EP1131483B1 - Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs - Google Patents

Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs Download PDF

Info

Publication number
EP1131483B1
EP1131483B1 EP99953767A EP99953767A EP1131483B1 EP 1131483 B1 EP1131483 B1 EP 1131483B1 EP 99953767 A EP99953767 A EP 99953767A EP 99953767 A EP99953767 A EP 99953767A EP 1131483 B1 EP1131483 B1 EP 1131483B1
Authority
EP
European Patent Office
Prior art keywords
pulp
paper
hydroxylamine
tert
acid
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
EP99953767A
Other languages
German (de)
English (en)
Other versions
EP1131483A1 (fr
Inventor
Raymond Seltzer
David Devore
Glen Thomas Cunkle
Cyril Heitner
John Alois Schmidt
Peter Francis Mcgarry
Jean-Pierre Wolf
Randall Bruce Nelson
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.)
BASF Schweiz AG
Ciba SC Holding AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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
Priority claimed from US09/234,253 external-priority patent/US20020088574A1/en
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of EP1131483A1 publication Critical patent/EP1131483A1/fr
Application granted granted Critical
Publication of EP1131483B1 publication Critical patent/EP1131483B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/143—Agents preventing ageing of paper, e.g. radiation absorbing substances
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds

Definitions

  • the instant invention pertains to a method for preventing the loss of brightness and for enhancing resistance to yellowing in pulp or paper, particularly pulp or paper which still contains lignin, by the addition of N,N-dialkylhydroxylamines, an ester, amide or thio substituted N,N-dialkylhydroxylamine or N,N-dibenzylhydroxylamine, or their salts and other coadditives.
  • High-yield and ultra-high yield wood pulps undergo rapid light-induced discoloration, particularly when they are exposed to near ultraviolet light (wave lengths 300-400 nm) in indoor fluorescent light and daylight. This characteristic restricts their use to short-life, low-value paper products.
  • High-yield and ultra-high yield wood pulps can be bleached to a high level of whiteness. If this whiteness could be stabilized against discoloration, these bleached high-yield pulps could displace significant amounts of more expensive fully-bleached, low-yield chemical pulps.
  • Phenoxy radicals are the key intermediates in the reaction mechanism.
  • Several light-induced reactions have been proposed to account for their formation such as cleavage of the aryl ether bond of phenacyl aryl ether groups, or breakdown of ketyl radicals formed from saturated aryl-glycerol ⁇ -aryl ether structures in lignin.
  • the phenoxy radicals are oxidized by other oxygen-centered radicals (alkoxy and perhydroxy) to form yellow chromophores.
  • thermomechanical (TMP) and chemithermomechical (CTMP) pulps summarizes the state of the art in the thermal and light-induced yellowing of lignin-containing pulps such as thermomechanical (TMP) and chemithermomechical (CTMP) pulps, showing the seriousness of these undesirable effects discusses generally the then current prior art methods used to attack this problem.
  • TMP thermomechanical
  • CMP chemithermomechical
  • WO 99/05108 describes a potential solution where the use of selected hindered amine nitroxides, hindered amine hydroxylamines or their salts in combination with selected UV absorbers and metal chelating agents is seen to prevent loss of brightness and to enhance resistance to yellowing in pulp or paper still containing lignin.
  • Canadian Patent Application No. 2,164,394 and WO 97/36041 teach a multicomponent system for modifying, degrading or bleaching lignin-containing materials.
  • This system includes an oxidation catalyst as an essential component.
  • the catalysts are selected enzymes such as oxidoreductases of classes 1.1.1 to 1.97.
  • the system also includes a number of mediators which inter alia include lower N,N-dialkylhydroxylamines and N,N-dibenzylhydroxylamine.
  • the instant invention describes another approach to this important problem where the use of N,N-dialkylhydroxylamine, an ester, amide or thio substituted N,N-dialkylhydroxyl-amine or N,N-dibenzylhydroxylamine or their salts in combination with selected coadditives also prevents the loss of brightness and enhances resistance to yellowing in pulp or paper, especially pulp or paper still containing lignin.
  • the ester, amide or thio substituted N,N-dialkylhydroxylamines are described in United States Patent Nos. 4,612,393; 4,720,517 and 5,019,285.
  • N,N-dialkylhydroxylamines, derivatives thereof or N,N-dibenzylhydroxylamine to pulp or paper either alone or in combinations with UV absorbers, metal chelating agents, fluorescent whitening agents and/or stabilizing polymers effectively achieves a distinctly improved light and thermal stability.
