EP2272644B1 - Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen - Google Patents
Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen Download PDFInfo
- Publication number
- EP2272644B1 EP2272644B1 EP09008805.5A EP09008805A EP2272644B1 EP 2272644 B1 EP2272644 B1 EP 2272644B1 EP 09008805 A EP09008805 A EP 09008805A EP 2272644 B1 EP2272644 B1 EP 2272644B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wood
- urea
- use according
- thiosulphate
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims description 45
- 150000001299 aldehydes Chemical class 0.000 title description 25
- 238000000034 method Methods 0.000 title description 12
- 150000002894 organic compounds Chemical class 0.000 title description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 80
- 239000002023 wood Substances 0.000 claims description 74
- 239000012855 volatile organic compound Substances 0.000 claims description 35
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 15
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims description 13
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 150000003672 ureas Chemical class 0.000 claims description 9
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 claims description 2
- GMKDNCQTOAHUQG-UHFFFAOYSA-L dilithium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=S GMKDNCQTOAHUQG-UHFFFAOYSA-L 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims description 2
- HMJMQKOTEHYCRN-UHFFFAOYSA-N formaldehyde;phenol;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 HMJMQKOTEHYCRN-UHFFFAOYSA-N 0.000 claims description 2
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- DSKJXGYAJJHDOE-UHFFFAOYSA-N methylideneurea Chemical compound NC(=O)N=C DSKJXGYAJJHDOE-UHFFFAOYSA-N 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 6
- 239000004133 Sodium thiosulphate Substances 0.000 claims 2
- 238000000748 compression moulding Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 2
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 238000007669 thermal treatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 23
- 235000013877 carbamide Nutrition 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 8
- 230000007774 longterm Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 among others Substances 0.000 description 4
- 238000002144 chemical decomposition reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000011093 chipboard Substances 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011094 fiberboard Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012084 conversion product Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012978 lignocellulosic material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229940062135 magnesium thiosulfate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
Definitions
- the present invention relates to the use of an additive in a process for producing wood-based materials from lignocellulose-containing comminution products, wherein a reduction of the emission of volatile organic compounds and aldehydes including formaldehyde from wood, the crushed products and the wood-based material produced is achieved. More particularly, the present invention relates to a use of an additive for reducing the emission of volatile organic compounds and aldehydes, including formaldehyde, wherein wood or the lignocellulose shredded products are treated with thiosulfates, preferably a certain combination of compounds of thiosulfates and ureas, to control the emission of these volatiles prevent organic compounds including aldehydes from the wood or the wood-based material produced.
- the present invention relates to using this additive producible wood materials.
- the present invention provides the use of treating agents for treating wood or lignocellulosic crushing products and wood-based materials made therefrom which are capable of reducing the emission of aldehydes including formaldehyde and volatile organic compounds and their corresponding use.
- Lignocellulosic or lignocellulosic materials such as wood and wood pulp products, and derived timber products, such as wood-based panels, include volatile organic compounds (VOCs) and very volatile organic compounds (VVOCs), such as formaldehyde. Volatile organic compounds are subsumed with all volatile organic compounds whose retention time in the gas chromatogram lies between C6 (hexane) and C16 (hexadecane). Among the very volatile organic compounds, among others, formic acid and formaldehyde are counted.
- aldehydes as used herein includes not only the volatile compounds but also all other aldehydes, especially formaldehyde, unless otherwise specified.
- Volatile organic compounds and very volatile organic compounds occur depending on the nature and condition of the lignocelluloses, such as the type of wood, the storage period, the storage conditions of the wood or the comminution products of lignocellulose, in different chemical compositions and quantities.
- the VOCs are derived essentially from extractives of the lignocelluloses, e.g. of wood or conversion products. Prominent representatives of these are substances such as alpha-pinene, beta-pinene, delta-3-carene. Especially in the wood of the conifers, these components are found again. Conversion products, e.g. during storage and processing of the wood and shredded products, e.g. Pentanal and hexanal.
- softwoods which mainly produce chipboard, medium-density fiberboard (MDF) or OSB boards, contain large quantities of resin and fats which lead to the formation of volatile organic terpene compounds and aldehydes. Some of these substances are also formed by degradation of the main components of the wood, such as lignin, cellulose and hemicellulose. VOCs including aldehydes and formaldehyde may also be formed by the use of certain adhesives for the manufacture of wood-based materials.
