EP2421995B1 - Procédé de tannage de peaux d'animaux - Google Patents
Procédé de tannage de peaux d'animaux Download PDFInfo
- Publication number
- EP2421995B1 EP2421995B1 EP10715707A EP10715707A EP2421995B1 EP 2421995 B1 EP2421995 B1 EP 2421995B1 EP 10715707 A EP10715707 A EP 10715707A EP 10715707 A EP10715707 A EP 10715707A EP 2421995 B1 EP2421995 B1 EP 2421995B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tanning
- process according
- range
- skin
- animal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 58
- 241001465754 Metazoa Species 0.000 title claims description 46
- 239000000243 solution Substances 0.000 claims description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 23
- 238000005554 pickling Methods 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003925 fat Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 238000010297 mechanical methods and process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 230000005226 mechanical processes and functions Effects 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000010698 whale oil Substances 0.000 claims 1
- 210000003491 skin Anatomy 0.000 description 78
- 239000010985 leather Substances 0.000 description 31
- 239000011651 chromium Substances 0.000 description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 229920001864 tannin Polymers 0.000 description 13
- 239000001648 tannin Substances 0.000 description 13
- 235000018553 tannin Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 10
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 241000283690 Bos taurus Species 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 206010000496 acne Diseases 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000283707 Capra Species 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 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
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000037336 dry skin Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C14C3/06—Mineral tanning using chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable tanning
-
- 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
- C14C3/30—Chemical tanning using physical means combined with chemical means
Definitions
- the present invention relates to a method of tanning animal skins.
- animal skin includes hides and skins of animal origin, for example of cattle, goats, sheep, buffaloes etc.
- the conventional production of ready-made leathers or skins is divided into processing steps that take place in the so-called water workshop, and in the subsequent finishing of the leather or fur.
- the water workshop in turn is divided into the areas of soft, hair removal (liming), skin digestion, first wash, descale, pickling, second wash, pimples and finally the tanning.
- the raw material is freed from dirt and preserving salt and gets back to its original water content.
- the switch is performed at a pH between 7 and 9.
- water-soluble proteins are dissolved out.
- the existing proteins are hydrolyzed, d. H. made water soluble, and washed out.
- the polypeptide chains of the dermis are attacked and broken up by the strongly reducing lime and sulfur compounds, which are also known as liming. This leads to a greater mobility of the fibers, which gives the leather increased elasticity and softness.
- This process is also referred to as skin digestion. During the entire liming process, the skin swells due to strong anionic charge and the associated repulsion of the same charged groups.
- the skin is split. Fleshing and splitting is done in a combination of manual labor and machine work for each piece of skin individually.
- the rawhide is called nakedness.
- the pelt has a water content of about 60 to about 80%.
- the dry matter is about 98% collagen.
- the last remnants of superficial skin protein are removed.
- the swelling caused by the strong alkalinity in the liming season must be removed before tanning, so that the tannins can penetrate into the fibrillar interstices of the skin fiber structure.
- weak organic acids eg. As aliphatic or aromatic dicarboxylic acids such as sulfophthalic acid, or by adding weakly acidic inorganic salts, eg. For example, ammonium sulfate, ammonium chloride or polyphosphates.
- Descaling removes the calcium hydroxide in the skin.
- the skin can be further digested by fermentation.
- Descaling and pickling are carried out in a slightly heated liquor, i. H. at about 30 to 35 ° C, performed.
- the duration of the pickling and pickling process is about 8 to 24 hours at a pH of 2.5.
- the skin obtained after pickling and pimpling, which is soaked with aqueous solution, is called Pickelblösse.
- the ratio between the mass of tanning solution and the mass of the pimpling skin to be tanned is between 8: 1 and 1: 1, with an excess of tanning solution typically being used.
- the tanning process is often done in rolling barrels and then called tanning.
- As salt formic acid, sulfuric acid, sodium bicarbonate and other additives used.
- the bondable groups of the collagens crosslink with the tannins.
- the pH is raised to values between 3.6 and 4 by addition of alkali.
- the excess, ie not absorbed by the leather or fur to be tanned soot solution represents wastewater, which must be disposed of.
- Tanning alone accounts for 160 to 200 million tonnes of wastewater worldwide. If this wastewater is not purified by suitable processes, it causes great environmental pollution.
