EP0085107B1 - Gerbmittel für häute und verfahren zu dessen herstellung - Google Patents
Gerbmittel für häute und verfahren zu dessen herstellung Download PDFInfo
- Publication number
- EP0085107B1 EP0085107B1 EP81903143A EP81903143A EP0085107B1 EP 0085107 B1 EP0085107 B1 EP 0085107B1 EP 81903143 A EP81903143 A EP 81903143A EP 81903143 A EP81903143 A EP 81903143A EP 0085107 B1 EP0085107 B1 EP 0085107B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonium
- sulphate
- titanium
- solution
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000010936 titanium Substances 0.000 claims abstract description 74
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 49
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 47
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010985 leather Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract 24
- 239000001166 ammonium sulphate Substances 0.000 claims abstract 13
- 239000001117 sulphuric acid Substances 0.000 claims abstract 10
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract 10
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims abstract 6
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 4
- 229910019982 (NH4)2TiO Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 10
- 239000001164 aluminium sulphate Substances 0.000 claims 5
- 235000011128 aluminium sulphate Nutrition 0.000 claims 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 13
- 239000000654 additive Substances 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 67
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 24
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 22
- OLULCGRZLCPQGF-UHFFFAOYSA-M S(=O)(=O)([O-])[O-].[Zr+].[NH4+] Chemical compound S(=O)(=O)([O-])[O-].[Zr+].[NH4+] OLULCGRZLCPQGF-UHFFFAOYSA-M 0.000 description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 12
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 5
- -1 Titanium-zirconium-aluminum Chemical compound 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 240000005852 Mimosa quadrivalvis Species 0.000 description 1
- ZWNZGTHTOBNSDL-UHFFFAOYSA-N N.[Ti+4] Chemical compound N.[Ti+4] ZWNZGTHTOBNSDL-UHFFFAOYSA-N 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-O hydridodioxygen(1+) Chemical compound [OH+]=O MYMOFIZGZYHOMD-UHFFFAOYSA-O 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical group 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910001773 titanium mineral Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
Definitions
- the tanning agents used in the leather industry include chrome tanning agents and vegetable tanning agents such as oak, spruce bark, chestnut, quebracho, mimosa extracts, etc.
- chrome tanning agents and vegetable tanning agents such as oak, spruce bark, chestnut, quebracho, mimosa extracts, etc.
- chromium is harmful to the operator, leads to environmental pollution
- vegetable Tanning agents require a large consumption of vegetable raw materials, which also damages the environment.
- a titanium tanning agent for leather which contains a double sulfate of titanyl and ammonium in the monohydrate form (NH 4 ) 2 TiO (SO 4 ) 2 .
- H 2 represents 0 (SU-PS 234598, published 1969).
- the use of the titanium tanning agent eliminates the need to use vegetable tanning agents and reduces the consumption of chrome tanning agents.
- the titanium tanning agent enables the tanning of the leather to be carried out effectively, the leather showing improved characteristic values, but the shrinking temperature of the tanned skin bare has not yet reached the desired value.
- a zirconium tanning agent for leather which, compared to the titanium tanning agent, increases the shrinking temperature of the tanned skin (AIMetelkin, NIKolesnikova.EV Kurmina "Zirconium tanning” published in 1972, publisher “Logkaya industrial, Moscow, p.220").
- the zirconium tanning agent is more expensive than the titanium tanning agent.
- a tanning agent containing titanium and zirconium is known, the use of which improves the quality of the leather (SU-PS 340 702, 1972).
- the process for preparing this tanning agent is to mix two solutions, a solution containing titanium salt and a solution containing a zirconium salt, after which the solutions are evaporated to dryness. This process requires high energy consumption.
- a tanning agent which contains 20 to 32% ammonium sulfato zirconate, 0.1 to 19.0% ammonium sulfato aluminate and 39 to 78.9% ammonium sulfate titanate. It is obtained by simply mixing the solid components. The leather tanned with this agent is not very elastic and has a contraction of the scars.
- the object of the present invention was to develop a tanning agent for leather which, in terms of its tanning properties, surpasses the known tanning agents, namely a titanium tanning agent which can be obtained by simple technology using accessible reaction agents and accessible starting raw materials.
