EP0615550B1 - Verfahren zur druckbehandlung von haeuten, ledern oder blattfoermigen, kollagenhaltigen materialien mit einem dichtem fluid - Google Patents

Verfahren zur druckbehandlung von haeuten, ledern oder blattfoermigen, kollagenhaltigen materialien mit einem dichtem fluid Download PDF

Info

Publication number
EP0615550B1
EP0615550B1 EP93921975A EP93921975A EP0615550B1 EP 0615550 B1 EP0615550 B1 EP 0615550B1 EP 93921975 A EP93921975 A EP 93921975A EP 93921975 A EP93921975 A EP 93921975A EP 0615550 B1 EP0615550 B1 EP 0615550B1
Authority
EP
European Patent Office
Prior art keywords
dense fluid
skins
process according
pressure
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93921975A
Other languages
English (en)
French (fr)
Other versions
EP0615550A1 (de
Inventor
Gérard Gavend
Bernard Vulliermet
Christian Perre
Maurice Carles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre Technique Cuir Chaussure Maroquinerie
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Centre Technique Cuir Chaussure Maroquinerie
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique CEA, Centre Technique Cuir Chaussure Maroquinerie filed Critical Commissariat a lEnergie Atomique CEA
Publication of EP0615550A1 publication Critical patent/EP0615550A1/de
Application granted granted Critical
Publication of EP0615550B1 publication Critical patent/EP0615550B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D06M23/105—Processes in which the solvent is in a supercritical state
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/647—Nitrogen-containing carboxylic acids or their salts
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
    • D06P1/67366—Phosphates or polyphosphates
    • 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
    • D06P1/94—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 dyes dissolved in solvents which are in the supercritical state
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3213—Material containing basic nitrogen containing amide groups leather skins using acid dyes monoazo
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3213—Material containing basic nitrogen containing amide groups leather skins using acid dyes monoazo
    • D06P3/322—Material containing basic nitrogen containing amide groups leather skins using acid dyes monoazo using monoazo premetallised dyes
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo
    • D06P3/3233—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo using dis-polyazo premetallised dyes
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/343—Material containing ester groups using vat or sulfur dyes

