewichtsverhältnis der Komponente (A) zur Komponente (C) die Gewichte der Komponente (C) vorteilhafterweise auf das Metallatom der entsprechenden Gerbesalze bezogen. Zudem kann bei Verwendung von Chromgerbesalzen als Komponente (C) höchstens 0,375 Teile Chrom pro Teil Komponente (A) eingesetzt werden. Höhere Chrommengen wären in der Zusammensetzung nicht mehr löslich und würden zu unhomogenen Zusammensetzungen führen. Somit enthalten bevorzugte Zusammensetzungen die Komponenten (A) und (C) in einem Gewichtsverhältnis (A):(C) von (1):(0,03 bis 0,5), bezogen auf das Metallatom der Komponente (C), wobei höchstens 0,375 Teile Chrom vorhanden sind. Erwünscht sind Zusammensetzungen, die möglichst hohe Gehalte an Gerbesalze aufweisen, da die Gerbesalze als Komponente (c) im Vergleich zu den Umsetzungsprodukten aus Phenol und Oleum als Komponente (A) billiger sind, wobei die Gerbwirkung der Zusammensetzung sowohl auf die Komponente (A) als auch auf die Komponente (C) zurückzuführen ist. Somit sind Zusammensetzungen besonders bevorzugt, welche die Komponenten (A) und (C) in einem Gewichtsverhältnis (A):(C) von (1):(0,3 bis 0,375) enthalten.Since the tanning salts of the type indicated have very different molecular weights as component (c), the weights of component (C) in the weight ratio of component (A) to component (C) are advantageously based on the metal atom of the corresponding tanning salts. In addition, when using chrome tanning salts as component (C), a maximum of 0.375 parts of chromium per part of component (A) can be used. Higher amounts of chromium would no longer be soluble in the composition and would lead to inhomogeneous compositions. Thus preferred compositions contain components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.03 to 0.5), based on the metal atom of component (C), at most 0.375 parts of chrome are present. Compositions which have the highest possible levels of tanning salts are desirable, since the tanning salts as component (c) are cheaper in comparison with the reaction products of phenol and oleum as component (A), the tanning effect of the composition on both component (A) and also on the component (C) is due. Thus, compositions are particularly preferred which contain the components (A) and (C) in a weight ratio (A) :( C) of (1) :( 0.3 to 0.375).
Sofern die fakultative Komponente (D) mitverwendet wird, ist der Einsatz von 0,04 Gewichtsteilen der Komponente (D) pro Gewichtsteil der Komponente (A) genügend, um die Komplexierwirkung der Komponente (D) zu erzielen. Somit enthalten in der Regel die Zusammensetzungen die Komponenten (A) und (D) in einem Gewichtsverhältnis (A):(D) von (1):(0 bis 0,04).If the optional component (D) is also used, the use of 0.04 part by weight of component (D) per part by weight of component (A) is sufficient to achieve the complexing effect of component (D). Thus, as a rule, the compositions contain components (A) and (D) in a weight ratio (A) :( D) of (1) :( 0 to 0.04).
Eine mit Wasser auf 1 %, bezogen auf Trockensubstanz der Komponenten (A), (B), (C) und gegebenenfalls (D), verdünnte erfindungsgemässe Zusammensetzung weist einen pH-Wert von höchstens 5 auf. Die 1%-igen wässrigen Lösungen von erfindungsgemässen Zusammensetzungen, welche die Komponenten (A) und (B) im bevorzugten Gewichtsverhältnis (A):(B) von (1):(0,05 bis 0,18) enthalten, weisen einen pH-Wert von 0 bis 3,5 auf.A composition according to the invention diluted with water to 1%, based on the dry substance of components (A), (B), (C) and optionally (D), has a pH of at most 5. The 1% aqueous solutions of compositions according to the invention which contain components (A) and (B) in the preferred weight ratio (A) :( B) of (1) :( 0.05 to 0.18) have a pH -Value from 0 to 3.5.
Im allgemeinen weisen die erfindungsgemässen Zusammensetzungen einen Wassergehalt von 40 bis 80, vorzugsweise 45 bis 62 Gewichtsprozent auf.In general, the compositions according to the invention have a water content of 40 to 80, preferably 45 to 62 percent by weight.