- Adhesives currently used in the manufacture of wood-based materials such as OSB boards, medium density fiberboard, etc. include aminoplast adhesives, such as urea-formaldehyde adhesives (UF adhesives), melamine-urea-phenol-formaldehyde adhesives (MUPF adhesives) or melamine-urea-formaldehyde adhesives (MUF adhesives).
- aminoplast adhesives such as urea-formaldehyde adhesives (UF adhesives), melamine-urea-phenol-formaldehyde adhesives (MUPF adhesives) or melamine-urea-formaldehyde adhesives (MUF adhesives).
- Other adhesives typically used in wood-based materials include diisocyanate-based adhesives (PMDI), polyurethane adhesives, phenol-formaldehyde (PF) adhesives, and / or tannin-formaldehyde (TF) adhesives, or mixtures thereof.
- PMDI diisocyanate-based adhesives
- VOCs and the formaldehyde take place both during the production of the wood-based materials as well as after their production or in their application.
- partial chemical degradation of the wood may occur.
- volatile compounds such as aldehydes and acids, then emit during the later manufacturing process or later use of the produced wood materials. They can also have a negative influence on the bond strength and thus adversely affect the properties of the produced wood materials.
- the WO 02/072323 describes methods for reducing the emission of formaldehyde from layered products containing at least two layers, wherein the surface of a plate or a veneer is treated with a solution containing sulfite or bisulfite.
- the examples illustrate that veneer is treated with a sulfite solution to lower formaldehyde emission.
- From the WO 2007/012350 are known processes for the production of wood-based articles with low emission of chemical compounds, namely low formaldehyde emission when using formaldehyde-containing resins.
- the treatment of wood chips or wood fibers with bisulfite is proposed.
- JP -A- 2001164235 Catcher for formaldehyde and process for the treatment of wood panels.
- the wood materials produced by methods of the prior art show an unsatisfactory VOC and aldehyde emission, especially during prolonged use.
- the object is achieved by using an additive according to claim 1, wherein a special composition is added to the wood or the lignocellulosic crushing products or the wood-based materials in order, by reaction with the VOCs and the aldehydes, to modify them so that they are no longer from the wood or emit the crushed products or derived from the wood materials produced from the crushed products.
- the resulting compounds are so high molecular weight that they are no longer volatile and thus no longer contribute in the long term to the VOC emissions or aldehyde emissions including formaldehyde emissions.
- the addition of the additive may take place before or after the comminution and work-up of the comminuted products, e.g. B. after the refiner in fibers done.
- the additives can be impregnated into the wood, the lignocellulosic crushing products can be treated with the additives z. B. be impregnated.
- the application of the additives takes place immediately before the hot pressing or before the dryer.
- the addition of the adhesive can be carried out before or after the application of the additive.
- the individual components of the additive can be applied simultaneously or separately. In other words, the additive can be applied in solution to the lignocellulose-containing comminution products by conventional means. Alternatively, the lignocellulose-containing comminution products can be treated individually with the components.
- the component from the group i) before or after the component from the group ii) are applied separately.
- This application or treatment can be carried out before or after application of the adhesive.
- the adhesive can also be effected between the application of a first component of the additive and the second component of the additive.
- An essential advantage of the present invention is that it is provided in additives which, in a reduction step, reduce aldehydes as well as other volatile organic compounds, in particular those with double bonds, so that the Emission of these VOCs and aldehydes including formaldehyde can also be reduced in the long term and a disruption of the technological process does not occur.
- thiosulfates in particular the general formula MeS 2 O 3 or Me 2 (S 2 O 3 wherein Me represents an alkali, alkaline earth metal or ammonium
- the emissions in particular the long-term emission of VOC and aldehydes including formaldehyde made of wood and wood materials can be reduced.
- the additive thus preferably contains at least one component in each case from the two groups i) and ii).
- Group i) comprises thiosulfates.
- they are thiosulfates of the general formula MeS 2 O 3 or Me 2 (S 2 O 3 ), where Me is an alkali metal, alkaline earth metal, or ammonium.
- Me is an alkali metal, alkaline earth metal, or ammonium.