Definitions

  • the present invention relates to a process for treating skins, leathers or sheet materials containing collagen, at different stages of the transformation of skins into leathers, and at different stages of finishing these products.
  • the different stages of transformation of skins into leather are in particular the degreasing which consists in removing a part of the fats from the skin to facilitate its transformation into leather, and the tanning which transforms the raw putrescible skin into resistant and rot-proof leather; this last operation is considered to be the most important in the chain of transformation of skins into leathers.
  • the different stages of finishing can be retanning, which is an operation to reinforce the mechanical strength of leathers, dyeing and waterproofing for waterproofing.
  • the quantity of mainly aqueous effluents currently discharged by the leather industry worldwide is around 400 to 500 million m 3 per year, or almost 40 million equivalent "daily inhabitants".
  • the present invention specifically relates to a method of treating skins, hides or sheet materials containing collagen, which makes it possible to avoid the use of solvents harmful, penalizing for the environment, and to significantly limit the volumes of effluent produced during these treatments.
  • the process of the invention applies in particular to the degreasing and tanning of hides and to the finishing treatments (retanning, strengthening of the structure, dyeing and water repellency) of hides, leathers and other sheet materials containing collagen .
  • step a) of this process the dense fluid is circulated continuously at the pressure Pi and at the temperature Ti in a treatment enclosure containing the skins, the dense fluid is purified at the outlet of the treatment enclosure in order to separate the dissolved fat therefrom and the purified dense fluid is recycled at the inlet of the enclosure.
  • the dense fluid can be purified by varying its pressure and / or its temperature in order to eliminate the dissolved products in liquid form. To recycle the dense fluid, it is then necessary to bring it back under the pressure conditions Pi and temperature Ti chosen.
  • step b the circulation of the dense fluid under pressure is interrupted and the enclosure is brought back to atmospheric pressure.
  • the dense fluid under pressure is used as a solvent to extract fats of a lipidic nature, but one operates in such a way that the extraction of fats is not total to keep the skin supple.
  • the process of the invention therefore makes it possible to perform the degreasing of the skins under good conditions.
  • step a) is advantageously carried out by continuously circulating the dense fluid containing the active substance (s) at the pressure Pi and at the temperature Ti in a treatment chamber containing skins, leathers or sheet materials, by treating the dense fluid at the outlet of the treatment chamber to readjust its content of active substance (s) to the desired value, and thereby recycling the dense fluid treated in the treatment enclosure.
  • the treatment of the dense fluid leaving the enclosure in order to readjust its content of active substance (s) to the desired value can be carried out in gas-liquid or liquid-liquid contactors such as exchange columns with against the current.
  • Step b) can be carried out as above by interrupting the circulation of the fluid dense in the enclosure and reducing it to atmospheric pressure.
  • step a) of impregnation with the active substance and / or before step b) decompression it may be advantageous to rinse the products treated in the enclosure with pure dense fluid, before performing step a) of impregnation with the active substance and / or before step b) decompression.
  • step a) can be carried out statically (soaking) or dynamically, that is to say with continuous circulation of the dense fluid containing the active substance.
  • the expression “dense fluid” means a fluid under a pressure P greater than the critical pressure Pc of this fluid, which is preferably under temperature conditions Ti close to the critical temperature Tc of the fluid, this temperature and this pressure being chosen to give the fluid either a high extraction power with respect to grease, or a high dissolution or transport power with respect to the active substance or substances used.
  • the dense fluid used is in the form of gas at pressure and at room temperature.
  • This dense fluid can be chosen, for example, from carbon dioxide, sulfur hexafluoride, nitrous oxide, ammonia and light alkanes, having for example from 2 to 5 carbon atoms.
  • carbon dioxide is used because it is non-toxic, non-flammable, not very reactive and inexpensive.
