EP2862944A1 - Ecological tanning and dyeing process and product obtained - Google Patents
Ecological tanning and dyeing process and product obtained Download PDFInfo
- Publication number
- EP2862944A1 EP2862944A1 EP20130188958 EP13188958A EP2862944A1 EP 2862944 A1 EP2862944 A1 EP 2862944A1 EP 20130188958 EP20130188958 EP 20130188958 EP 13188958 A EP13188958 A EP 13188958A EP 2862944 A1 EP2862944 A1 EP 2862944A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tanning
- leather
- ecological
- skins
- dyeing process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004043 dyeing Methods 0.000 title claims abstract description 24
- 239000010985 leather Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 235000013311 vegetables Nutrition 0.000 claims abstract description 23
- 239000003921 oil Substances 0.000 claims abstract description 18
- 239000000049 pigment Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001648 tannin Substances 0.000 claims abstract description 11
- 235000018553 tannin Nutrition 0.000 claims abstract description 11
- 229920001864 tannin Polymers 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 6
- 239000008103 glucose Substances 0.000 claims abstract description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 5
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 5
- 229920001194 natural rubber Polymers 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002023 wood Substances 0.000 claims description 7
- 241001465754 Metazoa Species 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 229920005615 natural polymer Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 16
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 239000003086 colorant Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000000284 extract Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 241001070941 Castanea Species 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 241001518926 Cladrastis Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 240000005852 Mimosa quadrivalvis Species 0.000 description 1
- 229930182559 Natural dye Natural products 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 206010040914 Skin reaction Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000004106 carminic acid Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940080423 cochineal Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 235000021268 hot food Nutrition 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000978 natural dye Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000430 skin reaction Toxicity 0.000 description 1
- 230000035483 skin reaction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000007063 yellowwood Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—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
- C14C3/08—Chemical tanning by organic agents
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/14—Fat tanning; Oil 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
- C14C3/28—Multi-step processes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/34—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using natural dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
Definitions
- the European patent EP0849365 is about a composition for preparing leather or hides comprises a retanning agent, a dubbing agent and optionally adjuvants, which when added to an at least 8-fold amount of water at 10-60 degrees C forms a homogeneous mixture.
- the patent application WO2010/130311 describes a tanned leather, skin or pelt which is produced by non-metal tanning, comprising the step of tanning with a non metallic tanning agent in a tanning bath, the tanning bath having a pH of from 6 to 10 at the beginning of tanning step.
- the invention relates to the defined tanning process, particular tanning agent compositions, the use of the tanned leather, skins or pelts for further processing and the produced tanned and optionally further processed leather, skins or pelts.
- tanning and dying skins, pelts or leather are two different steps.
- the well known natural pigments to dye hides are campeach wood extracts (red to black), chestnut (greenwish-brown), yellow wood (yellow to orange), indigo (blue), cochineal (red), tara.
- the purpose of the present invention is to provide a new process to tan leather, skins, hide or pelts to preclude the above drawbacks.
- the invention concerns an ecological tanning and dyeing process of leather, skins, hide or pelts which is chrome-free and combines vegetable and oil tanning, said ecological tanning process is based on a biodegradable composition comprising :
- Advantageously vegetable tanning uses vegetable tanning agents from wood, bark, fruit, leaf, gall or natural polymers.
- An other purpose of the invention is a product obtained by said ecological tanning and dyeing process.
- skins can be dye with non synthetic and originally natural pigments which are not containing any metal complexes. They are obtained from wood extracts for brown colours, mineral extracts for grey colours or vegetable extracts for brown, yellow and light colours. Skins are placed for 24 to 48 hours at 35 to 50°C in a dedicated drum with a mix of pigments to obtain desired colour and rubber to fix the colour.
- This dyeing process gives a specific colour and texture effect to the leather which cannot be obtained by other process, in particular with traditional vegetable tanning. Indeed, it allows to have light colours and more brilliant and more shiny colours.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
- a tanning composition comprising
○ 10 to 20% of glucose
○ 10 to 30% of a mix of oils
○ 2 to 15% of vegetable tannins
- and water
and said ecological dyeing process is based on a combination of :
- 1 to 10% of natural rubber
- 1 to 10% of originally natural pigments
- water
Description
- The invention relates to an ecological tanning and dyeing process of leather, hide, skins or pelts.