- the above-mentioned tanning agent is obtained by a process which is characterized in accordance with the invention in that a titanium-containing solution which contains 80-200 g / l of titanium, converted to its dioxide, is taken, and this with a solution of aluminum sulfate, the 80-130 g / I aluminum, converted to its oxide, contains and / or with a solution of zirconium sulfate containing 50-200 g / I zirconium, converted to its dioxide, in the presence of sulfuric acid and ammonium sulfate.
- the process according to the invention for the production of tanning agents has the advantage that it can be easily implemented under industrial conditions, since the process is carried out under normal conditions, at room temperature and under normal pressure, using readily available and inexpensive reactants and readily available mineral raw materials .
- composition of the sulfate tanning agent is proposed, depending on the combination of the sulfates taken, namely a tanning agent consisting of two or three components.
- This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 4-6 ° C. compared to the known titanium tanning agent.
- This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 10-12 ° C. compared to the known titanium tanning agent.
- the titanium-aluminum tanning agent can contain 1 to 10% by weight of silica, which serves as a filler for leather and makes it possible to increase its mass and thickness yield during tanning by 0.8-1.0% compared to the known one To increase titanium tanning agents.
- the limits of the content of the said sulfates in the tanning agent are due to the fact that activation of the tanning effect of the ammonium titanyl sulfate does not appear if the ammonium aluminum sulfate content is less than 3% by weight.
- An increase in the content of ammonium aluminum sulfate to more than 20% by weight leads to a reduction in the content of basic tanning component in ammonium titanyl sulfate - which in turn leads to a deterioration in the tanning properties.
- the tanning agent content of basic ammonium zirconium sulfate is less than 20% by weight, the tanning effect becomes weaker, and if this component contains more than 50% by weight, the tanning effect of titanium is suppressed by zirconium. This also increases the cost of the tanning agent.
- the limit of the content of the additives Ti0 2 , Zr0 2 and Al 2 O 3 , which are chemically bound in the sulfates, is due to the fact that, at a content below 0.001% by weight, their effect as activators in the tanning with sulfates is not is detected and the upper limit is determined by the conditions for carrying out the process for producing the tanning agents.
- tanning agent namely titanium-aluminum tanning agent, or titanium-zirconium tanning agent, or titanium-zirconium-aluminum tanning agent.
- the titanium-aluminum tanning agent is obtained according to the invention by a process which consists in taking a solution of the ammonium titanyl sulfate containing 80-140 g / l titanium, converted to its dioxide, and ammonium sulfate and sulfuric acid to this solution until Beginning of the crystallization of the ammonium titanyl sulfate is added, after which a solution of aluminum sulfate and additionally sulfuric acid and ammonium sulfate is obtained within 1 to 5 hours until a total content of free sulfuric acid and free aluminum sulfate of 400 to 600 g / l and a molar ratio are achieved in the reaction solution from aluminum to titanium from 0.03: 1 to 0.24: 1.
- the titanium-aluminum tanning agent can also be obtained from a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300 -520 g / l sulfuric acid, which is obtained from the digestion of raw materials containing titanium.
- a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300 -520 g / l sulfuric acid, which is obtained from the digestion of raw materials containing titanium.
- ammonium sulfate is introduced into this solution until the crystallization of the ammonium titanyl sulfate formed, after which a solution of aluminum sulfate and additional ammonium sulfate is obtained until the free ammonium sulfate content in the reaction solution is from 210 to 350 g / l and one Molar ratio of aluminum to titanium from 0.03: 1 to 0.24: 1 added.
- the production process is carried out with the addition of silica in an amount of 1 to 10% by weight or of its sodium salt.
- the silica contained in the tanning agent serves as a filler and increases the yield of leather by mass and thickness.
- the process for the preparation of titanium-zirconium tanning agent according to the invention consists in taking a solution containing zirconium and adding ammonium sulfate and sulfuric acid until crystallization of the ammonium-zirconium sulfate which forms, after which a solution of the ammonium is added within 1 to 5 hours Titanium sulfates, the 80 to 140 g / I titanium, converted to its dioxide, and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / I and a molar ratio of zirconium to titanium from 0.10: 1 to 0.65: 1.