- Preferred is the thiosulfate of one of the group of sodium thiosulfate, ammonium thiosulfate, lithium thiosulfate, potassium thiosulfate, calcium thiosulfate, magnesium thiosulfate.
- the thiosulfate salt used is sodium thiosulfate or ammonium thiosulfate and most preferably ammonium thiosulfate.
- antioxidant properties can suppress the VOC emission, which are caused for example by oxidation.
- the resulting from the thiosulfate intermediate Sulfite can z. B. with isolated double bonds, such as those contained in, inter alia, terpenes, fats or fatty acids, by reduction or addition with these compounds.
- At least one thiosulfate is added to the comminuted products in the use according to the invention.
- the salts used are preferably ammonium thiosulfate and / or sodium thiosulfate.
- Group ii) comprises urea and urea derivatives, such as monomethylolurea or methyleneurea. Preference is given to using urea.
- Urea also reacts with formaldehyde to form mono- and dimethylolurea. This reaction is very slow and thus also allows a long-term lowering of the formaldehyde levels in the wood materials.
- urea alone is not meaningful because the reaction with formaldehyde is very slow and it is an equilibrium reaction, so that formaldehyde can be released at a later date again.
- a combination of at least one component of group i) and at least one component from group ii) is used according to the invention for the wood or the comminution products or the wood-based materials. Due to the different reaction modes or reaction times of the added components in relation to formaldehyde and VOC, the long-term emission of VOC and formaldehyde can be very effectively changed, thereby optimizing the properties of the wood-based materials. Furthermore, thiosulfate salts of group i) are suitable for stabilizing ureas of group ii) by preventing urea hydrolysis. Thus, a better effectiveness of group ii) can be assumed.
- the at least one thiosulfate salt is added in an amount of from 0.1% by weight to 5% by weight, based on atro-lignocellulose. Particular preference is given to amounts of from 0.2% by weight to 1.5% by weight, for. For example, a mixture of about 57% Solids content with 1% dosed on atro wood.
- the amount of urea is preferably in the range of 0.5% by weight to 5% by weight, based on atorocellulose.
- the described treatment agents can be used to reduce emissions from wood, lignocellulose-containing crushed products or wood-based materials, eg. B. in the production of wood-based materials are used, wherein the addition is carried out according to the method according to the invention advantageously via standard equipment for binder dosing, such as Beleimtrommel, blow-line gluing or dry gluing.
- the addition of the solution to the mat via nozzles directly in front of the hot press is possible.
- the additive is not mixed with the adhesive, but added before or after application of the adhesive crushing products immediately prior to hot pressing. It is not limited only to formaldehyde-containing adhesives, but also extends to all other thermosetting or thermosetting adhesives used in wood-based materials, such as e.g. PMDI.
- the wood can be impregnated directly with the additives according to the invention. This impregnation can take place before the comminution of the wood; An impregnation after production of the wood material is also possible.
- VOC volatile organic compounds
- aldehydes including formaldehyde
- the thiosulfate salt is those derived from sodium and ammonia.
- a further preferred embodiment relates to a composition (treating agent) of the abovementioned type in which at least one thiosulfate salt is used in combination with urea and / or urea derivative.