Bei der Herstellung der erfindungsgemässen Zusammensetzung wird im allgemeinen so verfahren, dass man eine wässrige Lösung der Komponente (A) und gegebenenfalls die Komponente (D) zuerst mit der Komponente (B) und anschliessend mit der gegebenenfalls als wässrige Lösung vorliegenden Komponente (C) vermischt. Vor dem Vermischen mit der Komponente (B) und gegebenenfalls mit der Komponente (D) sollte die Komponente (A) aus sicherheitstechnischen Gründen zuerst mit Wasser verdünnt werden, wobei etwa 50 bis 70 gewichtsprozentige Lösungen der Komponente (A) erhalten werden. Hierbei wird in der Regel die Komponente (B) für sich allein oder in Gemisch mit der fakultativen Komponente (D) zur wässrigen Lösung der Komponente (A) langsam gegeben, sodass das Vermischen der Komponente (A) und gegebenenfalls der Komponente (D) mit der Komponente (B) in wässrigem Medium unter mässiger Aussenkühlung bei vorzugsweise 60 bis 90°C durchgeführt werden kann.In the preparation of the composition according to the invention, the procedure is generally such that an aqueous solution of component (A) and, if appropriate, component (D) are first mixed with component (B) and then with component (C), which may be present as an aqueous solution . Before mixing with component (B) and optionally with component (D), component (A) should first be diluted with water for safety reasons, giving about 50 to 70 percent by weight solutions of component (A). As a rule, component (B), alone or in admixture with the optional component (D), is slowly added to the aqueous solution of component (A), so that component (A) and optionally component (D) with component (B) can be carried out in an aqueous medium with moderate external cooling at preferably 60 to 90 ° C.
Erst am Schluss wird die Komponente (C) zum Gemisch der Komponenten (A), (B) und gegebenenfalls (D) gegeben. Hierbei kann die Komponente (D) als Feststoff unter intensivem Rühren zugegeben werden. Diese trifft insbesondere bei Einsatz von z.B. Aluminiumgerbesalzen als Komponente (C) zu. Bei Verwendung von Chromgerbesalzen hat es sich jedoch als besonders vorteilhaft erwiesen, die Komponente (C) als wässrige Lösung einzusetzen, wobei die wässrige Lösung der Komponente (C) vor dem Vermischen mit den Komponenten (A), (B) und gegebenenfalls (D) in der Regel auf 60 bis 90°C aufgeheizt wird. Nach dem Vermischen aller Komponenten wird die Zusammensetzung im allgemeinen mit Wasser auf den bevorzugten Wassergehalt von 40 bis 80 Gewichtsprozent verdünnt.Only at the end is component (C) added to the mixture of components (A), (B) and optionally (D). Component (D) can be added as a solid with vigorous stirring. This is particularly true when using e.g. Aluminum tanning salts as component (C). When using chrome tanning salts, it has proven to be particularly advantageous to use component (C) as an aqueous solution, the aqueous solution of component (C) before mixing with components (A), (B) and optionally (D) is usually heated to 60 to 90 ° C. After all the components have been mixed, the composition is generally diluted with water to the preferred water content of 40 to 80 percent by weight.
Die so erhaltenen, erfindungsgemässen Zusammensetzungen sind flüssig und eignen sich besonders gut zum Gerben von Blösse oder zum Nachgerben von Leder aller Art.The compositions according to the invention obtained in this way are liquid and are particularly suitable for tanning raw materials or for retanning leather of all kinds.
Hierbei geht man nach konventionellen Methoden so vor, dass man Blösse oder vorgegerbtes Leder mit einer wässrigen Lösung behandelt, welche die erfindungsgemässe, wässrige Zusammensetzung enthält, und anschliessend das so gegerbte Material auf übliche Weise z.B. durch Neutralisieren, Auswaschen, Fetten und Trocknen fertigstellt. Falls erwünscht, kann eine Färbung durchgeführt werden. In der Regel werden auf 100 Gewichtsteile Blösse oder Leder 100 bis 200, vorzugsweise 140 bis 180 Gewichtsteile Wasser und 5 bis 40 Gewichtsteile der wässrigen, erfindungsgemässen Zusammensetzung eingesetzt.The conventional method is used to treat pale or pretanned leather with an aqueous solution which contains the aqueous composition according to the invention, and then the material which has been tanned in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done. As a rule, 100 to 200, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the aqueous composition according to the invention are used per 100 parts by weight of leather or leather.
Im Speziellen werden 100 Gewichtsteile vorzugsweise entkalkte Blösse mit 140 bis 160 Gewichtsteilen Wasser und 10 bis 20 Teilen der erfindungsgemässen Zusammensetzung gegerbt oder 100 Gewichtsteile auf übliche Art und Weise mit z.B. Formiaten oder Bicarbonaten neutralisiertes chromgegerbtes Leder mit 140 bis 160 Gewichtsteilen Wasser und 5 bis 15 Teilen der erfindungsgemässen Zusammensetzung nachgegerbt. Das gegerbte Material wird nachgespült und gegebenenfalls anschliessend mit einem handelsüblichen Fettungsmittel auf der Basis von z.B. sulfoniertem Fischöl, Spermöl oder Klauenöl gefettet. Nach dem Trocknen erhält man ein helles, brillantes Leder, welches eine gute Lichtechtheit, einen festen, kompakten, glatten Narben und einen weichen Griff aufweist.In particular, 100 parts by weight, preferably descaled, of tanned material is tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the composition according to the invention, or 100 parts by weight in the usual manner with chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight Retanned water and 5 to 15 parts of the composition according to the invention. The tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
Neben den guten, erwähnten Eigenschaften der damit gegerbten Materialien bringt die erfindungsgemässe Zusammensetzung den wesentlichen Vorteil mit sich, dank der Gegenwart der Komponente (B) besonders lagerstabil zu sein. Selbst nach mehrmonatiger Lagerung können nämlich keine Trübungen oder Ausflockungen in der Zusammensetzung festgestellt werden.In addition to the good, mentioned properties of the materials tanned therewith, the composition according to the invention has the essential advantage of being particularly stable in storage thanks to the presence of component (B). Even after several months of storage, no clouding or flocculation can be found in the composition.