  • Addition to a kraft pulp or paper, which may still contain traces of lignin leads to a distinct improvement of the light and thermal stability.
  • N,N-dialkylhydroxylamines, derivatives thereof or N,N-dibenzylhydroxylamine to high-yield pulp or paper which still contain lignin either alone or in combinations with UV absorbers, metal chelating agents, fluorescent whitening agents and/or stabilizing polymers effectively achieves light and thermal stability which is similar to that found in papers made from kraft pulps.
  • Hydroxylamines are known to be efficient free radical traps and may limit the production of o-quinones; UV absorbers limit photochemistry in the underlying substrate to which they are applied, and ultimately reduce the production of free radicals. UV absorbers and hydroxylamines are each effective at stemming some of the free radical chemistry leading to paper yellowing when used singly. However, when they are used together, hydroxylamines and UV absorbers can act synergistically to effectively stop photochemical yellowing of lignin containing papers. The hydroxylamines show enhanced inhibiting activity when combined with a metal chelating agent such diethylenetriaminepentaacetic acid or citric acid, or polymeric inhibitors such as polyethylene glycol.
  • a metal chelating agent such diethylenetriaminepentaacetic acid or citric acid
  • polymeric inhibitors such as polyethylene glycol.
  • composition having enhanced resistance to yellowing which comprises
  • X is phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate.
  • acrylate polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic acid, an alkylsulfonate or an arylsulfonate.
  • the hydroxylamine is N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxylamine, N,N-bis(3-hydroxypropyl)hydroxylamine, N,N-dioctadecylhydroxylamine, the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine, N,N-dibenzylhydroxylamine, N,N-bis(2-carboxyethyl)hydroxylamine or N,N-bis(benzylthiomethyl)hydroxylamine.
  • the hydroxylamine is N,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxylamine, N,N-bis(3-hydroxypropyl)hydroxylamine or N,N-dibenzylhydroxylamine; most especially N,N-diethylhydroxylamine or its citric acid salt.
  • salts of these hydroxylamines are also beneficial in producing the increase in brightness and the resistance to yellowing in pulp or paper, especially when still containing lignin.
  • the effective stabilizing amounts of the hydroxylamine is 0.001 to 5% by weight based on the pulp or paper.
  • the effective stabilizing amount is 0.005 to 4% by weight; preferably 0.01 to 4% by weight.
  • the effective stabilizing amount of the coadditives is also 0.001 to 5% by weight based on the pulp or paper; preferably 0.005 to 3% by weight; most preferably 0.01 to 2% by weight.
  • the instant compounds may additionally include an effective stabilizing amount of at least one stabilizer selected from the group consisting of the UV absorbers, the polymeric inhibitors, the sulfur containing inhibitors, the phosphorus containing compounds, the nitrones, the benzofuran-2-ones, fluorescent whitening agents, hindered amine hydroxylamines and salts thereof, hindered amine nitroxides and salts thereof, hindered amines and salts thereof and metal chelating agents.
  • at least one stabilizer selected from the group consisting of the UV absorbers, the polymeric inhibitors, the sulfur containing inhibitors, the phosphorus containing compounds, the nitrones, the benzofuran-2-ones, fluorescent whitening agents, hindered amine hydroxylamines and salts thereof, hindered amine nitroxides and salts thereof, hindered amines and salts thereof and metal chelating agents.
  • compositions which also include a UV absorber are especially preferred.
  • the UV absorber is selected from group consisting of the benzotriazoles, the s-triazines, the benzophenones, the ⁇ -cyanoacrylates, the oxanilides, the benzoxazinones, the benzoates and the ⁇ -alkyl cinnamates.
  • the UV absorber is a benzotriazole, an s-triazine or a benzophenone, most especially a benzotriazole UV absorber or benzophenone UV absorber.
  • Typical and useful UV absorbers are, for example, 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-acumylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole; 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonic acid, sodium salt; 3-tert-butyl-4-hydroxy-5-(2H-benzotria
  • compositions which additionally contain a polymeric inhibitor; preferably poly(ethylene glycol), poly(propylene glycol), poly(butylene glycol) or poly(vinyl pyrrolidone).
  • a polymeric inhibitor preferably poly(ethylene glycol), poly(propylene glycol), poly(butylene glycol) or poly(vinyl pyrrolidone).