- the present invention provides wood materials available according to the use of the invention. These wood-based materials are characterized by a reduced emission of volatile organic compounds, in particular the aldehydes including formaldehyde. These are in particular fibreboard, such as HDF or MDF, chipboard or OSB boards.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUE09008805A HUE031829T2 (en) | 2009-07-06 | 2009-07-06 | A method for reducing emissions of aldehydes and volatile organic compounds in wood |
| PL12187385T PL2546039T3 (pl) | 2009-07-06 | 2009-07-06 | Sposób redukcji emisji aldehydów i lotnych związków organicznych z płyt OSB, stosowanie substancji dodatkowych do realizacji tego celu i płyta OSB |
| ES12187385.5T ES2468024T3 (es) | 2009-07-06 | 2009-07-06 | Procedimiento para reducir la emisión de aldehídos y compuestos orgánicos volátiles de placas osb, utilización de aditivos para este fin y placa OSB |
| PT90088055T PT2272644T (pt) | 2009-07-06 | 2009-07-06 | Processo para a redução da emissão de compostos orgânicos voláteis e de compostos aldeídicos a partir de materiais à base de madeira |
| PT121873855T PT2546039E (pt) | 2009-07-06 | 2009-07-06 | Processo para a redução da emissão de compostos orgânicos voláteis e de compostos aldeídicos a partir de painéis osb, uso de aditivos para este propósito bem como painéis osb |
| EP09008805.5A EP2272644B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen |
| EP12187385.5A EP2546039B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus OSB-Platten, Verwendung von Zusatzstoffen zu diesem Zweck und OSB-Platte |
| ES09008805.5T ES2611080T3 (es) | 2009-07-06 | 2009-07-06 | Procedimiento para reducir la emisión de aldehídos y compuestos orgánicos volátiles de materiales a base de madera |
| PL09008805T PL2272644T3 (pl) | 2009-07-06 | 2009-07-06 | Zastosowanie dodatków do zmniejszania emisji aldehydów i lotnych związków organicznych z materiałów drzewnych |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09008805.5A EP2272644B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12187385.5A Division EP2546039B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus OSB-Platten, Verwendung von Zusatzstoffen zu diesem Zweck und OSB-Platte |
| EP12187385.5A Division-Into EP2546039B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus OSB-Platten, Verwendung von Zusatzstoffen zu diesem Zweck und OSB-Platte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2272644A1 EP2272644A1 (de) | 2011-01-12 |
| EP2272644B1 true EP2272644B1 (de) | 2016-10-19 |
Family
ID=41338621
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09008805.5A Active EP2272644B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen |
| EP12187385.5A Active EP2546039B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus OSB-Platten, Verwendung von Zusatzstoffen zu diesem Zweck und OSB-Platte |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12187385.5A Active EP2546039B1 (de) | 2009-07-06 | 2009-07-06 | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus OSB-Platten, Verwendung von Zusatzstoffen zu diesem Zweck und OSB-Platte |
Country Status (5)
| Country | Link |
|---|---|
| EP (2) | EP2272644B1 (pt) |
| ES (2) | ES2468024T3 (pt) |
| HU (1) | HUE031829T2 (pt) |
| PL (2) | PL2272644T3 (pt) |
| PT (2) | PT2272644T (pt) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2111959A2 (de) * | 2008-04-24 | 2009-10-28 | Kronotec Ag | Verfahren zur Herstellung von Holzwerkstoffen und Holzwerkstoffe |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101214074B1 (ko) * | 2012-02-27 | 2012-12-20 | 백철기 | 무공해 갈대 합성 목재 및 그의 제조방법 |
| CN102615690B (zh) * | 2012-04-12 | 2014-03-12 | 文安县天华密度板有限公司 | 氨气熏蒸木纤维生产环保型人造板的方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164235A (ja) * | 1999-09-30 | 2001-06-19 | Kyokutoo International:Kk | ホルムアルデヒド捕捉剤、木質板の処理方法及び木質板 |
| DK1368168T3 (da) | 2001-03-12 | 2009-02-02 | Akzo Nobel Coatings Int Bv | Fremgangsmåde til at reducere emissionen af formaldehyd fra lagdelte produkter |
| WO2006010192A1 (en) * | 2004-07-27 | 2006-02-02 | Orica Australia Pty. Ltd. | System for providing powder coated reconstituted cellulosic substrate |
| PL1907178T3 (pl) | 2005-07-27 | 2017-01-31 | Kronoplus Technical Ag | Sposób wytwarzania wyrobu z tworzyw drzewnych o niewielkiej emisji związków chemicznych |