Die in der nachfolgenden Herstellungsvorschrift und in den nachfolgenden Beispielen angegebenen Prozente und Teile beziehen sich auf das Gewicht.The percentages and parts given in the following manufacturing instructions and in the following examples relate to the weight.
136,5 Teile Phenol (1,45 Mol) werden bei 45°C geschmolzen. Zu dieser Schmelze werden 193,4 Teile Oleum 20 % (2,08 Mol SO₃) langsam so gegeben, dass die Temperatur des Reaktionsgemisches nicht über 160°C steigt. Nun wird das Reaktionsgemisch unter vermindertem Druck bei 20 Torr und bei 160°C während 6 Stunden unter Rühren gehalten, wobei das durch die Reaktion gebildete Wasser zusammen mit geringen Anteilen geschmolzenen Phenols aus dem Reaktionsgemisch azeotropisch entfernt werden. Anschliessend wird das Reaktionsgemisch unter Normaldruck auf 40°C abgekühlt. Man erhält 253 Teile eines geschmolzenen Gemisches aus Polyhydroxy-polyphenylsulfon-Sulfonsäuren, das die Disulfonsäure der Formel
als Hauptbestandteil enthält.136.5 parts of phenol (1.45 moles) are melted at 45 ° C. To this melt 193.4 parts of 20% oleum (2.08 mol SO₃) are slowly added so that the temperature of the reaction mixture does not rise above 160 ° C. Now the reaction mixture is kept under reduced pressure at 20 torr and at 160 ° C. for 6 hours with stirring, the water formed by the reaction together with small amounts of molten phenol being removed from the reaction mixture azeotropically. The reaction mixture is then cooled to 40 ° C. under normal pressure. This gives 253 parts of a molten mixture of polyhydroxy-polyphenylsulfonic sulfonic acids, which is the disulfonic acid of the formula
contains as main ingredient.
Zu einer Lösung aus 166,5 Teilen des gemäss Vorschrift A hergestellten, Umsetzungsprodukts aus Phenol und Oleum, 100 Teilen Wasser und 4 Teilen Tetranatriumsalz der Ethylendiamintetraessigsäure werden 15 Teile Diethanolamin langsam so gegeben, das die Temperatur des Reaktionsgemisches nicht über 70°C steigt. Das Reaktionsgemisch wird bei 70°C während 15 Minuten unter Rühren gehalten, wobei eine klare Lösung ensteht. Nun wird zur Reaktionslösung eine auf 70°C vorgewärmte Lösung aus 198 Teilen Cr(OH)SO₄ (entsprechend 62,3 Teilen Chrom) in 360,5 Teilen Wasser gegeben. Die Reaktionslösung wird anschliessend bei 70°C während 20 Minuten unter Rühren gehalten, dann mit 156 Teilen Wasser verdünnt und auf 20°C abgekühlt. Man erhält 1000 Teile einer Zusammensetzung, die 166,5 Teile des Umsetzungsproduktes aus Phenol und Oleum, 15 Teile Diethanolamin, 198 Teile Cr(OH)SO₄ (entspr. 62,3 Teile Chrom), 4 Teile Tetranatriumsalz der Ethylendiamintetraessigsäure und 616,5 Teile Wasser enthält. Nach 3-monatiger Lagerung bleibt die Zusammensetzung homogen, d.h. weist keinerlei Trübungen oder Ausflockungen auf. Eine 1%-ige Lösung dieser Zusammensetzung weist einen pH-Wert von 2,9 auf.15 parts of diethanolamine are slowly added to a solution of 166.5 parts of the reaction product of phenol and oleum, 100 parts of water and 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid prepared in accordance with specification A in such a way that the temperature of the reaction mixture does not rise above 70.degree. The reaction mixture is kept under stirring at 70 ° C. for 15 minutes, a clear solution being formed. Now a solution of 198 parts of Cr (OH) SO₄ (corresponding to 62.3 parts of chromium) in 360.5 parts of water, preheated to 70 ° C., is added to the reaction solution. The reaction solution is then kept under stirring at 70 ° C. for 20 minutes, then diluted with 156 parts of water and cooled to 20 ° C. This gives 1000 parts of a composition comprising 166.5 parts of the reaction product from phenol and oleum, 15 parts of diethanolamine, 198 parts of Cr (OH) SO₄ (corresponds to 62.3 parts of chromium), 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and 616.5 parts Contains water. After 3 months of storage, the composition remains homogeneous, i.e. shows no cloudiness or flocculation. A 1% solution of this composition has a pH of 2.9.