  • compositions are those wherein the additional stabilizer is a sulfur containing inhibitor; preferably polyethylene glycol dithiolacetate, polypropylene glycol dithiolacetate, polybutylene glycol dithioacetate, 1-thioglycerol, 2-mercaptoethyl ether, 2,2'thiodiethanol, 2,2'-dithiodiethanol, 2,2'oxydiethanethiol, ethylene glycol bisthioglycolate, 3-mercapto-1,2-propanediol, 2-(2-methoxyethoxy)-ethanethiol, glycol dimercaptoacetate, 3,3'-dithiopropionic acid, polyethylene glycol dithiol, polypropylene glycol dithiol, polybutylene glycol dithiol or ethylene glycol bis(mercaptoacetate).
  • the additional stabilizer is a sulfur containing inhibitor
  • compositions are those wherein the additional stabilizer is a phosphorus containing compound; preferably tris(2,4-di-tert-butylphenyl) phosphite, 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, sodium hydroxymethyl phosphinate, tetrakis(2,4-di-butylphenyl) 4,4'-biphenylenediphosphonite, tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, 2,2'-ethylidenebis
  • compositions are those wherein the additional stabilizer is a benzofuran-2-one; preferably 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one.
  • compositions wherein the additional stabilizer is a metal chelating agent; preferably citric acid, keto acids, gluconates, heptagluconates, phosphates, phosphonates and aminocarboxylic acid chelates, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethlenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA) and diethylenetriaminepentamethylenephosphonic acid (DTPMPA).
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HEDTA hydroxyethylethlenediaminetriacetic acid
  • NTA nitrilotriacetic acid
  • DTPMPA diethylenetriaminepentamethylenephosphonic acid
  • compositions contain a mixture of additional stabilizers such as a mixture of a UV absorber and polymeric inhibitor; or a mixture of a UV absorber and a sulfur containing compound; or a mixture of a UV absorber and a phosphorus containing compound; or a mixture of a UV absorber and a metal chelating agent; or a mixture of a polymeric inhibitor and a sulfur containing compound; or a mixture of a polymeric inhibitor and a phosphorus containing compound; or a mixture of a sulfur containing compound and a phosphorus containing compound; or a mixture of a UV absorber, a polymeric inhibitor and a sulfur containing compound; or a mixture of a UV absorber, a polymeric inhibitor and a phosphorus containing compound; or a mixture of a UV absorber, a polymeric inhibitor, a sulfur containing compound; or a mixture of a UV absorber, a polymeric inhibitor and a phosphorus containing compound; or a mixture of a UV absorber,
  • compositions are those wherein the additional stabilizer is a mixture of a hindered amine hydroxylamine or hindered amine hydroxylamine salt with at least one other stabilizer selected from the group consisting of the UV absorbers, the polymeric inhibitors, the sulfur containing inhibitors, the phosphorus containing compounds, fluorescent whitening agents (optical brighteners), metal chelating agents and hindered amine nitroxides and salts thereof.
  • the additional stabilizer is a mixture of a hindered amine hydroxylamine or hindered amine hydroxylamine salt with at least one other stabilizer selected from the group consisting of the UV absorbers, the polymeric inhibitors, the sulfur containing inhibitors, the phosphorus containing compounds, fluorescent whitening agents (optical brighteners), metal chelating agents and hindered amine nitroxides and salts thereof.
  • compositions wherein the additional stabilizer is a mixture of a UV absorber, a polymeric inhibitor and a sulfur containing compound; or a UV absorber, a polymeric inhibitor and a phosphorus containing compound; or a UV absorber, a polymeric inhibitor and a metal chelating agent; or a UV absorber, a polymeric inhibitor, a sulfur containing compound and a phosphorus containing compound; or a UV absorber and a hindered amine nitroxide; or a UV absorber and a hindered amine hydroxylamine; or a UV absorber and a hindered amine hydroxylamine salt.
  • (Sterically) hindered amine nitroxides, hydroxylamines or hydroxylamine salts are mainly the compounds disclosed in WO 99/05108 (see formulae A to EE and A* to EE* therein, especially compounds (a) to (mm)).
  • compositions wherein the additional stabilizer is a mixture of a hindered amine hydroxylamine with at least one optical brightener such as 2,2'-[(1,1'-diphenyl)-4,4'-diyl-1,2-ethenediyl]bis-benzenesulfonic, disodium salt ⁇ or bis[4,4'-(2-stilbenesulfonic acid)], disodium salt ⁇ which is TINOPAL SK (Ciba Specialty Chemicals).
  • optical brightener such as 2,2'-[(1,1'-diphenyl)-4,4'-diyl-1,2-ethenediyl]bis-benzenesulfonic, disodium salt ⁇ or bis[4,4'-(2-stilbenesulfonic acid)], disodium salt ⁇ which is TINOPAL SK (Ciba Specialty Chemicals).