- the purification of the waste water produced during the tanning usually takes place in several stages, wherein first of all a solids separation, for example by means of decanters and then a biological clarification can take place. In any case, wastewater treatment is time-consuming and expensive and is often not carried out, especially in third world and emerging market countries. Instead, the wastewater is unpurified initiated into rivers or lakes and leads there to severe environmental damage.
- the tanning liquid adhered to and in the hides is removed from the hides by mechanical methods (so-called wilting).
- the hides present after the wilting are called "wet-blue" in the chrome tanning, in the tanning by vegetable tanning agents as “wet-brown” and in the aluminum tanning as “wet-white”.
- the acid originating from the tanning is neutralized and then the leather is put together to form dyeing parties. It follows, depending on the leather type, a filling and coloring with z. B. water-soluble dyes. By a subsequent addition of fats finally required for the finished leather softness is achieved. Finally, the leather is dried, for example by vacuum drying or hanging drying.
- the DE 30 27 637 A1 describes a tanning process in which tanning is carried out with a greatly reduced amount of liquid.
- the wet skins are contacted with dry chromium powder for tanning.
- the resulting chrome tanning results in the result of the conventionally performed chrome tanning.
- the tanning time is 6 hours, whereby the tanned hides must rest for at least 48 hours before the subsequent dressing.
- the inventors of the present application have leather according to the in DE 30 27 637 A1 treated doctrine.
- the leather obtained was of poor and by no means marketable quality.
- the resulting leather apparently due to the small amount of highly concentrated tanning solution, was tanned only superficially, a process of tanning in the tanning industry. referred to as.
- the skin layer of the leather detached which is known under the term "Losnarbmaschine".
- the DE 10 2006 008 190 A1 describes a process for the fatliquoring of leather, in which an oil, fat or polymer is first applied to the animal skin to be treated, for example by spraying, and then the skin is treated in a compressed gas in order to apply the applied oil, fat, etc. well distribute and remove excess oil, grease etc.
- the U.S. Patent 5,512,058 describes a similar process.
- a tanning of pickled and pickled animal skins with aqueous chromate solution in the presence of a compressed gas (preferably carbon dioxide) in a reactor under certain pressure and temperature conditions is known.
- the stained and pickled animal skins are fed directly to the tanning without an intermediate step.
- the present invention provides the novel tanning process specified in claim 1, which is characterized in that the animal skin to be treated is first pickled and pickled in aqueous solution, then the liquid content of the animal skin is reduced, whereupon at least one Part of the previously removed from the animal skin amount of liquid is replaced by a Gerbweed containing the absorbed by the animal skin tanning agent in an amount corresponding to a maximum of 80%, and finally containing the gerbösung animal skin in a pressure vessel with compressed gas for a period of at least 15 minutes.
- the liquor ratio which is defined as the mass of the tanning solution divided by the mass of the animal skins to be tanned and soaked with the aqueous solution, has a value of less than 1.
- treating generally refers to contacting the animal skin containing the tanning solution meant the compressed gas.
- the amount of tanning agent to be absorbed by the animal skin is determined by the desired percentage of tanning agent which the tanned ready-to-use animal skin is to contain in order to obtain the desired leather quality, verifiable by the shrinkage temperature of the finished treated leather.
- the method according to the invention preferably as much liquid is added in the tanning step as that which has previously been removed from the animal skin to be treated in the liquid content reduction step. In this way it is ensured that the total amount of liquid added from the animal skin to be treated can be included. There is therefore no excess of (tanning) solution in the pressure vessel.
- the method according to the invention surprisingly results in leathers and skins meeting the highest requirements, ie the resulting leathers or skins are excellently deep-tanned despite minimal or no wastewater attack.
- Another advantage is with the Process according to the invention a significantly reduced compared to conventional methods treatment time.
- the hides obtained after the pickling and pickling steps usually contain about 70 to 75% by weight of liquid, based on their total weight (dry skin plus liquid).
- the liquid content of the animal skin is reduced by 5% to 90%, preferably by 20% to 70% and particularly preferably by 30% to 50%.
- the soaked animal skin is deprived of about half of the liquid contained in it.