- The methods used in tanneries comprise the steps of:
- « working as river » which is a phase of cleaning the skin in an aqueous medium and / or via mechanical means to remove salts conservation, hair, flesh, fats, keratin, soluble proteins, bacteria and the superficial dirt. The skins are washed scraped and shaved if necessary, and called "Pelts"
- the "pickle" that reduce the pH of the skin to improve the preservation of skins by acid treatment aims,
- the "tanning" in which the collagen fibres are stabilized by the tanning agents so that the skin becomes rot, the "currying" which includes the following: neutralization and washing, followed by a re-tanning, of drying and a hot food, which are mostly conducted in a single treatment tank. At this stage, the leather is called "Crust" and "finishing" which includes several mechanical treatments, as well as the application of a surface layer to improve the appearance and feel of leather.
- The tanning step is considered the most important in the chain of processing raw hides that are stiff and after storage putrescible and are thus transformed into a soft rot and what the leather material. Systems most commonly used tanning are:
- mineral tanning which uses trivalent chromium salts,
- vegetable tanning based on tanning power plant extracts wood or bark of certain trees and
- tanning made via synthetic.
- The existing mineral tanning processes are implemented in an aqueous medium. The tanning chromium chloride or chromium sulfate is the most common. The tanning with chromium is often preceded by acid treatment in a step known as "pickling".
- Pickling keeps the gut and skin reactivity to decrease the reaction sites, vis-à-vis the chromium, so as not to interfere with its diffusion into the collagen. Indeed, in the tanning step, trivalent chromium is inserted between the collagen fibres and the reticle by forming complexes with the anionic sites of the polypeptide chains. Tanning with chromium salts leads to a leather with excellent physicochemical properties, including flexibility, tear resistance and high thermal resistance.
- However, it proves harmful to the environment due to the use of recycled or easily removable as chromium metal. Thus, tanning baths are never completely depleted chromium, which leads to the release of baths containing significant amounts of chromium (about 25 to 30% compared to the quantities introduced). However, chromium is a toxic pollutant releases and agent must undergo treatments statutorily disposal of chromium which are very expensive and do not allow direct recovery of chromium. In addition, we observe during finishing operations after the tanning (especially during dyeing) of salting-chromium polluting the bathroom and require removal treatments as for tanning baths. In addition, the use of metals such as chromium sometimes leads, due to the action of these allergenic, skin reactions in the user. It should be noted that, given a limited amount of chromium is attached to the skin to treat in a single tanning, it can undergo a new stage of tanning with chromium salts so that larger amount of chromium may be secured by the thus treated skin. This step retannage aims to ensure better penetration of dyes, improve the general feel, thickness, toughness, chemical resistance and heat resistance.
- Tanning is the process to make hide or skins non putrescible. Many tanning processes are known in the art. Among them, chrome-based tanning or vegetable tanning are widely used. However, chrome-based tanning are dangerous for human health and environment.
- Vegetable tanning is known since a long time and is considered as one of the best process to obtain a good quality and suppleness leather. But it is long and expensive. This process uses tannins from wood, bark, fruit, leaf, gall or natural polymers. The main used species are oak, chestnut, sumac, myrobollan or mimosa. Vegetable tanning consists in mixing skins or leather in water with an homogenate or extract of one or some of this species. It takes several months to tan a hide. So, this ancestral tanning process is not really adapted to industry. Moreover, natural dyes are not as efficient as synthetic dyes with fading problems during the life of the leather.
- New processes have been developed. Among them, chrome-based is the quicker and the cheaper way to tan hide or skins. But, leather obtained by this process cannot be used for every application. The obtained leather is not suppleness and could generate allergies. Because of the toxicity of the sludge generated by this process, new technics need to be developed to protect the environment.