Zu einer Lösung aus 166,5 Teilen des gemäss Vorschrift A hergestellten, Umsetzungsprodukts aus Phenol und Oleum (Molverhältnis Phenol:SO₃ 1:1,43), 150 Teilen Wasser und 4 Teilen Tetranatriumsalz der Ethylendiamintetraessigsäure werden 10 Teile Diethanolamin langsam so gegeben, das die Temperatur des Reaktionsgemisches nicht über 70°C steigt. Das Reaktionsgemisch wird bei 70°C während 15 Minuten unter Rühren gehalten, wobei eine klare Lösung ensteht. Nun wird zur Reaktionslösung eine filtrierte, auf 70°C vorgewärmte Lösung aus 139 Teilen Cr(OH)SO₄ (entsprechend 43,8 Teilen Chrom) und 45,78 Teilen Al₂(OH)₄SO₄ (entsprechend 11,3 Teilen Aluminium) in 484,72 Teile Wasser gegeben. Die Reaktionslösung wird anschliessend bei 70°C während 20 Minuten unter Rühren gehalten und dann auf 20°C abgekühlt. Man erhält 1000 Teile einer Zusammensetzung, die lagerstabil ist. Eine 1%ige Lösung dieser Zusammensetzung weist einen pH-Wert von 3 auf.10 parts of diethanolamine are slowly added to a solution of 166.5 parts of the reaction product of phenol and oleum (molar ratio of phenol: SO₃ 1: 1.43), 150 parts of water and 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid, prepared according to specification A, so that the Temperature of the reaction mixture is not rises above 70 ° C. The reaction mixture is kept under stirring at 70 ° C. for 15 minutes, a clear solution being formed. A filtered solution of 139 parts Cr (OH) SO₄ (corresponding to 43.8 parts chromium) and 45.78 parts Al₂ (OH) ₄SO₄ (corresponding to 11.3 parts aluminum) in 484 is now added to the reaction solution, preheated to 70 ° C, Given 72 parts of water. The reaction solution is then kept under stirring at 70 ° C. for 20 minutes and then cooled to 20 ° C. 1000 parts of a composition are obtained which are stable on storage. A 1% solution of this composition has a pH of 3.
Eine lagerstabile Zusammensetzung wird auch erhalten, wenn man anstelle der 4 Teile Tetranatriumsalz der Ethylendiamintetraessigsäure und der 10 Teile Diethanolamin, 3 Teile Trinatriumphosphat bzw. 7,5 Teile N,N'-Dimethyl-propan-diamin verwendet.A storage-stable composition is also obtained if instead of the 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid and the 10 parts of diethanolamine, 3 parts of trisodium phosphate or 7.5 parts of N, N'-dimethyl-propane-diamine are used.
Man verfährt wie in Beispiel 2 angegeben, verwendet jedoch eine filtrierte auf 70°C vorgewärmte Lösung, die anstelle der 45,78 Teile Al₂(OH)₄SO₄ und der 484,72 Teile Wasser folgende Teile Gerbesalz bzw. Wasser enthält :
Man erhält so ähnlich gute, lagerstabile Lösungen.This gives similarly good, storage-stable solutions.
Zu einer Lösung aus 116 Teilen des gemäss Vorschrift A hergestellten Umsetzungsprodukts aus Phenol und Oleum (Molverhältnis Phenol:SO₃ 1:1,43), 120 Teilen Wasser und 4 Teilen Tetranatriumsalz der Ethylendiamintetraessigsäure werden 15 Teile Diethanolamin oder 8,5 Teile N-(2-Hydroxyethyl)-ethylendiamin langsam so gegeben, dass die Temperatur des Reaktionsgemisches nicht über 70°C steigt. Das Reaktionsgemisch wird bei 70°C während 15 Minuten unter Rühren gehalten, wobei eine klare Lösung ensteht. Nun wird zur Reaktionslösung eine filtrierte, auf 70°C vorgewärmte Lösung aus 145,46 Teilen Cr(OH)SO₄ (entsprechend 45,82 Teilen Chrom) und 65,36 Teilen Zr(OH)₂SO₄ (entsprechend 26,82 Teilen Zirkonium) in 493 Teile Wasser gegeben. Die Reaktionslösung wird anschliessend bei 70°C während 20 Minuten unter Rühren gehalten und dann auf 20°C abgekühlt. Man erhält 1000 Teile einer Zusammensetzung, die lagerstabil ist.