- the reduction of the liquid content of the animal skin can be done in any suitable manner. Thermal, adsorptive or mechanical methods as well as any combination of these methods may be used.
- a mechanical crimping method is used, by means of which the desired amount of liquid is pressed out of the animal skin.
- the liquor ratio should not be greater than 2, more preferably it has a value less than 1, d. H. a mass of tanning solution is added which corresponds at most to the amount of liquid removed and which is always smaller than the mass of the skin of the animal soaked with aqueous solution from the pickling and pickling step.
- the liquor ratio in such a case assumes values of 0.05 to 0.9, more preferably the value of the liquor ratio is in the range of 0.1 to 0.7, and more preferably in the range of 0.3 to 0.6.
- the tanning solution can be added, for example by spraying, but also by immersing the animal skin in an appropriate amount of Gerb diseases.
- the added tanning solution may contain vegetable and / or synthetic tanning agents.
- the tanning solution contains tannins containing metal cations, for example chromium or aluminum salts.
- the tanning solution may contain additives which impart certain desired properties to the animal skin to be treated.
- additives may include dyes, adhesives, moisture control formulations, flame retardants, microparticles, nanoparticles, emulsifiers, emulsions, water repellents, lipophilicating agents, Brightening agents, fats, tears or oils and a suitable combination of such substances.
- the tannin content in the added tanning solution is preferably such that it corresponds approximately to the tannin content which the animal skin to be treated is to absorb in order to achieve a good leather quality.
- a tannery content of 4% by weight based on the ready-to-use leather, is aimed at in this respect.
- Leathers with such a tannin content have shrinkage temperatures of about 95 degrees Celsius. If one takes certain reductions in the shrinkage temperature into account, i. If one is satisfied with lower shrinkage temperatures, tannin contents of 3% by weight can also lead to passable leather qualities. Sometimes a certain excess of tannin may be beneficial. Thus, the excess tannin content may be up to about 80%, but more preferably at most 20%.
- the excess of tannin is considerably lower than that used in the classical procedure. Accordingly, in the process according to the invention, the tanning agent contained in the tanning solution (liquor) passes almost completely into the treated animal skin. This ensures, on the one hand, that the animal skin to be treated receives the amount of tanning agent required for complete tanning and, on the other hand, it avoids having to treat significant amounts of unused tanning agent.
- the period during which the animal skin containing the tanning solution is treated with compressed gas under pressure in a pressure vessel is preferably 30 minutes to 30 hours and more preferably 1 to 3 hours.
- the pressure in the pressure treatment step may be in the range of 10 bar to 200 bar, but is preferably in the range of 15 bar to 100 bar and more preferably in the range of 20 bar to 60 bar.
- the temperature in the pressure treatment step may be in the range of 0 ° C to 80 ° C, but is preferably in the range of 10 ° C to 60 ° C, and more preferably in the range of 25 ° C to 40 ° C.
- Particularly suitable compressed gas are carbon dioxide and nitrogen and mixtures thereof.
- the animal skins are preferably moved to achieve uniform tanning.
- the treated animal skins may be removed from the pressure vessel and dressed in a conventional manner.
- the liquid contained in the pressure-treated animal hides can be separated mechanically or thermally. If the separated liquid is recovered, which is easily possible, for example, during the thermal separation and drying, it can be returned to the process, so that the tanning step is completely free of wastewater.
- the pickling and pickling step is carried out in a pressure vessel in the presence of a compressed gas
- the gas is preferably carbon dioxide, but z. B. can also be nitrogen or a mixture of CO 2 and N 2 .
- dissolved carbon dioxide in the liquid phase causes an increase in the pH to about 3.3, so that the otherwise usual buffering of the pH by added alkalis is unnecessary. In this way, the inventive method can achieve a further saving of chemicals.
- the degree of dissolving in the liquid phase carbon dioxide can be adjusted by the pressure in the pressure vessel, which dissolves more carbon dioxide at higher pressure.
- tanning chemicals into the animal skin which is required for tanning the quality.
- the tanning process is shortened to a few hours and a deep tanning is achieved at liquor ratios that are far below the values technically previously considered feasible.
- commonly used chemicals to adjust the pH may be partially or completely be replaced by carbon dioxide and / or nitrogen, whereby the environmental impact is significantly reduced.