- For example, the international patent application
WO2006/067801 deals with a bio-tanning process for leather making. Conventionally skins/hides are tanned with metal-ions and vegetable tannins. Environmental constraints on the discharge of toxic metal-ions and poor biodegradable vegetable tannins in the wastewater have become serious issue. In this invention, the pelts are tanned using eco-benign bio-molecules other than vegetable tannins to reduce the pollution loads. Performance of the leathers is on par with conventionally processed leathers. - The European patent
EP0849365 is about a composition for preparing leather or hides comprises a retanning agent, a dubbing agent and optionally adjuvants, which when added to an at least 8-fold amount of water at 10-60 degrees C forms a homogeneous mixture. - Some solutions of the previous art deal with new kind of molecules, design to be as efficient as chrome but less polluting. The patent application
WO2010/130311 describes a tanned leather, skin or pelt which is produced by non-metal tanning, comprising the step of tanning with a non metallic tanning agent in a tanning bath, the tanning bath having a pH of from 6 to 10 at the beginning of tanning step. The invention relates to the defined tanning process, particular tanning agent compositions, the use of the tanned leather, skins or pelts for further processing and the produced tanned and optionally further processed leather, skins or pelts. - An other challenge of eco-friendly tanning processes is pigments. Usually, tanning and dying skins, pelts or leather are two different steps. The well known natural pigments to dye hides are campeach wood extracts (red to black), chestnut (greenwish-brown), yellow wood (yellow to orange), indigo (blue), cochineal (red), tara. There are also synthetic colours based on basic dyes, acid dyes, direct dyes and sulphur dyes.
- The patent application
WO2005/038124 deals with a process for the production of pigment-dyed leather wherein a tanned leather is retanned at a pH GBP 4.5 with a combined retanning agent, which is a combination of a syntan or syntan precursor with a basic metal tanning agent, and is pigment-dyed in an aqueous dye bath with at least one pigment in the form of an aqueous dispersion of a colour pigment, in which the average particle size of the dispersed particles is < 5 microm, in the presence of a surface active aliphatic mono-, di- or triamine containing a C12-30-hydrocarbon radical and at least one polyethyleneglycolether chain, or an amphoteric derivative thereof, at a pH GBP 4.5, provides pigment-dyeings of outstanding colour yield, levelness and reproducibility of the pigment-dyeing, with satisfactory surface penetration, and also of satisfactory hiding properties with respect of any irregular previous dyeings of the substrate, while the typical leather structure is substantially maintained and visible, suitable compositions therefor, and the pigment-dyed substrates. - Some news technics emerged combining tanning and dyeing in the same bath.
- For example, the patent application
NZ193940 - The patent application
EP0543689 describes compositions to simultaneously tan and dye hides, characterized by the fact that they contain at least one tanning compound able to form chromophore groups and at least one coupler able to develop with the chromophore groups of the compound tanning the final colour. - But this combination technics are not necessary environment friendly by mixing natural and synthetic products.
- The purpose of the present invention is to provide a new process to tan leather, skins, hide or pelts to preclude the above drawbacks. Indeed, the invention concerns an ecological tanning and dyeing process of leather, skins, hide or pelts which is chrome-free and combines vegetable and oil tanning, said ecological tanning process is based on a biodegradable composition comprising :
- a tanning composition comprising
- ○ 10 to 20% of glucose
- ○ 10 to 30% of a mix of oils
- ○ 2 to 15% of vegetable tannins
- and water and said ecological dyeing process is based on a combination of :
- 1 to 10% of natural rubber
- 1 to 10% of originally natural pigments
- water
- Percentages are essentially related to weight of skins to be tanned.
- Different types of skins can be tanned and dyed by this process but it is particularly adapted to sheep.
- Advantageously oils are from animals.
- Advantageously oils are vegetal oils.
- Advantageously vegetable tanning uses vegetable tanning agents from wood, bark, fruit, leaf, gall or natural polymers.
- In a preferred embodiment originally natural pigments are non synthetic and do not contain any metal complexes.
- An other purpose of the invention is a composition for ecological tanning process of leather, skins, hide or pelts, which comprises in percentage of weight :
- 10 to 20% of glucose
- 10 to 30% of animal or vegetal oils
- 2 to 15% of vegetable tannins
- 50 to 70% of water
- An other purpose of the invention is a composition for ecological dyeing process of leather, skins, hide or pelts which comprises in percentage of weight :
- 1 to 10% of natural rubber
- 1 to 10% of originally natural pigments
- water
- An other purpose of the invention is a product obtained by said ecological tanning and dyeing process.
- The invention will be better understood with the description of the best embodiment.
- The ecological tanning and dyeing process disclosed by the invention comprises several steps.