Eine 1%-ige Lösung dieser Zusammensetzung weist einen pH-Wert von 2,4 auf.To a solution of 116 parts of the reaction product of phenol and oleum (molar ratio phenol: SO₃ 1: 1.43), 120 parts of water and 4 parts of tetrasodium salt of ethylenediaminetetraacetic acid, 15 parts of diethanolamine or 8.5 parts of N- (2 -Hydroxyethyl) -ethylenediamine slowly added so that the temperature of the reaction mixture does not rise above 70 ° C. The reaction mixture is kept under stirring at 70 ° C. for 15 minutes, a clear solution being formed. Now a filtered solution of 145.46 parts of Cr (OH) SO₄ (corresponding to 45.82 parts of chromium) and 65.36 parts of Zr (OH) ₂SO₄ (corresponding to 26.82 parts of zirconium) is added to the reaction solution Given 493 parts of water. The reaction solution is then kept under stirring at 70 ° C. for 20 minutes and then cooled to 20 ° C. 1000 parts of a composition are obtained which are stable on storage.
A 1% solution of this composition has a pH of 2.4.
Ebenfalls gut lagerstabile Zusammensetzungen werden erhalten, wenn man anstelle der 65,36 Teile Zr(OH)₂SO₄, 95,0 Teile ZrOCl₂·8H₂O oder 106 Teile Zr(SO₄)₂·4H₂O (alle entsprechend 26,82 Teilen Zirkonium) verwendet.Compositions with good storage stability are also obtained if, instead of the 65.36 parts of Zr (OH) ₂SO₄, 95.0 parts of ZrOCl₂ · 8H₂O or 106 parts of Zr (SO₄) ₂ · 4H₂O (all corresponding to 26.82 parts of zirconium) are used.
Zu einer Lösung aus 150 Teilen des gemäss Vorschrift A hergestellten Umsetzungsprodukts aus Phenol und Oleum (Molverhältnis Phenol:SO₃ 1:2,2), 100 Teilen Wasser werden 30 Teile Diethanolamin oder 10,5 Teile Triethylentetramin langsam so gegeben, dass die Temperatur des Reaktionsgemisches nicht über 70°C steigt. Das Reaktionsgemisch wird bei 70°C während 15 Minuten unter Rühren gehalten, wobei eine klare Lösung ensteht. Nun wird zur Reaktionslösung eine filtrierte, auf 90°C vorgewärmte Lösung aus 238,36 Teilen Cr(OH)SO₄ (entsprechend 75,09 Teilen Chrom) in 450 Teile Wasser gegeben. Die Reaktionslösung wird anschliessend bei 90°C während 20 Minuten unter Rühren gehalten, dann mit 1120 Teilen Wasser verdünnt und auf 20°C abgekühlt. Man erhält eine Zusammensetzung, die lagerstabil ist. Eine 1%-ige Lösung dieser Zusammensetzung weist einen pH-Wert von 2,1 auf.30 parts of diethanolamine or 10.5 parts of triethylenetetramine are slowly added to a solution of 150 parts of the reaction product of phenol and oleum (molar ratio phenol: SO₃ 1: 2.2), 100 parts of water, prepared according to regulation A, such that the temperature of the reaction mixture does not rise above 70 ° C. The reaction mixture is kept under stirring at 70 ° C. for 15 minutes, a clear solution being formed. A filtered solution of 238.36 parts of Cr (OH) SO₄ (corresponding to 75.09 parts of chromium) in 450 parts of water is then added to the reaction solution and preheated to 90 ° C. The reaction solution is then kept at 90 ° C for 20 minutes with stirring, then diluted with 1120 parts of water and cooled to 20 ° C. A composition is obtained which is stable on storage. A 1% solution of this composition has a pH of 2.1.
Zu einer Lösung aus 150 Teilen des gemäss Vorschrift A hergestellten, Umsetzungsprodukts aus Phenol und Oleum (Molverhältnis Phenol:SO₃ 1:1,35), 100 Teilen Wasser und 6 Teilen Tetranatriumsalz der Ethylendiamintetraessigsäure werden 7,5 Teile Diethanolamin langsam so gegeben, das die Temperatur des Reaktionsgemisches nicht über 70°C steigt. Das Reaktionsgemisch wird bei 70°C während 15 Minuten unter Rühren gehalten, wobei eine klare Lösung ensteht. Nun wird zur Reaktionslösung eine filtrierte auf 90°C vorgewärmte Lösung aus 14,3 Teilen Cr(OH)SO₄ (entsprechend 4,5 Teilen Chrom) in 50 Teilen Wasser gegeben. Die Reaktionslösung wird anschliessend bei 60°C während 20 Minuten unter Rühren gehalten, dann mit 156 Teilen Wasser verdünnt und auf 20°C abgekühlt. Man erhält eine Zusammensetzung, die lagerstabil ist. Eine 1%-ige Lösung dieser Zusammensetzung weist einen pH-Wert von 1,05 auf.7.5 parts of diethanolamine are slowly added to a solution of 150 parts of the reaction product of phenol and oleum (molar ratio phenol: SO₃ 1: 1.35), 100 parts of water and 6 parts of tetrasodium salt of ethylenediaminetetraacetic acid, prepared according to regulation A, so that the Temperature of the reaction mixture does not rise above 70 ° C. The reaction mixture is kept under stirring at 70 ° C. for 15 minutes, a clear solution being formed. Now a filtered solution of 14.3 parts of Cr (OH) SO₄ (corresponding to 4.5 parts of chromium) in 50 parts of water is added to the reaction solution and preheated to 90 ° C. The reaction solution is then kept under stirring at 60 ° C. for 20 minutes, then diluted with 156 parts of water and cooled to 20 ° C. A composition is obtained which is stable on storage. A 1% solution of this composition has a pH of 1.05.