  • the dense fluid can be in the subcritical or supercritical state.
  • Subcritical fluid is understood to mean a fluid at a temperature T lower than the critical temperature Tc of the fluid, which in the process of the invention corresponds to the liquid state, since the pressure Pi of the fluid is always greater than the pressure critic Pc.
  • supercritical fluid is meant a fluid whose temperature T is greater than the critical temperature, which, in the process of the invention, corresponds to the supercritical state since the pressure Pi of the fluid is always greater than the critical pressure.
  • the state diagram (in dashed lines) of pressure (in MPa) - temperature (in ° C.) of carbon dioxide CO 2 has been shown .
  • the critical point C of CO 2 corresponds to a critical temperature Tc of 31 ° C and to a critical pressure Pc of 7.3 MPa.
  • the supercritical fluid in the supercritical state according to the invention corresponds to the hatched area A.
  • the subcritical fluid in the liquid state according to the invention corresponds to the hatched area B.
  • the density of the fluid and therefore its power can be adjusted. solvent vis-à-vis the fat to dissolve or its capacity for dissolution and transportability of the active substances used, while further optimizing its capacity for dissolution so that it is not penalizing vis-à-vis the products to be treated.
  • the densities obtained under pressure are around 1 kg / cm 3 for the liquid state and adjustable from 0.2 to 1 kg / cm 3 for the supercritical state, ie a solvent power equivalent to that of traditional liquid solvents for the densest states; moreover, the fact that this solvent power is adjustable by pressure and / or temperature, can be judiciously used in the purification and impregnation operations with the active substance (s), during the recycling of dense fluid.
  • a dense fluid is used in the supercritical state.
  • the dense fluid also has viscosities ten times lower and diffusion coefficients 10 to 100 times greater than in the liquid state, which constitutes an important advantage for the kinetics of extraction and for the operations. impregnation.
  • the pressure Pi can be chosen, for example in the range from 6 to 5OMPa, and the temperature Ti can be, for example from 10 to 300 ° C.
  • the pressure variation ⁇ P can represent around 10% of Pi, for example over a period of 5 to 50s.
  • the active substances used are chosen according to the objective to be reached.
  • these active substances are organic materials or organo-mineral complexes, and the dense fluid used is also chosen according to the active substance so as to dissolve this substance or to be able to ensure its transport on the products to be treated in the pregnant.
  • the active substance is advantageously chosen from tanning agents, reinforcing agents, coloring agents, water-repellent agents and the precursors of these agents.
  • the tanning or reinforcing agents can be aldehyde compounds such as formaldehyde and glutaraldehyde; condensation products of the acrylate-diisocyanate, methylol-urea, or methylol-melamine type, of the telechelic oligomer type or of the precursors of these products, for example polyethylene glycols (PEG) and polytetraethylene glycols (PTEG) or methylene glycols (PTMG ) modified in the case of telechelic oligomers; phenol, naphthol, naphthalene or dihydroxyphenylsulfone products; vegetable tannins for example based on pyrogallics or catechism, or their precursors, tannins of chromium, of aluminum, of zirconium, titanium and iron.
  • aldehyde compounds such as formaldehyde and glutaraldehyde
  • nitrated and nitrosated compounds such as mono and polyazo dyes and with metal complexes; stilbenic derivatives; derivatives of diphenyl and triphenylmethane; oxazine, thiazine and azine compounds; pyridine, quinoline and acridine; phthalocyanic compounds; anthraquinone compounds, sulfur dyes; and their precursors.
  • water-repellent agents which can be used in the invention, mention may be made of chromium and fluorinated fatty acid complexes, chromium and aluminum alkylphosphate, imidoacetic acid derivatives, phosphoric acid esters, polysiloxane resins, fluorocarbon compounds or their precursors.
  • the dense fluid can also comprise an additive to modify the solvent or dehydrating power of the dense fluid, or to facilitate the dissolution or the transport of the active substance (s) in the dense fluid.
  • the active substance when it is not directly soluble in the dense fluid used, it can be dissolved in an additive acting as an auxiliary solvent, the whole being soluble or transported in the dense fluid.