- a rawhide (bovine pimples) weighing 1,000 g has been mechanically decoked.
- the skin weight after this procedure was 600 g.
- the skin was brought into contact with 400 g of tanning solution.
- the skin has taken up the 400 g solution after about one hour.
- the skin was treated in an autoclave at 30 bar and 40 ° C with carbon dioxide for 2 hours.
- the tanning solution consisted of 310g of water, 65g of chromium sulphate and 25g of salt.
- the calculation of the minimum chromium sulfate to be used is listed as an example.
- the pH has been adjusted to 3.6 by means of sodium carbonate.
- the following example shows the calculation of the necessary amount of tanning chemicals with an overdose of 80%.
- the skin content in wet blue is on average 35 wt .-%.
- Example 1 The procedure and setting of all the parameters of Example 1 have also been used for Example 2 (withering from 1,000 g to 600 g with subsequent tanning dipping and taking in 400 g). Only the adjustment of the pH of the tanning solution by means of alkalis was dispensed with. After a one-hour dipping of the skin at pH 2.5 and subsequent treatment of the drained skin with compressed carbon dioxide at 30 bar, 40 ° C for 2 hours, a chromium content of> 4% Cr 2 O 3 was achieved. The shrinkage temperature was T s > 95 ° C with very good tensile strength of 40 N / mm 2 .
- a cowhide weighing 1.5 kg has been prepared according to the tanning method described in Example 1. Weakened and then added to tanning solution 600 g. The process was carried out similarly to that in Example 1, with the difference that in the autoclave, a pressure of 20 bar has been set. Both the shrinkage temperature (T s ⁇ 90 ° C) and the tensile strength (14 N / mm 2 ) have shown that the leather has not been tanned.
- a bovine skin with a wet weight of 1.2 kg was wilted (480 g) and dipped by the method described in Example 1. The skin was then moved pressure-free for 2.5 h and rested for more than 24 h after the experiment. This skin was not tanned. Optically and haptically, a horn-like drying of the untreated skin collagen could be determined after finishing.
- Example 2 The procedure, parameters and mass ratios chosen in Example 2 have been used.
- the wet weight of the skin was 3.5 kg. Wounded and absorbed were 1,400 g.
- the leather also has a shrinkage temperature of T s > 90 ° C and the optical and haptic analysis of the dressed leather has shown high leather quality.
- Example 1 The parameters used in Example 1 were used (pimpling size of 1,000 g, after withering to 600 g, followed by absorption of 400 g of tanning solution, 30 bar and 40 ° C for 2 hours). Instead of taking carbon dioxide, it has been tanned under a nitrogen atmosphere. Haptic and optical control gave good leather quality. The shrinkage test confirmed this (TS> 90 ° C).
- a tanning with vegetable tannin has been done for beef and goat skin. Each 1 kg of skin was used. It has not withered away but has been tanned with liquor. Based on the weight of the skin, 2.5% by weight of Picaltal dandruff (as a salt substitute), 15% of vegetable tanning agent (Tara) and 500% of water have been added. The pH has been raised to 4.0. The process parameters have been set to 200 bar, 40 ° C and 10 revolutions per minute. After a process time of 4 h, a high leather quality was achieved. The leathers have been tested by shrinkage temperature (T Svegetabil > 70 ° C), optical and haptic analysis.
- a rawhide (bovine pimples) with a weight of 1000g has been mechanically wilted off. The weight after this process was 600g. Then it is the skin has been contacted with 400g of tanning solution. In this tanning solution so much chromium sulfate was dissolved that a quantity of 10.06 g chromium III ions was present. This corresponds to 1.05 times the target value of 4% chromium oxide in the leather, which was chosen as a guideline for achieving a good leather quality. After the skin had taken up the tanning solution, it was treated with carbon dioxide in an autoclave for 3 hours at 60 bar and 40 ° C.
- the insert basket in which the piece of skin was located, rotated at a speed of 10 revolutions per minute. Immediately after releasing the pressure and opening the autoclave, a shrinkage temperature of 99 ° C was measured. The contact of the tanned cowhide with boiling water left the latter completely clear, which is an indication that neither chromium nor proteins are boiled out of the skin.