Aehnliche gut lagerstabile Zusammensetzungen werden erhalten, wenn man im obigen Beispiel a) anstelle von 14,3 Teilen Cr(OH)SO₄, 23,06 Teile [CrCl₂(OH₂)₄]Cl·2H₂O, 11,68 Teile Cr₂(OH)₄SO₄ oder 43,5 Teile KCr(SO₄)₂·12H₂O;
b) anstelle der 6 Teile Tetranatriumsalz der Ethylendiamintetraessigsäure 5 Teile Natriumpyrophosphat oder Dinatriumpyrophosphat und
c) anstelle von 7,5 Teilen Diethanolamin, 12,7 Teile Dimethylethanolamin, 1,5 Teile Ethylendiamin, 2,5 Teile N-(2-Hydroxyethyl)-ethanolamin, 3 Teile N,N-Dimethylpropandiamin, 2 Teile Pentamethylendiamin, 2,2 Teile Hexamethylendiamin oder 6,2 Teile Morpholin verwendet.Similar compositions with good storage stability are obtained if, in Example a) above, instead of 14.3 parts of Cr (OH) SO₄, 23.06 parts of [CrCl₂ (OH₂) ₄] Cl · 2H₂O, 11.68 parts of Cr₂ (OH) ₄SO₄ or 43.5 parts KCr (SO₄) ₂ · 12H₂O;
b) instead of the 6 parts of tetrasodium salt of ethylenediaminetetraacetic acid, 5 parts of sodium pyrophosphate or disodium pyrophosphate and
c) instead of 7.5 parts of diethanolamine, 12.7 parts of dimethylethanolamine, 1.5 parts of ethylenediamine, 2.5 parts of N- (2-hydroxyethyl) ethanolamine, 3 parts of N, N-dimethylpropane diamine, 2 parts of pentamethylene diamine, 2, 2 parts of hexamethylenediamine or 6.2 parts of morpholine were used.
100 Teile entkalkte Kalbsblösse werden mit 150 Teilen Wasser und 15 Teilen der gemäss Beispiel 1 hergestellten Zusammensetzung während 24 Stunden bei 20°C im rollenden Fass behandelt. Nach dem Neutralisieren, Waschen, Fetten, Ausrecken, Trocknen, Konditionieren, Stollen und Spermen erhält man ein gegerbtes, leicht gedecktes Leder, das einen vollen Narben und einen weichen Griff aufweist.100 parts of decalcified veal pellet are treated with 150 parts of water and 15 parts of the composition prepared according to Example 1 for 24 hours at 20 ° C. in a rolling barrel. After neutralizing, washing, greasing, stretching, drying, conditioning, studs and sperm, you get a tanned, lightly covered leather that has a full grain and a soft feel.
Man verfährt wie in Beispiel 12 beschrieben, verwendet man aber auf 100 Teile Kalbsblösse folgende Mengen Zusammensetzung:
Man erhält so ein Leder mit ähnlichen Eigenschaften wie dasjenige von Beispiel 12.A leather with properties similar to that of Example 12 is thus obtained.
100 Teile gefalztes Chromnarbenkalbsleder werden mit 150 Teilen Wasser und 10 Teilen der gemäss Beispiel 1 hergestellten Zusammensetzung während 2 Stunden bei 50°C im rollenden Fass behandelt. Nach dem Auswaschen wird das Leder mit Natriumformiat und Natriumbicarbonat nach üblichen Methoden neutralisiert, gewaschen, mit 1 Teil des Lederfarbstoffes C.I. Acid Brown 189 gefärbt und mit einem handelsüblichen Fettungsmittel auf Basis von sulfoniertem Fischöl nachbehandelt. Nach Fertigstellung des Leders wie in Beispiel 12 angegeben, erhält man ein gegerbtes, braun gefärbtes, brillantes Leder, das ebenfalls einen vollen Narben und einen weichen Griff aufweist.100 parts of folded chrome grain calf leather are treated with 150 parts of water and 10 parts of the composition prepared according to Example 1 for 2 hours at 50 ° C. in a rolling barrel. After washing out, the leather is neutralized with sodium formate and sodium bicarbonate using customary methods, washed, dyed with 1 part of the leather dye CI Acid Brown 189 and aftertreated with a commercially available fatliquor based on sulfonated fish oil. After completion of the leather as indicated in Example 12, a tanned, brown-colored, brilliant leather is obtained, which also has a full grain and a soft handle.