  • the additive used can also be water, which makes it possible to modulate the drying power of the dense fluid. This possibility of regulating the water content of the treated products by modulating the drying power of the dense fluid constitutes a significant improvement in the chain of transformation of skins into leathers.
  • the active substance (s) can be included in the treated products, either by capillary action or direct absorption in these products when they have a particular affinity for the active substance, either by reaction of the active substance with compounds of the treated product, or by means of an appropriate treatment which transforms the active substance into a form retained by the product to be treated.
  • the active substance may consist of a precursor of a tanning, reinforcing, coloring or water repellency agent.
  • Treatments capable of modifying the active substance so that it is retained in the treated product can consist of chemical, physicochemical, photochemical treatment, irradiation, or even heat treatment.
  • the method of the invention is very advantageous for the treatment of skins, leathers, and other sheet products containing collagen, since it can be implemented at different stages of the processing and finishing chain of these products.
  • pressure and temperature conditions suitable for the treatment carried out are used in each stage, and these conditions may be the same or different when passing from one stage treatment to another.
  • the same dense fluid can be used in all stages or different dense fluids.
  • the installation includes a treatment enclosure (1) in which the products (2) to be treated, such as skins, leathers or sheet products containing collagen, can be placed on a support. appropriate to promote the flow of dense fluid in the products.
  • the products (2) to be treated such as skins, leathers or sheet products containing collagen
  • the dense fluid is introduced into the enclosure (1) by an inlet pipe (3) coming from a storage container (4) after having been brought to the pressure Pi desired by the compressor (5) and to the temperature Ti required by the heat exchanger (7).
  • This dense fluid was optionally charged with active substance (s) and / or additive (s) in contactors such as contactors (9) and (11).
  • the contactor (9) in which circulates for example water or an additive such as an alcohol through the pipes (13) and (15), can be connected by the pipe (17) to the inlet pipe (3 ) dense fluid in the enclosure (1).
  • the dense fluid introduced by the pipe (17) is evacuated by the pipe (19) then recycled in the inlet pipe (3), either by the pipe (21), or by the pipe ( 23).
  • the lines 17, 19, 21 and 23 and the pipe (3) are provided with suitable valves, not shown in the drawing, to allow the dense fluid to follow the desired circuit before it enters the enclosure (1).
  • the contactor (11) which is traversed for example by an active substance introduced by a pipe (25) and evacuated by a pipe (27), can be connected to the inlet pipe (3) by a pipe (29 ).
  • the dense fluid loaded with active substance leaving the contactor (11) via the pipe (31) is then recycled into the inlet pipe (3) through the pipe (23).
  • the lines (29) and (31) have suitable valves.
  • the dense fluid which is discharged into the outlet pipe (33) can be recycled without pressure loss other than the pressure losses, at the inlet of the enclosure (1) by the line (34), the circulator (35), the heat exchanger (7) and possibly the contactors (9) and (11).
  • the dense fluid is preferably recycled in the enclosure after having purified it from the dissolved products that it contains.
  • the dense fluid leaving via the pipe (33) is expanded in the valve (37), then introduced into the enclosure (39) for recovering the dissolved products which are separated from the dense fluid and discharged through the pipe (41 ). After this separation, the dense fluid which is in the gaseous state is brought back to the temperature suitable for recycling by the exchanger (43) and conveyed in the storage container (4) to be recycled in the enclosure (1) to desired temperature and pressure.
  • the contactors 9 and 11 are not connected to the supply pipe (3).
  • the contactor (9) can be replaced by a contactor (40) supplied with additive by the lines (42) and (44), which is placed on the dense fluid recycling circuit.
  • an additive for example water, can be added in small quantities to the fluid, when it is in the gaseous state after expansion in the valve 37.
  • the compressor (5) is stopped and the dense fluid leaving the enclosure (1) is decompressed by the expansion valve (37) to evacuate it in gaseous form as previously in the storage container (4 ) and bring the treated products to atmospheric pressure.