- The
figure 1 describes the process steps according to the invention. - The skins are pre-tanned as usually done in that technical field. Dehaired sheep skins are placed in a wood or polycarbon drum with a tanning mix comprising 10 to 20% of glucose, 10 to 30% of a mix of several natural oils, 2 to 15% of vegetable tannins and 50 to 70% of water. The mix of oils is composed by animals and vegetables oils but each proportion depends on the nature of the skins and the desired colour. Indeed, oil combination influences the result of the tanned skin. The tanning step is between 2 and 3 days long at ambient temperature.
- At the end of this step, the tanned skins are hanged and dried by air for several hours or days.
- Then, skins can be dye with non synthetic and originally natural pigments which are not containing any metal complexes. They are obtained from wood extracts for brown colours, mineral extracts for grey colours or vegetable extracts for brown, yellow and light colours. Skins are placed for 24 to 48 hours at 35 to 50°C in a dedicated drum with a mix of pigments to obtain desired colour and rubber to fix the colour. This dyeing process gives a specific colour and texture effect to the leather which cannot be obtained by other process, in particular with traditional vegetable tanning. Indeed, it allows to have light colours and more brilliant and more shiny colours.
- Leathers are then dried on air as previously.
- Some additional steps can be done as softening the leather by leaving leather in a drum for several hours or as fixing the colours. Leathers are then ready to be used for many different applications.
Claims (8)
- An ecological tanning and dyeing process of leather, skins, hide or pelts which is chrome-free and combines vegetable and oil tanning, said ecological tanning process is based on a biodegradable composition comprising :- a tanning composition comprising○ 10 to 20% of glucose○ 10 to 30% of a mix of oils○ 2 to 15% of vegetable tannins- and water
and said ecological dyeing process is based on a combination of :- 1 to 10% of natural rubber- 1 to 10% of originally natural pigments- water - An ecological tanning and dyeing process of leather, skins, hide or pelts wherein oils are from animals.
- An ecological tanning and dyeing process of leather, skins, hide or pelts wherein oils are vegetal oils.
- An ecological tanning and dyeing process of leather, skins, hide or pelts wherein vegetable tanning uses vegetable tanning agents from wood, bark, fruit, leaf, gall or natural polymers.
- An ecological tanning and dyeing process of leather, skins, hide or pelts wherein originally natural pigments are non synthetic and do not contain any metal complexes.
- A composition for ecological tanning process of leather, skins, hide or pelts, which comprises in percentage of weight :- 10 to 20% of glucose- 10 to 30% of animal or vegetal oils- 2 to 15% of vegetable tannins- 50 to 70% of water
said composition is totally biodegradable and environment-friendly. - A composition for ecological dyeing process of leather, skins, hide or pelts which comprises in percentage of weight :- 1 to 10% of natural rubber- 1 to 10% of originally natural pigments- water
said composition is totally biodegradable and environment-friendly. - Product obtained by said ecological tanning and dyeing process.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RS20170275A RS55791B1 (en) | 2013-10-16 | 2013-10-16 | Ecological tanning and dyeing process and product obtained |
EP13188958.6A EP2862944B1 (en) | 2013-10-16 | 2013-10-16 | Ecological tanning and dyeing process and product obtained |
ES13188958.6T ES2625320T3 (en) | 2013-10-16 | 2013-10-16 | Ecological process of tanning and dyeing and product obtained |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13188958.6A EP2862944B1 (en) | 2013-10-16 | 2013-10-16 | Ecological tanning and dyeing process and product obtained |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2862944A1 true EP2862944A1 (en) | 2015-04-22 |
EP2862944B1 EP2862944B1 (en) | 2016-12-14 |
Family
ID=49356326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13188958.6A Active EP2862944B1 (en) | 2013-10-16 | 2013-10-16 | Ecological tanning and dyeing process and product obtained |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2862944B1 (en) |
ES (1) | ES2625320T3 (en) |
RS (1) | RS55791B1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITUA20162349A1 (en) * | 2016-04-06 | 2017-10-06 | Glycolor S R L | USE OF LACTOSE IN COMBINATION WITH NATURAL VEGETABLE EXTRACTS FOR THE METAL FREE TANNING OF ANIMAL SKINS |
WO2021010815A1 (en) * | 2019-07-16 | 2021-01-21 | Curtidos Treviño, S.A. De C.V. | Method for manufacturing sustainable leather using by-products of parts of all the genus persea plant varieties and species, including both the american species and the hass variety |
EP4180541A1 (en) | 2021-11-15 | 2023-05-17 | Cyclica S.r.l. | Method for obtaining a tanned product |