Man verfährt wie in Beispiel 17 beschrieben, verwendet man aber auf 100 Teile gefalztes Chromnarbenkalbsleder folgende Mengen Zusammensetzung:
Man erhält so ein Leder mit ähnlichen Eigenschaften wie dasjenige von Beispiel 17.A leather with properties similar to that of Example 17 is thus obtained.
Claims (17)
- A process for the preparation of an aqueous composition for tanning pelts or for retanning leather, which comprises first mixing an aqueous solution of (A) a reaction product of phenol and a sulfonating agent having a molar ratio of (phenol):(SO₃) of (1):(1.1-2.2) and optionally (D) an alkali metal salt of ethylenediaminetetraacetic acid or of a pyrophosphate with (B) a water soluble, primary, secondary or tertiary C₁-C₄alkylamine, C₂-C₃alkanolamine or C₂-C₆alkylenediamine, a poly-C₂-C₃alkylenepolyamine having 3 to 5 nitrogen atoms or a heterocyclic amine, not more than 0.2 parts by weight of component (B) being used per part by weight of component (A), with cooling at from 60 to 90°C, and subsequently admixing the resultant mixture with (C) an aqueous solution, optionally preheated to from 60 to 90°C, of a chromium, aluminium, iron or zirconium tanning salt or mixtures thereof.
- A process according to claim 1, wherein the component (A) used is a reaction product of phenol and oleum having a molar ratio of (phenol):(SO₃) of (1):(1.4 to 1.8).
- A process according to claim 1, wherein the component (B) used is mono-, di- or triethanolamine, dimethylethanolamine, ethylenediamine, N-hydroxyethylethylenediamine, N,N-dimethylpropylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine or morpholine
- A process according to claim 1, wherein the component (C) used is basic chromium(III) chloride or sulfate, a chromium alum, optionally basic aluminium chloride or sulfate, an alum, iron(III) chloride or sulfate, zirconium oxychloride or optionally basic zirconium sulfate or mixtures of the abovementioned chromium and aluminium salts.
- A process according to claim 4, wherein the component (C) used is [CrCl₂(OH₂)₄]Cl·2 H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄, KCr(SO₄)₂·12 H₂O, AlCl₃·6 H₂O, Al₂(SO₄)₃·16 H₂O, Al₂(OH)₄SO₄, Al(OH)₂Cl, Al(OH)Cl₂, KAl(SO₄)₂·12 H₂O, Fe₂(SO₄)₃·9 H₂O, ZrOCl₂·8 H₂O or Zr(SO₄)₂·4 H₂O.
- A process according to claim 1, wherein the optional component (D) used is tetrasodium ethylenediaminetetraacetate or neutral or acid sodium pyrophosphate.
- A process according to claim 1, for the preparation of a composition which, as a 1 % aqueous solution based on the dry matter content of components (A), (B), (C) and optionally (D), has a pH of not more than 5.
- A process according to claim 1 for the preparation of a composition which contains components (A) and (B) in a weight ratio of (A):(B) of (1):(0.05 to 0.18).
- A process according to claim 8 for the preparation of a composition which, as a 1 % aqueous solution based on the dry matter content of components (A), (B), (C) and optionally (D), has a pH of from 0 to 3.5.
- A process according to claim 1 for the preparation of a composition which contains components (A) and (C) in a weight ratio of (A):(C) of (1):(0.03 to 0.5), based on the metal atom of component (C), such that not more than 0.375 parts of chromium are present.
- A process according to claim 10, wherein components (A) and (C) are contained in a weight ratio of (A): (C) of (1):(0.3 to 0.375).
- A process according to claim 1, wherein components (A) and (D) are contained in a weight ratio of (A):(D) of (1):(0 to 0.04).
- A process according to any one of claims 1 to 12 for the preparation of a composition which has a water content of 40 to 80 percent by weight.