- Example 1 The remaining piece of skin was then trimmed.
- the shrinkage temperature of the dressed piece increased to 100 ° C. Also in this test, no discoloration of the boiling water was observed.
- the other quality parameters were comparable to Example 1 and showed a very high quality of tanned leather.
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)
- Coloring (AREA)
Claims (14)
- Procédé pour le tannage de peaux animales, présentant les étapes :- décapage et picklage de la peau animale en solution aqueuse,- réduction de la teneur en liquide de la peau animale de 5% à 90%,- remplacement d'au moins une partie de la quantité liquide retirée de la peau animale dans l'étape précédente par une solution de tannage, de telle manière que le rapport de bain, défini par
présente une valeur inférieure à 1, la solution de tannage contenant la substance de tannage à absorber par la peau animale en une quantité qui correspond au maximum à un excès de 80%, et- traitement de la peau animale contenant la solution de tannage avec du gaz comprimé dans un récipient sous pression pendant un laps de temps d'au moins 15 minutes. - Procédé selon la revendication 1, caractérisé en ce qu'on élimine, dans l'étape de réduction, 20% à 70% et de préférence 30% à 50% de la teneur en liquide de la peau animale.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que dans l'étape de réduction, la teneur en liquide est diminuée par un procédé thermique et/ou par adsorption et/ou mécanique.
- Procédé selon la revendication 3, caractérisé en ce que le procédé mécanique est un procédé d'écrasement.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le remplacement de la quantité de liquide éliminée de la peau animale par la solution de tannage est réalisé de manière telle que le rapport de bain se situe dans la plage de 0,05 à 0,9, de préférence dans la plage de 0,1 à 0,7 et encore plus préférablement dans la plage de 0,3 à 0,6.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le laps de temps de traitement à la pression est de 30 minutes à 30 heures, de préférence de 1 à 3 heures.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le gaz comprimé est le dioxyde de carbone et/ou l'azote.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la pression dans l'étape de traitement à la pression se situe dans la plage de 10 bars à 200 bars, de préférence dans la plage de 15 bars à 100 bars et de manière particulièrement préférée dans la plage de 20 bars à 60 bars.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la température dans l'étape de traitement à la pression se situe dans la plage de 0°C à 80°C, de préférence dans la plage de 10°C à 60°C et de manière particulièrement préférée dans la plage de 25°C à 40°C.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution de tannage contient des substances de tannage végétales et/ou synthétiques.
- Procédé selon la revendication 10, caractérisé en ce que la solution de tannage contient des substances de tannage présentant des cations métalliques.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution de tannage contient une ou plusieurs des substances suivantes : colorants, adhésifs, préparations régulatrices de l'humidité, agents ignifuges, microparticules, nanoparticules, émulsifiants, émulsions, agents d'hydrofugation, agents de lipophilisation, agents brillants, graisses, suints, huiles.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution de tannage contient la substance de tannage à absorber par la peau animale en un excès d'au plus 20%.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape de décapage et de picklage est également réalisée dans un récipient sous pression en présence d'un gaz comprimé.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009018232A DE102009018232B8 (de) | 2009-04-21 | 2009-04-21 | Verfahren zur Gerbung von Tierhäuten |
PCT/EP2010/002452 WO2010121804A1 (fr) | 2009-04-21 | 2010-04-21 | Procédé de tannage de peaux d'animaux |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2421995A1 EP2421995A1 (fr) | 2012-02-29 |
EP2421995B1 true EP2421995B1 (fr) | 2013-01-30 |
Family
ID=42315550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10715707A Active EP2421995B1 (fr) | 2009-04-21 | 2010-04-21 | Procédé de tannage de peaux d'animaux |