  • the installation can be supplied with treatment fluid through the pipe (45) and drained through the pipe (47).
  • Example 1 Degreasing of sheep skins in a pickled state.
  • the lipid and water content of the treated skins is determined. We aknowledge as well as the lipid content decreased by 40% and that the water content decreased by 17%.
  • the skins retain a beautiful supple appearance with a few small deposits of mineral salts.
  • Example 2 Degreasing of skins in the White Stabilized Wet state (BSH).
  • 1.5 kg of whole BSH skins are wound around an axis in the treatment enclosure (1) and the degreasing operation is carried out using dry and pure CO 2 in the supercritical state under a pressure of 30 MPa, at a temperature of 60 ° C, for a period such that the amount of CO 2 used is 300 kg.
  • the lipid and water content of the skins is determined. It is found that the lipid content has decreased by 26% and that the water content has decreased by 21%.
  • the skins retain a beautiful supple appearance with a very slight deposit of mineral salts.
  • the skins treated in Examples 1 and 2 were transformed into finished leather and were compared to skins having undergone the same treatments but for which the degreasing had been carried out in a conventional fashion in tanning by using white spirit associated with an emulsifying agent consisting of a base alkyl-oxyethylenated.
  • the skins degreased according to the conventional route or according to the route of Examples 1 and 2 were tanned with chromium salt (10% basic sulfate at 33% basicity), then wrung, thickened by stripping; they were then retanned, dyed and fed under the same conditions. During these operations, all the skins were treated in the same material in a single batch.
  • the colors are identical and no stain related to the presence of excess fat has been observed.
  • the process of the invention is used to impregnate skins and leathers by using, as active substance, reinforcing agents constituted by telechelic oligomers of the polyethylene glycol (PEG) type having molecular weights in the range from 200 to 1500.
  • PEG polyethylene glycol
  • the use of these oligomers is interesting because they are liquid products which can be dissolved in a dense fluid under pressure unlike the high solid polymers generally used for the reinforcement of leather products.
  • the pressure conditions Pi and the temperature conditions Ti are chosen to have good solubility of the active substance (PEG) in the dense fluid consisting of carbon dioxide.
  • the impregnation of skins and leathers is carried out under satisfactory conditions to obtain their reinforcement by passing 300 kg of dense fluid loaded with oligomer per kg of treated products.
  • these oligomers are liquid products which are more easily dissolved in the dense fluid than the high solid polymers usually used.
  • solubility values indicated in table 1 are not the maximum solubility values of the products concerned.
  • Examples 10 to 13 which follow illustrate the impregnation of an active substance constituted by a nourishing principle in skins and leathers.
  • skins and hides are treated using as nourishing product an oil of animal origin sulfitated at 60% content of active materials marketed under the name Lipoderm-Licker PK.
  • carbon dioxide is introduced into the treatment enclosure containing the skins and leathers as well as the oil, at a pressure of 25 MPa, at a temperature of 40 ° C. and the operation is carried out under static conditions for 16 hours. .
  • the skins and leathers are then brought to atmospheric pressure and their fat content is determined.
  • Skins and hides are treated using as active substance the same nourishing product as in Example 10, but in this case performing the impregnation under dynamic conditions as follows.
  • Carbon dioxide is passed under a pressure of 25 MPa, at a temperature of 40 ° C, with a flow rate of 15 kg / h in a first autoclave comprising the oil and then in the treatment chamber containing the hides and skins , for 4 hours.
  • Skins and hides are treated using as active substance the same nourishing product as in Example 11, but in this case the impregnation is carried out in pulsed dynamic regime by circulating CO 2 in a first autoclave containing the oil, then in the treatment chamber containing the hides and skins, under the same temperature (40 ° C.) and flow rate (15 kg / h) conditions as in Example 11, by varying the pressure siniusoidally, at a frequency of 10 s, 1 MPa around the average value of 19 MPa.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (20)