  • compositions are those wherein the compound of formula I, II, III, IA, IIA or IIIA is of low molecular weight or contains hydrophilic moieties or is both of low molecular weight and contains hydrophilic moieties.
  • the instant invention also pertains to a process for preventing the loss of brightness and for enhancing resistance to yellowing of a pulp or paper, particularly a chemimechanical or thermomechanical pulp or paper which still contain lignin, or a chemical pulp or paper or kraft pulp or paper which still contains traces of lignin, which comprises treating said pulp or paper with an effective stabilizing amount of a compound of formula I, II or III, or formula IA, IIA or IIIA as described above.
  • the instant inhibitor additive system can be added to pulp or paper at a number of places during the manufacturing or processing operations. These include
  • the precise location where the stabilizer additives should be added will depend on the specific equipment involved, the exact process conditions being used and the like. In some cases, the additives may be added at one or more locations for most effectiveness.
  • stabilizer or other coadditives are not themselves “water-soluble", they may be dispersed or emulsified by standard methods prior to application. Alternatively, the stabilizer and/or coadditives may be formulated into a paper sizing or paper coating formulation.
  • All additives are applied by syringe-injecting the appropriate weight % of additive combination in either an aqueous solution when the additive is water soluble, or a solution in 1:1 ethanol/dioxane, onto bleached thermomechanical pulp (BTMP) or chemical (kraft) pulp brightness squares (4 cm x 4cm). The clamped sheets are allowed to air dry for one day.
  • BTMP bleached thermomechanical pulp
  • chemical pulp brightness squares (4 cm x 4cm
  • the brightness of the handsheets is recorded before and after treatment by light exposure under controled intensity conditions.
  • Accelerated testing is carried out by subjecting the treated sheets to accelerated light induced yellowing in a fan-cooled light box containing eight fluorescent lamps with a spectral maximum output at 5700 ⁇ with a total output approximately 43 times greater than normal office fluorescent lamps.
  • the lamps are about ten inches away from the handsheets being illuminated.
  • Ambient testing is carried out by placing the treated handsheets on a desk under normal cool-white fluorescent office lights at a nominal distance of six feet.
  • ISO brightness is tracked as a function of photolysis time and converted to post color number (PC number) in the usual manner.
  • untreated BTMP handsheets When, using the ambient test conditions, untreated BTMP handsheets are compared to Kraft handsheets after 60 days, the BTMP handsheets have a PC number which is about 10 while the Kraft paper has a PC number which is about 0.39. The Kraft handsheets are clearly less yellow than untreated BTMP handsheets after exposure to ambient light.
  • the incident light flux for the accelerated yellowing experiments (Examples 1-10) is 43 times greater than normal office fluorescent lamps as measured by the A. W. Speery SLM-110 digital light power meter.
  • the brightness of the handsheets is tracked and compared to that of untreated sheets exposed in the same manner.
  • the treated sheets exhibit significant resistance to yellowing as is seen below.
  • Compound A is N,N-diethylhydroxylamine.
  • Compound B is N,N-dibenzylhydroxylamine.
  • Compound C is N,N-dioctadecylhydroxylamine.
  • Compound D is the N,N-dialkylhydroxylamine product made by the direct oxidation of N,N-di(hydrogenated tallow)amine.
  • Compound E is tris(N,N-diethylhydroxylammonium) citrate.
  • PEO is poly(ethylene glycol) of molecular weight 300.
  • TINUVIN®328 (Ciba) is 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.
  • TINOPAL® SK (Ciba) is 2,2'-[(1,1'-diphenyl)-4,4'-diyl-1,2-ethenediyl]bis-benzenesulfonic, disodium salt ⁇ or bis[4,4'-(2-stilbenesulfonic acid)], disodium salt ⁇ .
  • CIBAFAST® W (Ciba) is 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-sec-butylbenzenesulfonic acid, sodium salt.
  • Compound F is N,N-bis(2-carboxyethyl)hydroxylamine.
  • Compound G is N,N-bis(benzylthiomethyl)hydroxylamine.
  • a BTMP sheet is treated with 1.0% by weight of N,N-diethylhydroxylamine (Compound A) and exposed to accelerated aging as described above.
  • the treated sheet in exhibits a substantial inhibition of yellowing compared to the untreated control sheet as seen by inspection of the PC numbers given in the table below. Lower PC numbers indicate less color.
  • Time hours Compound A PC number Control PC number 0 0 0 23.6 2.28 5.14 29.4 2.86 6.07 48.7 5.00 9.01 97.8 10.40 15.75 120.3 12.95 18.54 144.0 15.77 21.48 172.2 19.10 24.95