Country Status (7)
Country | Link |
---|---|
US (1) | US9206486B2 (fr) |
EP (1) | EP2421995B1 (fr) |
CN (1) | CN102405297B (fr) |
DE (1) | DE102009018232B8 (fr) |
DK (1) | DK2421995T3 (fr) |
ES (1) | ES2400075T3 (fr) |
WO (1) | WO2010121804A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020207615A1 (fr) | 2019-04-10 | 2020-10-15 | Uvex Safety Gloves Gmbh & Co. Kg | Augmentation de la résistance chimique à l'aide de complexes d'inclusion |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015127935A1 (fr) | 2014-02-25 | 2015-09-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Procédé de tannage de peaux d'animaux et cuir tanné produit à partir de celles-ci |
CN104711383A (zh) * | 2015-03-27 | 2015-06-17 | 陕西科技大学 | 基于纳米复合高吸收铬鞣助剂的三明治式无盐鞣制工艺 |
DE102016004237A1 (de) * | 2016-04-08 | 2017-10-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Gerbvorrichtung mit drehbar gelagertem Druckbehälter |
CN106399598A (zh) * | 2016-06-24 | 2017-02-15 | 安徽创荣服装辅料有限公司 | 一种制造植鞣黄牛皮圈革的方法 |
CN106755618A (zh) * | 2016-12-28 | 2017-05-31 | 宁夏开司米科技开发有限公司 | 绒山羊皮毛一体加工工艺 |
US20220194642A1 (en) * | 2019-04-17 | 2022-06-23 | Ecco Sko A/S | A method and a packaging for packing one or more animal hides |
CN114231673A (zh) * | 2021-11-10 | 2022-03-25 | 中牛集团有限公司 | 一种无盐无铬的利用废液进行浸酸鞣制的制革工艺 |
CN114574636B (zh) * | 2022-02-25 | 2023-08-29 | 中国皮革制鞋研究院有限公司 | 一种生态彩色透明软皮革及其加工方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3840433A (en) * | 1968-09-23 | 1974-10-08 | Novo Terapeutisk Labor As | Dehairing of leather |
IT1121190B (it) | 1979-07-24 | 1986-03-26 | Torrini Ottavio | Procedimento di conciatura di pelli con sali di gromo trivalente entro botti ruotanti senza bagno residuo per motivi di ordine ecologico |
US5300121A (en) * | 1987-04-28 | 1994-04-05 | Commonwealth Scientific And Industrial Research Organisation | Process for the treatment of wool skins |
FR2696477B1 (fr) | 1992-10-02 | 1994-11-18 | Commissariat Energie Atomique | Procédé de traitement de peaux, de cuirs ou de matériaux en feuilles contenant du collagène, par un fluide dense sous pression. |
DE19507572A1 (de) | 1995-03-03 | 1996-09-12 | Helmut Geihsler | Verfahren zur Zurichtung von tierischen Häuten oder Fellen |
FR2800389B1 (fr) * | 1999-10-29 | 2002-04-12 | Commissariat Energie Atomique | Procede de tannage de peaux ou de materiaux contenant du collagene, avec un fluide dense sous pression |
US6854301B1 (en) * | 2004-04-13 | 2005-02-15 | Albany International Corp. | Extended nip press for the leather industry |
CN1281766C (zh) | 2005-03-07 | 2006-10-25 | 四川大学 | 以二氧化碳超临界流体为介质的制革方法 |
DE102006008190A1 (de) | 2006-02-22 | 2007-08-23 | Linde Ag | Verfahren zum Fetten von Leder |
-
2009
- 2009-04-21 DE DE102009018232A patent/DE102009018232B8/de not_active Expired - Fee Related
-
2010
- 2010-04-21 DK DK10715707.5T patent/DK2421995T3/da active
- 2010-04-21 CN CN201080017504.4A patent/CN102405297B/zh active Active
- 2010-04-21 ES ES10715707T patent/ES2400075T3/es active Active
- 2010-04-21 US US13/380,803 patent/US9206486B2/en active Active
- 2010-04-21 WO PCT/EP2010/002452 patent/WO2010121804A1/fr active Application Filing
- 2010-04-21 EP EP10715707A patent/EP2421995B1/fr active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020207615A1 (fr) | 2019-04-10 | 2020-10-15 | Uvex Safety Gloves Gmbh & Co. Kg | Augmentation de la résistance chimique à l'aide de complexes d'inclusion |
DE102019109425B4 (de) | 2019-04-10 | 2022-01-05 | Uvex Safety Gloves Gmbh & Co. Kg | Verfahren zur Herstellung eines imprägnierten Polymersubstrats, Verfahren zur Herstellung von Chemikalienschutzhandschuhen und Verwendung eines imprägnierten Polymersubstrats für Schutzkleidung |
Also Published As
Publication number | Publication date |
---|---|
WO2010121804A1 (fr) | 2010-10-28 |
DK2421995T3 (da) | 2013-05-06 |
CN102405297A (zh) | 2012-04-04 |
US9206486B2 (en) | 2015-12-08 |
EP2421995A1 (fr) | 2012-02-29 |
CN102405297B (zh) | 2014-02-12 |
ES2400075T3 (es) | 2013-04-05 |
US20120144597A1 (en) | 2012-06-14 |
DE102009018232A1 (de) | 2010-10-28 |
DE102009018232B8 (de) | 2011-11-10 |
DE102009018232B4 (de) | 2011-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2421995B1 (fr) | Procédé de tannage de peaux d'animaux | |