  1. Verfahren zum Entfetten von Häuten hinsichtlich ihrer Umwandlung in Leder,
    dadurch gekennzeichnet, daß es die folgenden Schritte umfaßt:
    a) die Häute in Kontakt zu bringen mit einem dichten Fluid, das fähig ist, die Fette unter einem Druck Pi und einer Temperatur Ti zu zusetzen bzw. aufzulösen, wobei der Druck Pi wenigstens gleich dem kritischen Druck Pc des Fluids ist und die Temperatur Ti derart ist, daß das Fluid eine ausreichende Dichte aufweist, um das partielle Solubilisieren der Fette sicherzustellen, und
    b) die Häute auf den atmosphärischen Druck zurückzuführen, um das dichte Fluid gasförmig zu eliminieren.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in Schritt a) das dichte Fluid mit dem Druck Pi und mit der Temperatur Ti kontinuierlich zirkulieren läßt in einem die Häute enthaltenden Behandlungsbehälter, man das dichte Fluid am Ausgang des Behandlungsbehälters reinigt, um die aufgelösten Fette von diesem zu trennen und man das gereinigte Fluid zum Eingang des Behälters zurückleitet.
  3. Verfahren zur Behandlung von Produkten, gebildet durch Häute, Leder oder Materialien in Form von Folien, Kollagen enthaltend, hinsichtlich ihrer Umwandlung in Leder oder ihrer Endbearbeitung, dadurch gekennzeichnet, daß es die folgenden Schritte umfaßt:
    a) die Häute, die Leder oder die Folienmaterialien in Kontakt zu bringen mit einem dichten Fluid, das wenigstens eine aktive Substanz zur Umwandlung oder Endbearbeitung der Häute, der Leder oder der Folienmaterialien enthält, unter einem Druck Pi wenigstens gleich dem kritischen Druck Pc des Fluids und mit einer derartigen Temperatur Ti, daß das Fluid eine ausreichende Dichte hat, um die Häute, die Leder oder die Folienmaterialien mit der (den) aktiven Substanz(en) zu imprägnieren, und
    b) die Häute, die Leder oder die Folienmaterilien auf den atmosphärischen Druck zurückzuführen, um das dichte Fluid gasförmig zu eliminieren.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man in Schritt a) das dichte, die aktive(n) Substanz(en) enthaltende Fluid mit dem Druck Pi und mit der Temperatur Ti kontinuierlich zirkulieren läßt in einem die Häute, die Leder oder die Folienmaterialien enthaltenden Behandlungsbehälter, man das dichte Fluid am Ausgang des Behandlungsbehälters behandelt, um seinen Gehalt an aktiver Substanz (aktiven Substanzen) wieder auf den gewünschten Wert einzustellen und man das so behandelte dichte Fluid in den Behandlungsbehälter zurückleitet.
  5. Verfahren nach einem der Ansprüche 3 und 4, dadurch gekennzeichnet, daß es außerdem einen zusätzlichen Reinigungsschritt der Leder, der Häute oder der Folienmaterialien mit Hilfe eines reinen dichten Fluids umfaßt, ausgeführt vor der Durchführung des Schritts a) und/oder vor der Durchführung des Schritts b).
  6. Verfahren nach einem der Ansprüche 2 und 4, dadurch gekennzeichnet, daß man in Schritt b) die Zirkulation des dichten Druckfluids unterbricht und man den Behälter auf den atmosphärischen Druck zurückführt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das dichte Fluid ausgewählt wird unter Kohlendioxid, Schwefelhexafluorid, Stickstoffoxid, Ammoniak und den leichten Alkanen.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das dichte Fluid Kohlendioxid ist.
  9. Verfahren nach einem der Ansprüche 7 und 8, dadurch gekennzeichnet, daß das dichte Fluid im superkritischen Zustand ist.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das dichte Fluid außerdem ein Additiv enthält, um die Lösungs- oder Wasserentziehungsfähigkeit des dichten Fluids zu modifizieren oder um die Auflösung oder den Transport der aktiven Substanz(en) in dem dichten Fluid zu erleichtern.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß das Additiv durch Wasser oder einen Alkohol gebildet wird.
  12. Verfahren nach einem der Ansprüche 3 bis 11, dadurch gekennzeichnet, daß die aktive Substanz ausgewählt wird unter den Gerbwirkstoffen, den Festigungs- bzw. Versteifungswirkstoffen, den Färbwirkstoffen, den Wasserabstoßungswirkstoffen und den Vorläufern dieser Wirkstoffe.
  13. Verfahren nach einem der Ansprüche 3 bis 12, dadurch gekennzeichnet, daß die aktive Substanz mit den zu behandelnden Produkten reagiert.
  14. Verfahren nach einem der Ansprüche 3 bis 12, dadurch gekennzeichnet, daß die aktive Substanz so beschaffen ist, daß sie durch eine geeignete Behandlung umgewandelt werden kann in eine Form, die durch die zu behandelnden Produkte zurückgehalten wird.
  15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Behandlung eine chemische, eine physikalisch-chemische oder photochemische, eine Bestrahlungsbehandlung oder eine Wärmebehandlung ist.
  16. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß man bei der Kontaktherstellung der zu behandelnden Produkte mit dem dichten Fluid periodisch den Druck des dichten Fluids um ΔP um Pi herum verändert.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die Druckveränderung ΔP 10% von Pi darstellt.
  18. Verfahren nach einem der Ansprüche 1 und 3, dadurch gekennzeichnet, daß der Druck Pi von 6 bis 50MPa geht und die Temperatur Ti von 10 bis 300°C geht.
  19. Verfahren nach einem der Ansprüche 1, 3 und 18, dadurch gekennzeichnet, daß der Druck Pi und die Temperatur Ti gewählt werden, um die Fettzersetzungsfähigkeit oder die Auflösungsfähigkeit aktiver Substanz(en) durch das dichte Fluid auf den gewünschten Wert einzustellen.
  20. Verfahren nach einem der Ansprüche 3 und 12, dadurch gekennzeichnet, daß die aktive Substanz ein telechelisches Oligomer ist, das zu der Gruppe der Polyethylen-Glykole und der Polytetraethylen-(oder Methylen-)Glykole gehört.
EP93921975A 1992-10-02 1993-10-01 Verfahren zur druckbehandlung von haeuten, ledern oder blattfoermigen, kollagenhaltigen materialien mit einem dichtem fluid Expired - Lifetime EP0615550B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9211703A FR2696477B1 (fr) 1992-10-02 1992-10-02 Procédé de traitement de peaux, de cuirs ou de matériaux en feuilles contenant du collagène, par un fluide dense sous pression.
FR9211703 1992-10-02
PCT/FR1993/000960 WO1994008054A1 (fr) 1992-10-02 1993-10-01 Procede de traitement de peaux, de cuirs, ou de materiaux en feuilles contenant du collagene, par un fluide dense sous pression