  • a BTMP sheet is treated with 0.3% by weight of Compound B and 2.0% by weight of poly(ethylene glycol), molecular weight 300 (PEO). Again, the treated sheet exhibits an excellent resistance to yellowing as compared to the untreated control sheet.
  • PEO poly(ethylene glycol), molecular weight 300
  • a BTMP sheet is treated with 0.3% by weight of Compound C and 1.0% by weight of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN® 328, Ciba).
  • the treated sheet shows surprisingly excellent resistance to yellowing especially in contrast to the untreated control sheet.
  • a BTMP sheet is treated with 0.6% by weight of Compound D, 2.0% by weight of poly(ethylene glycol), molecular weight 300 (PEO), and 1.0% by weight of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN® 328, Ciba).
  • the treated sheet shows extraordinary resistance to yellowing especially in contrast to the untreated control sheet.
  • Example 5 Accelerated Yellowing with High Intensity Lamps
  • a BTMP sheet is treated with 0.3% by weight of Compound A and 1.0% by weight of TINOPAL® SK. Again, the treated sheet exhibits an excellent resistance to yellowing as compared to the untreated control sheet.
  • a BTMP sheet is treated with 0.3% by weight of Compound B and 1.0% by weight of CIBAFAST® W.
  • the treated sheet shows surprisingly excellent resistance to yellowing especially in contrast to the untreated control sheet.
  • a BTMP sheet is treated with 0.33% and with 0.66% by weight of N,N-diethylhydroxylamine (Compound A) and 0.5% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet as seen by inspection of the PC numbers given in the table below. Lower PC numbers indicate less color.
  • a BTMP sheet is treated with 0.33% and with 0.66% by weight of tris(N,N-diethylhydroxylammonium) citrate (Compound E) and 0.5% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet as seen by inspection of the PC numbers given in the table below. Lower PC numbers indicate less color.
  • a BTMP sheet is treated with 1.0% by weight of N,N-bis(2-carboxyethyl)hydroxylamine (Compound F) and 1.0% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • a BTMP sheet is treated with 1.0% by weight of N,N-bis(benzylthiomethyl)hydroxylamine (Compound G) and 1.0% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • the following examples 11-20 describe accelerated yellowing tests with high intensity lamps conducted on chemical (Kraft) pulp:
  • a kraft sheet is treated with 1.0% by weight of N,N-diethylhydroxylamine (Compound A) and exposed to accelerated aging as described above.
  • the treated sheet in exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • a kraft sheet is treated with 0.3% by weight of Compound B and 2.0% by weight of poly(ethylene glycol), molecular weight 300 (PEO). Again, the treated sheet exhibits an excellent resistance to yellowing as compared to the untreated control sheet.
  • a kraft sheet is treated with 0.3% by weight of Compound C and 1.0% by weight of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN® 328, Ciba).
  • the treated sheet shows surprisingly excellent resistance to yellowing especially in contrast to the untreated control sheet.
  • a kraft sheet is treated with 0.6% by weight of Compound D, 2.0% by weight of poly(ethylene glycol), molecular weight 300 (PEO), and 1.0% by weight of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN® 328, Ciba).
  • the treated sheet shows extraordinary resistance to yellowing especially in contrast to the untreated control sheet.
  • a kraft sheet is treated with 0.3% by weight of Compound A and 1.0% by weight of TINOPAL® SK. Again, the treated sheet exhibits an excellent resistance to yellowing as compared to the untreated control sheet.
  • a kraft sheet is treated with 0.3% by weight of Compound B and 1.0% by weight of CIBAFAST® W.
  • the treated sheet shows surprisingly excellent resistance to yellowing especially in contrast to the untreated control sheet.
  • a kraft sheet is treated with 0.33% and with 0.66% by weight of N,N-diethylhydroxylamine (Compound A) and 0.5% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • a kraft sheet is treated with 0.33% and with 0.66% by weight of tris(N,N-diethylhydroxylammonium) citrate (Compound E) and 0.5% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • a kraft sheet is treated with 1.0% by weight of N,N-bis(2-carboxyethyl)hydroxylamine (Compound F) and 1.0% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.
  • a kraft sheet is treated with 1.0% by weight of N,N-bis(benzylthiomethyl)hydroxylamine (Compound G) and 1.0% by weight of CIBAFAST® W and then exposed to accelerated aging as described above.
  • the treated sheet exhibits a substantial inhibition of yellowing compared to the untreated control sheet.