DE3013912A1 (de) | Polymerprodukte zur behandlung von bloessen und leder | |
EP2956558B1 (fr) | Procédé pour la fabrication de cuir | |
DE2930342C2 (fr) | ||
EP3924523B1 (fr) | Adjuvants dans la fabrication du cuir pour le travail de rivière | |
DE1297274B (de) | Verfahren zur Herstellung von chromgegerbtem Leder | |
EP1029930B1 (fr) | Procédé de tannage | |
EP3110978B1 (fr) | Procédé de tannage de peaux d'animaux et cuir tanné ainsi obtenu | |
DE69201945T2 (de) | Anwendung von Kieselsäuresolen zur Erhaltung eines Hauts unter der Bezeichnung "blanc pickle stabilise" oder "blanc stabilise". | |
DE1233530B (de) | Verfahren zum enzymatischen Enthaaren und bzw. oder Beizen von Haeuten und Fellen | |
DE69704026T2 (de) | Gerbprozess | |
DE3929366A1 (de) | Verfahren zur herstellung von chromfreiem weichleder | |
DE2424301C3 (de) | Verfahren zum Chromgerben und Gerbmischung dafür | |
DD296706A5 (de) | Biologisch stabile, in feuchter form vorliegende ungegerbte haeute | |
AT239428B (de) | Verfahren zum Gerben tierischer Häute und Felle bzw. Blößen | |
DE1284028C2 (de) | Verfahren zum schnellgerben von haeuten | |
DE716747C (de) | Verfahren zum Entkaelken von geaescherten Bloessen | |
AT227862B (de) | Verfahren zum Gerben von Häuten und Fellen mit Chromsalzen | |
AT249243B (de) | Verfahren zum Enthaaren von Häuten und Fellen und zum Vorbereiten derselben für die Gerbung | |
DE1800891C (de) | Verfahren zum Weichen oder Beizen von Häuten oder Fellen oder Nachbeizen von vorgegerbtem Hautmaterial | |
DE1191071B (de) | Verfahren zur Herstellung von Schuhunterleder durch Schnellgerbung schwerer Haeute | |
DE3440750A1 (de) | Verfahren zum hautaufschluss von grossviehhaeuten und kalbfellen | |
DE2831475B2 (de) | Gegenüber Calciumchlorid widerstandsfähiges, nachbehandeltes Chromleder, Verfahren zu seiner Herstellung und dessen Verwendung | |
DE1494841A1 (de) | Verfahren zum Schnellgerben von Leder | |
WO2001002533A1 (fr) | Agent et procede pour la fabrication de demi-produits de cuir |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110919 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 595730 Country of ref document: AT Kind code of ref document: T Effective date: 20130215 Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502010002262 Country of ref document: DE Effective date: 20130321 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2400075 Country of ref document: ES Kind code of ref document: T3 Effective date: 20130405 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20130130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130530 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130430 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130530 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
BERE | Be: lapsed |
Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWAN Effective date: 20130430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20131031 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130430 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502010002262 Country of ref document: DE Effective date: 20131031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130421 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20100421 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130421 Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130130 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20190425 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20190416 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP Effective date: 20200430 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 595730 Country of ref document: AT Kind code of ref document: T Effective date: 20200421 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200421 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230524 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20230418 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240423 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240418 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240517 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20240430 Year of fee payment: 15 Ref country code: FR Payment date: 20240419 Year of fee payment: 15 |