- the titanium-zirconium tanning agent can also be obtained according to a variant which consists in that a solution containing zirconium is added within 6 to 10 hours with a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300- Contains 520 g / l of sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, and at the same time ammonium sulfate until a content of free ammonium sulfate in the reaction solution of 400 to 580 g / l and a molar ratio of zirconium to titanium of 0.10: 1 is achieved up to 0.65: 1.
- a variant of the process consists in taking a solution containing zirconium and adding this ammonium sulfate and sulfuric acid until the crystallization of the ammonium zirconium sulfate which forms, after which a solution of the ammonium titanyl sulfate is added to this solution within 1 to 5 hours 80 to 140 g / l titanium, converted to its dioxide content, a solution of aluminum sulfate and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / l and a molar ratio of aluminum are obtained Titanium from 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.
- Another variant of the process for the preparation of titanium-zirconium-aluminum tanning agents is that a solution containing zirconium is mixed with a sulfuric acid solution, the 100 to 200 g / l titanium, converted to its dioxide, and 300 to within 6 to 10 hours Contains 520 g / l sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, a solution of aluminum sulfate and ammonium sulfate until a free ammonium sulfate content in the reaction solution of 400 to 580 g / l and a molar ratio of aluminum and titanium of 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.
- ammonium-titanyl sulfate is used, which is obtained by digesting a raw material containing titanium, or this raw material immediately after its treatment with sulfuric acid.
- Ilmenite, Sphen, Leukoxen concentrate and other concentrates of titanium minerals can be considered as raw materials.
- Zirconium sulfate is used to prepare a zirconium-containing solution, obtained when a zirconium-containing raw material, for example zirconium concentrate, is digested.
- Ammonium sulfate and sulfuric acid are introduced into the resulting solution until the crystallization of the ammonium titanyl sulfate begins, after which 0.04 liter of aluminum sulfate, which contains 113 g / l of aluminum, converted to its oxide, and aluminum sulfate are added over the course of 2 hours and sulfuric acid until a total content of free sulfuric acid and free ammonium sulfate in the reaction solution of 550 g / I and a molar ratio of aluminum sum titanium of 0.05: 1 is achieved.
- the precipitate formed is separated from the solution by filtration.
- the weight ratio of silica to titanium dioxide in the end product is 0.05: 1.
- zirconium sulfate solution containing 180 g / l of zirconium, converted to the amount of dioxide, is used.
- 1 liter of sulfuric acid solution is passed into the solution over the course of 8 hours, obtained when processing a titanium-containing raw material which contains 160 g / l titanium, converted to its dioxide, and 400 g / l sulfuric acid, and ammonium sulfate until a content is achieved the solution of free ammonium sulfate of 500 g / I and a molar ratio of zirconium to titanium of 0.35: 1.
- the suspension is kept for 35 hours.
- the precipitate is separated off by filtration.
- the basic ammonium zirconium sulfate which forms is crystallized from the solution.
- 1.5 liters of a solution of ammonium titanyl sulfate containing 100 g / l titanium, converted to its dioxide, and 0.05 liter of a solution of aluminum sulfate, the 113 g / l aluminum, are converted into the reaction solution
- Its oxide contains and additionally sulfuric acid and ammonium sulfate until a total content of free sulfuric acid and free ammonium sulfate of 820 g / l and a molar ratio of aluminum to titanium of 0.05: 1 of zirconium to titanium of 0.40: 1 is achieved.
- the suspension is held for 20 hours.
- the precipitate is separated off by filtration.
- the tanning properties of the products are given in accordance with the shrinkage temperature of the skin exposed with them (see table). From the experimental data for the shrinkage temperature of the tanned skin, it follows that the tanning agent according to the invention, which is obtained according to Examples 1 to 7, increases the quality of the leather compared to the known titanium tanning agent.
- the improved tanning properties of the tanning agent are achieved in comparison to the known tanning agents by using a combination of sulfates which contain the additives Ti0 2 , Zr0 2 and Al 2 O 3 in the composition.
- the present invention can be used in the leather industry in leather manufacture.