Claims (12)

  1. Composition ayant une perte réduite de brillance et une résistance améliorée au jaunissement qui comprend :
    (a) une pâte à papier ou un papier ; et
    (b) une quantité stabilisante efficace d'une N,N-dialkylhydroxylamine, un ester, une N,N-dialkylhydroxylamine ou une N,N-dibenzylhydroxylamine substituée par un groupe amide ou thio de formule I, II ou III : R1R2N-OH (T1SCH2) (T2SCH2)N-OH (E1COCH2CH2)(E2COCH2CH2)N-OH
       où
       R1 et R2 représentent, indépendamment l'un de l'autre, un groupe alkyle de 1 à 18 atomes de carbone, un groupe alkyle ayant 1 à 18 atomes de carbone substitués par un groupe hydroxyle ; ou un groupe benzyle ;
       T1 et T2 représentent, indépendamment l'un de l'autre, un groupe alkyle ayant 1 à 4 atomes de carbone, un groupe phényle, 3,5-di-tert-butyl-4-hydroxyphényle, benzyle ou -CH2COOH ;
       E1 et E2 représentent, indépendamment l'un de l'autre, - OE3, -NHE3 ou -NE3E4, où E3 et E4 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle ayant 1 à 4 atomes de carbone ou ledit groupe alkyle substitué par un groupe hydroxyle ; ou d'un sel d'acide de formule IA, IIA ou IIIA : (R1R2NH-OH)h + (X-)j [(T-1SCH2) (T2SCH2)NH-OH]h + (X-)j [(E1COCH2CH2) (E2COCH2CH2)NH-OH]h + (X-)j    où
       R1, R2, T1, T2, E1 et E2 sont tels que définis ci-dessus,
       X est un anion inorganique ou organique, et la charge totale des cations h est égale à la charge totale des anions j,
       à condition que la composition ne contienne aucune enzyme ajoutée.
  2. Composition selon la revendication 1, dans laquelle le composant (a) est une pâte à papier ou un papier qui contient encore de la lignine.
  3. Composition selon la revendication 1, dans laquelle le composant (a) est une pâte à papier ou un papier chimique, thermomécanique ou au sulfate.
  4. Composition selon la revendication 1, où, dans la formule IA, IIA ou IIIA, X est le phosphate, le phosphonate, le carbonate, le bicarbonate, le nitrate, le chlorure, le bromure, le bisulfite, le sulfite, le bisulfate, le sulfate, le borate, le formiate, l'acétate, le benzoate, le citrate, l'oxalate, le tartrate, l'acrylate, le polyacrylate, le fumarate, le maléate, l'itaconate, le glycolate, le gluconate, le malate, le mandélate, le tiglate, l'ascorbate, le polyméthacrylate, un carboxylate d'acide nitrilotriacétique, d'acide hydroxy-éthyléthylène-diaminetriacétique, d'acide éthylènediamine-tétraacétique ou d'acide diéthylènetriaminepentaacétique, d'un acide diéthylènediaminetétraacétique ou d'acide diéthylènetriaminepentaacétique, un alkylsulfonate ou un arylsulfonate.
  5. Composition selon la revendication 1, dans laquelle le composant b est la N,N-diméthylydroxylamine, la N,N-diéthylhydroxylamine, la N,N-bis(2-hydroxypropyl)-hydroxylamine, la N,N-bis(3-hydroxypropyl)hydroxylamine, la N,N-dioctadécylhydroxylamine, le produit de la N,N-dialkylhydroxylamine étant fait par oxydation directe de N,N-di(suif hydrogéné)amine, la N,N-dibenzylhydroxylamine, la N,N-bis(2-carboxyéthylhydroxylamine ou la N,N-bis-(benzylthiométhyl)hydroxylamine, ou un sel d'acide correspondant.
  6. Composition selon la revendication 1, qui comprend de plus une quantité stabilisante efficace d'au moins un co-additif choisi dans le groupe constitué par les stabilisants anti-UV, les inhibiteurs polymères, les inhibiteurs contenant du soufre, les composés contenant du phosphore, les nitrones, les benzofuran-2-ones, les agents blanchissants fluorescents, les hydroxylamines d'amine encombrée et leurs sels, les nitroxydes d'amine encombrée et leurs sels, les aminés encombrées et leurs sels et les agents chélatants métalliques.
  7. Composition selon la revendication 6, dans laquelle le stabilisant supplémentaire est