Publications (2)

Publication Number Publication Date
EP0615550A1 EP0615550A1 (de) 1994-09-21
EP0615550B1 true EP0615550B1 (de) 1997-06-11

Family

ID=9434085

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93921975A Expired - Lifetime EP0615550B1 (de) 1992-10-02 1993-10-01 Verfahren zur druckbehandlung von haeuten, ledern oder blattfoermigen, kollagenhaltigen materialien mit einem dichtem fluid

Country Status (9)

Country Link
US (1) US5512058A (de)
EP (1) EP0615550B1 (de)
AT (1) ATE154397T1 (de)
CA (1) CA2124354A1 (de)
DE (1) DE69311532D1 (de)
ES (1) ES2105323T3 (de)
FR (1) FR2696477B1 (de)
GR (1) GR3024556T3 (de)
WO (1) WO1994008054A1 (de)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19507572A1 (de) * 1995-03-03 1996-09-12 Helmut Geihsler Verfahren zur Zurichtung von tierischen Häuten oder Fellen
US6165560A (en) 1997-05-30 2000-12-26 Micell Technologies Surface treatment
CA2291146C (en) 1997-05-30 2008-09-09 Micell Technologies Surface treatment
US6287640B1 (en) 1997-05-30 2001-09-11 Micell Technologies, Inc. Surface treatment of substrates with compounds that bind thereto
US6344243B1 (en) 1997-05-30 2002-02-05 Micell Technologies, Inc. Surface treatment
US6010542A (en) * 1997-08-29 2000-01-04 Micell Technologies, Inc. Method of dyeing substrates in carbon dioxide
NL1008363C2 (nl) * 1998-02-19 1999-08-20 Tno Werkwijze voor het reinigen van vaste materialen en inrichting voor het toepassen van deze werkwijze.
TW426775B (en) * 1998-03-16 2001-03-21 Ind Tech Res Inst Method of fibers scouring
US6048369A (en) * 1998-06-03 2000-04-11 North Carolina State University Method of dyeing hydrophobic textile fibers with colorant materials in supercritical fluid carbon dioxide
US6083565A (en) * 1998-11-06 2000-07-04 North Carolina State University Method for meniscus coating with liquid carbon dioxide
US6497921B1 (en) 1998-11-06 2002-12-24 North Carolina State University Method for meniscus coating with liquid carbon dioxide
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
US6261326B1 (en) 2000-01-13 2001-07-17 North Carolina State University Method for introducing dyes and other chemicals into a textile treatment system
US6676710B2 (en) 2000-10-18 2004-01-13 North Carolina State University Process for treating textile substrates
ITVI20010060A1 (it) * 2001-03-13 2002-09-13 Ge Ma Ta Spa Procedimento di tintura ingrasso e fissaggio delle pelli
WO2003093513A1 (fr) * 2002-05-02 2003-11-13 Masaki Minamiura Materiau du type peau, cuir ou fourrure, pour la fabrication d'un produit en cuir, produit en cuir, procede de preparation du materiau, et procede de fabrication du produit en cuir
WO2004082858A1 (en) * 2003-03-21 2004-09-30 Linde Aktiengesellschaft Parts cleaning
EP1462185A1 (de) * 2003-03-25 2004-09-29 Linde Aktiengesellschaft Waschmitteleinspritzsystem
ES2238926B1 (es) * 2004-02-18 2006-12-16 Universidad De Burgos Desengrasado de piel de cerdo mediante dioxido de carbono comprimido para la posterior obtencion de pasta de colageno de uso alimentario.
DE102006008190A1 (de) * 2006-02-22 2007-08-23 Linde Ag Verfahren zum Fetten von Leder
HK1104900A2 (en) * 2007-10-15 2008-01-25 Hong Kong Productivity Council A super-critical co2 waterless beam dyeing system
DE102009018232B8 (de) 2009-04-21 2011-11-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Gerbung von Tierhäuten
DE102016000243A1 (de) * 2016-01-12 2017-07-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Lederhydrophobierungsverfahren und damit hergestelltes Leder
CN107142757A (zh) * 2017-05-27 2017-09-08 刘振 一种皮革无水染色方法
DK201970267A1 (en) * 2019-04-29 2020-05-13 Ecco Sko A/S APPARATUS FOR DYEING OF LEATHER
DK180537B1 (en) 2019-04-29 2021-06-10 Ecco Sko As Method for dyeing of leather

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4776173A (en) * 1985-12-20 1988-10-11 Angio-Medical Corporation Method for extracting a substance from animal derived material
US5169687A (en) * 1988-09-16 1992-12-08 University Of South Florida Supercritical fluid-aided treatment of porous materials
DE4004111C2 (de) * 1989-02-15 1999-08-19 Deutsches Textilforschzentrum Verfahren zur Vorbehandlung von textilen Flächengebilden oder Garnen
DE3904514C2 (de) * 1989-02-15 1999-03-11 Oeffentliche Pruefstelle Und T Verfahren zum Reinigen bzw. Waschen von Bekleidungsteilen o. dgl.