- A process for tanning pelts or for retanning leather, which comprises using a process according to one of claims 1-13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH182586 | 1986-05-05 | ||
| CH1825/86 | 1986-05-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0245205A2 EP0245205A2 (en) | 1987-11-11 |
| EP0245205A3 EP0245205A3 (en) | 1989-05-10 |
| EP0245205B1 true EP0245205B1 (en) | 1992-09-02 |
Family
ID=4219478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87810273A Expired - Lifetime EP0245205B1 (en) | 1986-05-05 | 1987-04-29 | Aqueous composition comprising a sulfonated phenol, an amine and a tanning salt, its manufacture and its use as a tanning agent |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4830632A (en) |
| EP (1) | EP0245205B1 (en) |
| JP (1) | JP2886161B2 (en) |
| AU (1) | AU604697B2 (en) |
| BR (1) | BR8702226A (en) |
| DE (1) | DE3781453D1 (en) |
| ES (1) | ES2033920T3 (en) |
| MX (1) | MX167001B (en) |
| PT (1) | PT84821B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2045544T3 (en) * | 1988-06-06 | 1994-01-16 | Ciba Geigy Ag | AQUEOUS SOLUTIONS OF SYNTHETIC TANNING MATERIALS. |
| US5264000A (en) * | 1988-06-06 | 1993-11-23 | Ciba-Geigy Corporation | Aqueous solutions of synthetic tanning agents |
| ES2066189T3 (en) * | 1989-11-13 | 1995-03-01 | Ciba Geigy Ag | PROCEDURE FOR THE PREPARATION OF LEATHERS AND SKINS. |
| DE4025344A1 (en) * | 1990-08-10 | 1992-02-13 | Bayer Ag | Post-tanning mineral-tanned leather - with phenol sulphonic acid deriv. or naphthol sulphonic acid deriv. |
| EP0554218B1 (en) * | 1992-01-28 | 1996-07-24 | Ciba-Geigy Ag | Process for pickling hides |
| ATE140268T1 (en) * | 1992-01-28 | 1996-07-15 | Ciba Geigy Ag | METHOD FOR PICKLING AND PRE-TANNING SKIN BARE |
| US5490865A (en) * | 1994-07-25 | 1996-02-13 | Scheiwiller; Jurg P. | Method of treating and dyeing animal fibers |
| DE10140551A1 (en) | 2001-08-17 | 2003-02-27 | Basf Ag | Process for the production of tannins containing sulfones |
| AU2002348767B2 (en) * | 2002-12-23 | 2006-11-23 | Council Of Scientific And Industrial Research | Process for preparing a synthetic aluminium tanning agent |
| US7169191B2 (en) * | 2003-03-20 | 2007-01-30 | Council Of Scientific And Industrial Research | Process for preparing a synthetic aluminium tanning agent |
| CN102747172B (en) * | 2012-07-05 | 2015-04-01 | 湖南省怀其皮革集团制革有限公司 | Manufacturing method for chromium-free aldehyde-free tanned pigskin shoe lining leather |
| CN110117905B (en) * | 2019-04-29 | 2022-02-01 | 陕西科技大学 | Method for obtaining high-filling-power down feather based on multi-metal salt treatment of down feather |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE429249A (en) * | 1936-03-10 | |||
| GB683084A (en) * | 1949-06-20 | 1952-11-19 | Geigy Ag J R | Manufacture of new condensation products, being more especially improved tanning agents and their application |
| DE2508195A1 (en) * | 1974-03-08 | 1975-09-11 | Sandoz Ag | LEATHER PREPARATIONS, IN PARTICULAR CHROME AND ZIRCON TANKS |
| CH603796A5 (en) * | 1976-04-22 | 1978-08-31 | Ciba Geigy Ag |
-
1987
- 1987-04-27 US US07/042,770 patent/US4830632A/en not_active Expired - Lifetime
- 1987-04-29 DE DE8787810273T patent/DE3781453D1/en not_active Expired - Lifetime
- 1987-04-29 EP EP87810273A patent/EP0245205B1/en not_active Expired - Lifetime
- 1987-04-29 ES ES198787810273T patent/ES2033920T3/en not_active Expired - Lifetime
- 1987-04-30 MX MX006305A patent/MX167001B/en unknown
- 1987-05-01 JP JP62106462A patent/JP2886161B2/en not_active Expired - Fee Related
- 1987-05-04 AU AU72468/87A patent/AU604697B2/en not_active Ceased
- 1987-05-04 BR BR8702226A patent/BR8702226A/en not_active IP Right Cessation
- 1987-05-04 PT PT84821A patent/PT84821B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU604697B2 (en) | 1991-01-03 |
| AU7246887A (en) | 1987-11-12 |
| JP2886161B2 (en) | 1999-04-26 |
| EP0245205A2 (en) | 1987-11-11 |
| PT84821B (en) | 1989-12-29 |
| DE3781453D1 (en) | 1992-10-08 |
| ES2033920T3 (en) | 1993-04-01 |
| MX167001B (en) | 1993-02-22 |
| BR8702226A (en) | 1988-02-17 |
| JPS62267400A (en) | 1987-11-20 |
| EP0245205A3 (en) | 1989-05-10 |
| US4830632A (en) | 1989-05-16 |
| PT84821A (en) | 1987-06-01 |
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