       un stabilisant anti-UV choisi dans le groupe constitué par les benzotriazoles, les s-triazines, les benzophénones, les α-cyanoacrylates, les oxanilides, les benzoxazinones, les benzoates et les α-alkylcinnamates ;
       un inhibiteur polymère choisi parmi le poly-(éthylèneglycol), le poly(propylèneglycol), le poly-(butylèneglycol) ou la poly(vinylpyrrolidone) ;
       un inhibiteur contenant du soufre choisi dans le groupe constitué par le dithiolacétate de poly-(éthylèneglycol), le dithiolacétate de poly(propylène-glycol), le dithiolacétate de poly(butylèneglycol), le 1-thioglycérol, l'éther 2-mercaptoéthylique, le 2,2'-thio-diéthanol, le 2,2'-dithiodiéthanol, le 2,2'-oxydiéthane-thiol, le bisthioglycolate d'éthylèneglycol, le 3-mercapto-1,2-propanediol, le 2-(2-méthoxyéthoxy)-éthane-thiol, le dimercaptoacétate de glycol, l'acide 3,3'-dithiopropionique, le poly(éthylèneglycol dithiol), le poly(propylèneglycol dithiol), le poly(butylèneglycol dithiol) et le bis(mercaptoacétate) d'éthylèneglycol ; et/ou
       un composé contenant du phosphore choisi dans le groupe constitué par le tris(2,4-di-tert-butylphényl)-phosphite, le 2,2',2"-nitrilo[triéthyl-tris(3,3',5,5'-tétra-tert-butyl-1,1'-biphényl-2,2'-diyl)phosphite], le tris(2,4-di-tert-butyl-6-éthylphényl)phosphite, l'hydroxy-méthylphosphinate de sodium, le tétrakis(2,4-di-butylphényl)-4,4'-biphénylènediphosphonite, le tris(nonylphényl)phosphite, le bis(2,4-di-tert-butylphényl)pentaérythrityldiphosphite, le 2,2'-éthylidènebis(2,4-di-tert-butylphényl)fluorophosphite et le 2-butyl-2-éthylpropan-1,3-diyl-2,4,6-tri-tert-butylphénylphosphite.
  8. Composition selon la revendication 6, dans laquelle le stabilisant supplémentaire est un mélange contenant deux des composants suivants :
    un stabilisant anti-UV et un inhibiteur polymère ; un stabilisant anti-UV et un composé contenant du soufre ; un stabilisant anti-UV et un composé contenant du phosphore ; un stabilisant anti-UV et un agent chélatant métallique ; un inhibiteur polymère et un composé contenant du soufre ; un inhibiteur polymère et un composé contenant du phosphore ; un composé contenant du soufre et un composé contenant du phosphore ; un stabilisant anti-UV et une amine encombrée.
  9. Composition selon la revendication 1, dans laquelle la quantité stabilisante efficace de l'hydroxylamine ou du sel d'hydroxylamine du composant b va de 0,001 à 5% en poids par rapport à la pâte ou au papier.
  10. Composition selon la revendication 7, dans laquelle la quantité stabilisante efficace d'un co-additif va de 0,001 à 5% en poids par rapport à la pâte ou au papier.
  11. Procédé pour empêcher la perte de brillance et pour améliorer la résistance au jaunissement d'une pâte ou d'un papier qui consiste à :
    traiter ladite pâte ou ledit papier avec une quantité stabilisante efficace d'un composé hydroxylamine de formule I, II ou III ou d'un sel d'hydroxylamine de formule IA, IIA ou IIIA selon la revendication 1.
  12. Utilisation d'un composé hydroxylamine de formule I, II ou III ou d'un sel hydroxylamine de formule IA, IIA ou IIIA selon la revendication 1 pour stabiliser une pâte ou un papier contre une perte de brillance et le jaunissement.
EP99953767A 1998-10-22 1999-10-11 Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs Expired - Lifetime EP1131483B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US17701698A 1998-10-22 1998-10-22
US177016 1998-10-22
US11668899P 1999-01-20 1999-01-20
US116688P 1999-01-20
US234253 1999-01-20
US09/234,253 US20020088574A1 (en) 1998-10-22 1999-01-20 Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
PCT/EP1999/007594 WO2000024963A1 (fr) 1998-10-22 1999-10-11 Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs

Publications (2)

Publication Number Publication Date
EP1131483A1 EP1131483A1 (fr) 2001-09-12
EP1131483B1 true EP1131483B1 (fr) 2003-11-05

Family

ID=27381865

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99953767A Expired - Lifetime EP1131483B1 (fr) 1998-10-22 1999-10-11 Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs

Country Status (10)

Country Link
EP (1) EP1131483B1 (fr)
JP (1) JP2002528657A (fr)
CN (1) CN1324419A (fr)
AT (1) ATE253662T1 (fr)
AU (1) AU754737B2 (fr)
BR (1) BR9914721A (fr)
CA (1) CA2346211A1 (fr)
DE (1) DE69912633T2 (fr)
RU (1) RU2222654C2 (fr)
WO (1) WO2000024963A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8361571B2 (en) 2008-06-20 2013-01-29 International Paper Company Composition and recording sheet with improved optical properties

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7657379B2 (en) 2000-07-05 2010-02-02 Microsoft Corporation Methods and systems for determining the biological function of cell constituents using response profiles
WO2004024810A2 (fr) 2002-09-11 2004-03-25 Ciba, Specialty Chemicals Holding Inc. Stabilisation de matières organiques
WO2004056931A1 (fr) * 2002-12-20 2004-07-08 Ciba Specialty Chemicals Holding Inc. Encre pour imprimante a jet d'encre et materiau d'enregistrement
CN1901876B (zh) * 2003-10-30 2013-04-10 西巴特殊化学制品控股公司 稳定的身体护理品,家用制品,纺织品和织物
WO2005042828A2 (fr) * 2003-11-03 2005-05-12 Ciba Specialty Chemicals Holding Inc. Produits de soins corporels, produits menagers, textiles et tissus stabilises
FI20031904A (fi) * 2003-12-23 2005-06-24 Kemira Oyj Menetelmä lignoselluloosatuotteen muokkaamiseksi
CA2601507C (fr) * 2005-04-08 2013-09-03 Nalco Company Composition amelioree et procedes de production de papier
US8092649B2 (en) * 2005-12-14 2012-01-10 Nalco Company Method of decreasing the rate of photoyellowing with thiocyanic acid
CN101182693B (zh) * 2007-12-12 2010-06-02 中冶纸业银河有限公司 一种稳定纸浆白度的方法
CN104871097B (zh) * 2012-12-13 2018-05-18 Abb 技术有限公司 用于监测和/或诊断工业工厂生产线操作的系统和方法
FI127900B (en) * 2014-05-27 2019-05-15 Upm Kymmene Corp A method for reducing phosphorus load from waste water from a pulp production process
CN105155338A (zh) * 2015-09-10 2015-12-16 上海晶华胶粘新材料股份有限公司 抗uv水性纸张浸渍剂及其制备方法
CN105839431A (zh) * 2016-06-13 2016-08-10 东莞市博科纺织科技有限公司 一种防酚黄剂及其制备方法
CN109440458A (zh) * 2018-10-08 2019-03-08 淮海工学院 一种多功能柔软剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832277A (en) * 1972-02-24 1974-08-27 Fmc Corp Hydroxylamine treated hemicellulose-containing regenerated cellulose product
JPS5926464A (ja) * 1982-07-22 1984-02-10 ユニチカ株式会社 ポリアミド繊維等の包装材
US4612393A (en) * 1985-04-29 1986-09-16 Ciba-Geigy Corporation Bis(substituted thioalkyl)hydroxylamines and stabilized polyolefin compositions
EP0717143A1 (fr) * 1994-12-16 1996-06-19 Lignozym GmbH Système à plusieurs composants pour modifier, dégrader ou blanchir la lignine, des matériaux contenant de la lignine ou des produits similaires de même que leur procédé d'utilisation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8361571B2 (en) 2008-06-20 2013-01-29 International Paper Company Composition and recording sheet with improved optical properties
US8906476B2 (en) 2008-06-20 2014-12-09 International Paper Company Composition and recording sheet with improved optical properties

Also Published As

Publication number Publication date
AU1034600A (en) 2000-05-15
WO2000024963A1 (fr) 2000-05-04
CA2346211A1 (fr) 2000-05-04
ATE253662T1 (de) 2003-11-15
DE69912633T2 (de) 2004-09-23
DE69912633D1 (de) 2003-12-11
EP1131483A1 (fr) 2001-09-12
JP2002528657A (ja) 2002-09-03
AU754737B2 (en) 2002-11-21
BR9914721A (pt) 2001-07-10
CN1324419A (zh) 2001-11-28
RU2222654C2 (ru) 2004-01-27

Similar Documents

Publication Publication Date Title
US6599326B1 (en) Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
EP1131483B1 (fr) Enraiement du jaunissement de pulpe de papier et de papier a l'aide d'hydroxylamines et d'autres co-additifs
US6500303B1 (en) Inhibition of pulp and paper yellowing using nitroxides, hydroxylamines and other coadditives
US20020088574A1 (en) Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
US6447644B1 (en) Inhibition of pulp and paper yellowing using nitroxides, hydroxylamines and other coadditives
EP1212486B1 (fr) Chlorohydrine et composes cationiques presentant une excellente affinite pour la pate ou le papier
US6416627B1 (en) Polymeric stabilizers with high affinity to pulp
US7776182B2 (en) Chlorohydrin and cationic compounds having high affinity for pulp or paper
MXPA01003954A (en) Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
KR20010080292A (ko) 히드록실아민 및 기타의 공첨가제를 이용하여 펄프 및종이의 황화를 방지하는 방법

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: 20010322

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

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: 20031105

Ref country code: LI

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: 20031105

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20031105

Ref country code: FR

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: 20031105

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: 20031105

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: 20031105

Ref country code: CH

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: 20031105

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: 20031105

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: 20031105

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

REF Corresponds to:

Ref document number: 69912633

Country of ref document: DE

Date of ref document: 20031211

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040205

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040216

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
LTIE Lt: invalidation of european patent or patent extension

Effective date: 20031105

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

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

Ref country code: LU

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

Effective date: 20041011

Ref country code: IE

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

Effective date: 20041011

Ref country code: GB

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

Effective date: 20041011

Ref country code: FI

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

Effective date: 20041011

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

Ref country code: SE

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

Effective date: 20041012

26N No opposition filed

Effective date: 20040806

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 NON-PAYMENT OF DUE FEES

Effective date: 20041031

EN Fr: translation not filed
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: 20050503

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20041011

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: PT

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

Effective date: 20040405