Landscapes
- 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)
- Ultra Sonic Daignosis Equipment (AREA)
- Eye Examination Apparatus (AREA)
- Measuring Pulse, Heart Rate, Blood Pressure Or Blood Flow (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Dental Preparations (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81903143T ATE21935T1 (de) | 1981-05-19 | 1981-05-19 | Gerbmittel fuer haeute und verfahren zu dessen herstellung. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/SU1981/000043 WO1982004071A1 (en) | 1981-05-19 | 1981-05-19 | Tanning agent for skins and method of obtaining it |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0085107A1 EP0085107A1 (de) | 1983-08-10 |
| EP0085107A4 EP0085107A4 (de) | 1983-09-20 |
| EP0085107B1 true EP0085107B1 (de) | 1986-09-03 |
Family
ID=21616737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81903143A Expired EP0085107B1 (de) | 1981-05-19 | 1981-05-19 | Gerbmittel für häute und verfahren zu dessen herstellung |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4504271A (da) |
| EP (1) | EP0085107B1 (da) |
| AT (1) | ATE21935T1 (da) |
| BR (1) | BR8109018A (da) |
| DE (1) | DE3175255D1 (da) |
| DK (1) | DK156585C (da) |
| FI (1) | FI66431C (da) |
| WO (1) | WO1982004071A1 (da) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306435A (en) * | 1991-07-11 | 1994-04-26 | Nihon Junyaku Co., Ltd. | Treating agent composition for leather, for fibrous materials |
| DE19546946A1 (de) | 1995-12-15 | 1997-06-19 | Hoechst Ag | Precursor für Alkoxylierungskatalysatoren |
| DE19624821A1 (de) * | 1996-06-21 | 1998-01-02 | Bayer Ag | Verfahren zur Gerbung von Leder |
| DE19849577C2 (de) | 1998-10-27 | 2000-12-07 | Agie Sa | Verfahren und Vorrichtung zum dreidimensionalen Bearbeiten eines Werkstücks mittels elektroerosiver oder elektrochemischer Bearbeitung |
| CN104357596B (zh) * | 2014-11-11 | 2016-05-18 | 陕西科技大学 | Pickering乳液法制备的绿色皮革加脂剂及其方法 |
| CN107649799A (zh) * | 2017-09-22 | 2018-02-02 | 攀钢集团研究院有限公司 | 焊接材料用钛系原料及其制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1257353B (de) * | 1965-03-26 | 1967-12-28 | Bayer Ag | Verfahren zum Gerben |
| SU783342A1 (ru) * | 1979-01-04 | 1980-11-30 | Институт Химии И Технологии Редких Элементов И Минерального Сырья Ордена Ленина Кольского Филиала Им. С.М.Кирова Ан Ссср | Состав дл дублени кожи |
| SU859455A1 (ru) * | 1979-10-29 | 1981-08-30 | Джамбульский Технологический Институт Легкой И Пищевой Промышленности | Способ получени минерального дубител |
-
1981
- 1981-05-19 AT AT81903143T patent/ATE21935T1/de not_active IP Right Cessation
- 1981-05-19 BR BR8109018A patent/BR8109018A/pt unknown
- 1981-05-19 WO PCT/SU1981/000043 patent/WO1982004071A1/en active IP Right Grant
- 1981-05-19 EP EP81903143A patent/EP0085107B1/de not_active Expired
- 1981-05-19 US US06/460,235 patent/US4504271A/en not_active Expired - Fee Related
- 1981-05-19 DE DE8181903143T patent/DE3175255D1/de not_active Expired
-
1983
- 1983-01-11 FI FI830092A patent/FI66431C/fi not_active IP Right Cessation
- 1983-01-18 DK DK019083A patent/DK156585C/da active
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 94, Nr. 5, März 1981, Zusammenfassung Nr. 67306p, Seite 90 COLUMBUS OHIO (US) * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1982004071A1 (en) | 1982-11-25 |
| US4504271A (en) | 1985-03-12 |
| BR8109018A (pt) | 1983-04-12 |
| DK156585B (da) | 1989-09-11 |
| FI830092A0 (fi) | 1983-01-11 |
| DE3175255D1 (en) | 1986-10-09 |
| EP0085107A1 (de) | 1983-08-10 |
| ATE21935T1 (de) | 1986-09-15 |
| DK19083A (da) | 1983-01-18 |
| DK156585C (da) | 1990-01-29 |
| FI66431B (fi) | 1984-06-29 |
| FI830092L (fi) | 1983-01-11 |
| DK19083D0 (da) | 1983-01-18 |
| EP0085107A4 (de) | 1983-09-20 |
| FI66431C (fi) | 1984-10-10 |
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