IT202200003698A1 (en) * | 2022-02-28 | 2023-08-28 | Stazione Sperimentale Per Lindustria Delle Pelli E Delle Materie Concianti S R L | Preparation and application process of tanning vegetable oil |
IT202200007187A1 (en) * | 2022-04-11 | 2023-10-11 | Fgl Int S P A | TANNING PROCESS WITH LOW ENVIRONMENTAL AND HEALTH RISK, AND COMPOSITIONS FOR SAID PROCESS |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US196339A (en) * | 1877-10-23 | Improvement in tanning and dyeing leather | ||
GB405315A (en) * | 1932-08-02 | 1934-02-02 | Ici Ltd | Improved method of marking textile goods and marking compositions therefor |
NZ193940A (en) | 1979-06-06 | 1982-03-30 | Ciba Geigy Ag | Dyeing with an anionic dye and tanning pelts in a single bath |
US4784664A (en) * | 1986-06-24 | 1988-11-15 | Seton Company | Non-chrome tanning method |
DE3929366A1 (en) * | 1988-09-09 | 1990-03-22 | Simontornyai Boergyar | Prodn. of chrome free soft leather - by treatment with oil, fat or fatty oil before tanning |
EP0543689A1 (en) | 1991-10-30 | 1993-05-26 | Unitan S.A.I.C.A. | Compositions to simultaneously tan and dye hides and their production process |
EP0849365A1 (en) | 1996-12-20 | 1998-06-24 | TFL Ledertechnik GmbH & Co. KG | Preparation agent for leather |
WO2005038124A1 (en) | 2003-10-21 | 2005-04-28 | Clariant International Ltd | Process and compositions for pigment-dyeing of leather |
WO2006067801A1 (en) | 2004-12-24 | 2006-06-29 | Council Of Scientific And Industrial Research | Bio-tanning process for leather making |
WO2010130311A1 (en) | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Tanning process and tanning composition |
-
2013
- 2013-10-16 RS RS20170275A patent/RS55791B1/en unknown
- 2013-10-16 ES ES13188958.6T patent/ES2625320T3/en active Active
- 2013-10-16 EP EP13188958.6A patent/EP2862944B1/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US196339A (en) * | 1877-10-23 | Improvement in tanning and dyeing leather | ||
GB405315A (en) * | 1932-08-02 | 1934-02-02 | Ici Ltd | Improved method of marking textile goods and marking compositions therefor |
NZ193940A (en) | 1979-06-06 | 1982-03-30 | Ciba Geigy Ag | Dyeing with an anionic dye and tanning pelts in a single bath |
US4784664A (en) * | 1986-06-24 | 1988-11-15 | Seton Company | Non-chrome tanning method |
DE3929366A1 (en) * | 1988-09-09 | 1990-03-22 | Simontornyai Boergyar | Prodn. of chrome free soft leather - by treatment with oil, fat or fatty oil before tanning |
EP0543689A1 (en) | 1991-10-30 | 1993-05-26 | Unitan S.A.I.C.A. | Compositions to simultaneously tan and dye hides and their production process |
EP0849365A1 (en) | 1996-12-20 | 1998-06-24 | TFL Ledertechnik GmbH & Co. KG | Preparation agent for leather |
WO2005038124A1 (en) | 2003-10-21 | 2005-04-28 | Clariant International Ltd | Process and compositions for pigment-dyeing of leather |
WO2006067801A1 (en) | 2004-12-24 | 2006-06-29 | Council Of Scientific And Industrial Research | Bio-tanning process for leather making |
WO2010130311A1 (en) | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Tanning process and tanning composition |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITUA20162349A1 (en) * | 2016-04-06 | 2017-10-06 | Glycolor S R L | USE OF LACTOSE IN COMBINATION WITH NATURAL VEGETABLE EXTRACTS FOR THE METAL FREE TANNING OF ANIMAL SKINS |
WO2021010815A1 (en) * | 2019-07-16 | 2021-01-21 | Curtidos Treviño, S.A. De C.V. | Method for manufacturing sustainable leather using by-products of parts of all the genus persea plant varieties and species, including both the american species and the hass variety |
US11976339B2 (en) | 2019-07-16 | 2024-05-07 | Curtidos Trevino, S.A. De C.V. | Method for producing sustainable leather using by-products from parts of all varieties and species of the genus Persea plant including among them both the american species and the hass variety as well |
EP4180541A1 (en) | 2021-11-15 | 2023-05-17 | Cyclica S.r.l. | Method for obtaining a tanned product |
IT202200003698A1 (en) * | 2022-02-28 | 2023-08-28 | Stazione Sperimentale Per Lindustria Delle Pelli E Delle Materie Concianti S R L | Preparation and application process of tanning vegetable oil |
IT202200007187A1 (en) * | 2022-04-11 | 2023-10-11 | Fgl Int S P A | TANNING PROCESS WITH LOW ENVIRONMENTAL AND HEALTH RISK, AND COMPOSITIONS FOR SAID PROCESS |
Also Published As
Publication number | Publication date |
---|---|
ES2625320T3 (en) | 2017-07-19 |
RS55791B1 (en) | 2017-08-31 |
EP2862944B1 (en) | 2016-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2862944B1 (en) | Ecological tanning and dyeing process and product obtained | |
CN109628653B (en) | Production process of environment-friendly high-grade sofa leather | |
Duraisamy et al. | A review of bio-tanning materials for processing of fish skin into leather | |
Sathiyamoorthy et al. | Preparation of eco-friendly leather by process modifications to make pollution free tanneries | |
Thomson | The manufacture of leather | |
Nazhmutdinovna | Environmental Problems of Chewing Chrome Tanned Leather | |
CN108892649A (en) | A kind of preparation method of modified amido acid derivative tanning agent | |