Also Published As

Publication number Publication date
FR2696477B1 (fr) 1994-11-18
FR2696477A1 (fr) 1994-04-08
CA2124354A1 (fr) 1994-04-14
ATE154397T1 (de) 1997-06-15
GR3024556T3 (en) 1997-12-31
EP0615550A1 (de) 1994-09-21
ES2105323T3 (es) 1997-10-16
DE69311532D1 (de) 1997-07-17
US5512058A (en) 1996-04-30
WO1994008054A1 (fr) 1994-04-14

Similar Documents

Publication Publication Date Title
EP0615550B1 (de) Verfahren zur druckbehandlung von haeuten, ledern oder blattfoermigen, kollagenhaltigen materialien mit einem dichtem fluid
Hu et al. Application of supercritical carbon dioxide for leather processing
US5900027A (en) Process for preparing animal hides or pelts
FR2543974A1 (fr) Procede pour le degraissage au mouille de peaux par attaque enzymatique
EP0422954B1 (de) Verwendung von Fluorchemikalien bei der Lederherstellung
FR2501717A1 (fr) Procede de protection de l'environnement pour le chaulage de peaux brutes
WO2001031067A1 (fr) Procede de tannage de peaux ou de materiaux contenant du collagene, avec un fluide dense sous pression
KR100763118B1 (ko) 동물 가죽의 처리 방법
US3770372A (en) Process for lubricating leather
US5505864A (en) Tanning agent containing a dialdehyde
EP0578736B1 (de) Verfahren und anlage zur behandlung von papierprodukten mit flüssigkeiten grosser dichte
EP0563139B1 (de) Verfahren zur behandlung von häuten oder leder durch einsatz von methansulfonationen.
KR101599092B1 (ko) 하이드 보존방법
US3292271A (en) Dehydration and preservation of animal hides and skins
Saran et al. Biotechnology of leather: an alternative to conventional leather processing
RU2401865C2 (ru) Способ жирования кож
US20070294835A1 (en) Process and Compositions for Wet Degreasing of Pelts, Skins, Hides, Leather Intermediate Products and Non-Finished Leather
EP0408097B1 (de) Gerbungsverfahren von Pelzen
EP0281486A1 (de) Biologisch stabilisierte, ungegerbte Häute und Verfahren zu deren Herstellung
WO2024062184A1 (fr) Procédé de tannage de peaux, méthode de préparation de cuir et procédé de détannage
FR2770171A1 (fr) Procede et installation de traitement d'un materiau poreux par un produit d'impregnation
FR2795082A1 (fr) Procede d'impregnation d'un latex par un additif, latex obtenu et son application en optique
CN115449568B (zh) 一种皮革浸水剂及其制备方法和应用
EP0632135A1 (de) Verfahren und Mittel zum Schutz von ungegerbten Häuten
FR2461756A1 (fr) Procede de tannage des peaux avec des sels de chrome trivalents dans des cuves tournantes, sans bain residuaire pour des motifs d'ordre ecologique

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: 19940506

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT DE ES FR GB GR IT PT

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19960823

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT DE ES FR GB GR IT PT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970611

Ref country code: AT

Effective date: 19970611

REF Corresponds to:

Ref document number: 154397

Country of ref document: AT

Date of ref document: 19970615

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69311532

Country of ref document: DE

Date of ref document: 19970717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970912

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2105323

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19970903

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3024556

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19970611

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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20010928

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030506

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20100921

Year of fee payment: 18

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20120402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120402

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20121205

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20121023

Year of fee payment: 20

Ref country code: ES

Payment date: 20121022

Year of fee payment: 20

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20131002