Li et al. | A novel approach to clean tanning technology | |
WO2023248148A1 (en) | Dyeing composition, process for its preparation, indigo dyeing of leather and indigo dyed leather | |
JPH01500130A (en) | Non-chrome tanning method | |
AU2003298467A1 (en) | A process for making leather | |
EP3094754B1 (en) | A composition for water free, pickle free chrome tanning of hides/skins | |
US20060288494A1 (en) | Process for producing leather | |
CN107109498B (en) | Dispersant composition for tanning hides/pelts and method for preparing same | |
US20040237208A1 (en) | Leather production | |
Burkinshaw et al. | Further studies of the use of chitosan in the dyeing of full chrome and heavily retanned leather with anionic dyes | |
US7252687B2 (en) | Process for making wet-pink leather | |
NL2024293B1 (en) | Process for dehairing and liming of hides, skins or pelts | |
KR101312940B1 (en) | Method for manufacture of horse skin dyed with natural dye and the horse skin obtained thereby | |
KR20060127416A (en) | A process for making leather | |
NL2033083B1 (en) | Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather | |
US20030038085A1 (en) | Methods for lowering pH in leather processing solutions | |
EP4192984B1 (en) | Retanning and fatliquoring compositions comprising a hemp oil derivative | |
Chala et al. | A Systematic Study on Nile Crocodile (CrocodylusNiloticus) Skins for the Preparation of Leather Products | |
Navarro Tovar | Bath exhaustion in metal-free leather processes |
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: 20131016 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL 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 RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
17Q | First examination report despatched |
Effective date: 20160504 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20160810 |
|
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): AL 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 RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 853644 Country of ref document: AT Kind code of ref document: T Effective date: 20170115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013015274 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 |
|
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: MP Effective date: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 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: 20170314 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: 20170315 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: 20161214 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 853644 Country of ref document: AT Kind code of ref document: T Effective date: 20161214 |
|
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: 20161214 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: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2625320 Country of ref document: ES Kind code of ref document: T3 Effective date: 20170719 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20170414 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: 20161214 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: 20161214 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: 20161214 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: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 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: 20170314 Ref country code: BE 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: 20161214 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: 20170414 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: 20161214 Ref country code: AT 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: 20161214 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013015274 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
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: 20170915 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161214 |
|
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: 20161214 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602013015274 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180501 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171031 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171016 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20171016 |
|
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: 20171016 |
|
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: 20131016 |
|
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: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20161214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL 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: 20161214 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230920 Year of fee payment: 11 Ref country code: GB Payment date: 20230920 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230920 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231102 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: RS Payment date: 20231011 Year of fee payment: 11 |