| DE102007038041A1 (de) | 2007-08-10 | 2009-02-12 | Kronotec Ag | Verfahren zur Vermeidung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen |
-
2009
- 2009-07-06 PT PT90088055T patent/PT2272644T/pt unknown
- 2009-07-06 PL PL09008805T patent/PL2272644T3/pl unknown
- 2009-07-06 PL PL12187385T patent/PL2546039T3/pl unknown
- 2009-07-06 EP EP09008805.5A patent/EP2272644B1/de active Active
- 2009-07-06 ES ES12187385.5T patent/ES2468024T3/es active Active
- 2009-07-06 HU HUE09008805A patent/HUE031829T2/en unknown
- 2009-07-06 EP EP12187385.5A patent/EP2546039B1/de active Active
- 2009-07-06 ES ES09008805.5T patent/ES2611080T3/es active Active
- 2009-07-06 PT PT121873855T patent/PT2546039E/pt unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2111959A2 (de) * | 2008-04-24 | 2009-10-28 | Kronotec Ag | Verfahren zur Herstellung von Holzwerkstoffen und Holzwerkstoffe |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2546039B1 (de) | 2014-03-26 |
| PL2546039T3 (pl) | 2014-08-29 |
| ES2468024T3 (es) | 2014-06-13 |
| EP2546039A3 (de) | 2013-03-20 |
| PL2272644T3 (pl) | 2017-09-29 |
| PT2546039E (pt) | 2014-06-09 |
| EP2272644A1 (de) | 2011-01-12 |
| ES2611080T3 (es) | 2017-05-04 |
| HUE031829T2 (en) | 2017-08-28 |
| PT2272644T (pt) | 2017-01-10 |
| EP2546039A2 (de) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2176354B2 (de) | Verfahren zur verminderung der emission von aldehyden und flüchtigen organischen verbindungen aus holzwerkstoffen | |
| DE102006020612B4 (de) | Verfahren zur Herstellung von Holzwerkstoffen mit verringerter Emission an flüchtigen organischen Verbindungen, damit erhältliche Holzwerkstoffe sowie die Verwendung bestimmter Additive zur Verminderung der Freisetzung von flüchtigen organischen Verbindungen aus Holzwerkstoffen und Holzzerkleinerungsprodukten von Lignocellulosen | |
| EP2111959A2 (de) | Verfahren zur Herstellung von Holzwerkstoffen und Holzwerkstoffe | |
| WO2006039914A1 (de) | Verfahren zur verminderung der abgabe von flüchtigen organischen verbindungen (voc) aus holz und holzzerkleinerungsprodukten und aus daraus hergestellten holzwerkstoffen, insbesondere holzspanplatten | |
| EP2272644B1 (de) | Verfahren zur Verminderung der Emission von Aldehyden und flüchtigen organischen Verbindungen aus Holzwerkstoffen | |
| EP1874513B1 (de) | Verfahren zur herstellung von mitteldichten faserplatten und faserformteilen mit verringerter emission und niedriger dickenquellung | |
| DE102007055415B4 (de) | Verfahren zur Verminderung der Emission von gesättigten und ungesättigten Aldehyden aus Holzwerkstoffen | |
| EP2193899B1 (de) | Verfahren zur Herstellung von Holzwerkstoffen aus Lignocellulose-haltigen Zerkleinerungsprodukten und solche Holzwerkstoffe | |
| EP3268190B1 (de) | Verfahren zur herstellung eines holzspanwerkstoffs und darin verwendete härter für aminoplaste | |
| EP2053075A1 (de) | Verfahren zur Verringerung der Emission von Aldehyden und anderen flüchtigen organischen Verbindungen aus Holzwerkstoffen und Zusammensetzungen hierfür | |
| DE102007054123B4 (de) | Verfahren zur Herstellung von Holzfaserplatten mit verringerter Formaldehydemission, hoher Feuchtebeständigkeit und Hydrolyseresistenz der Verleimung | |
| EP2607032B1 (de) | Verfahren zur Verminderung der Emission von flüchtigen organischen Verbindungen aus Holzwerkstoffen und Holzwerkstoffe | |
| DE102008050428A1 (de) | Verfahren zur Herstellung von mitteldichten Faserplatten (MDF) mit alkalisch härtenden Phenolformaldehydharzen | |
| EP3352957B1 (de) | Verfahren zur herstellung von osb-platten sowie osb-platte | |
| EP1944144B1 (de) | Verfahren zur Herstellung eines cellulosehaltigen Formkörpers | |
| WO2024046878A2 (de) | Verfahren zur herstellung einer mit einem flammenschutzmittel versehenen holzwerkstoffplatte | |
| DE102008023007A1 (de) | Verfahren zur Herstellung von Holzfaserplatten mit verringerter Formaldehydemission, hoher Feuchtebeständigkeit und Hydrolyseresistenz der Verleimung | |
| DE102005062173A1 (de) | Verfahren zur Herstellung von formaldehydarmen Holzspanplatten und Horzfaserplatten mit Tanninformaldehydharzen als Bindemittel |
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: 20100427 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTG | Intention to grant announced |
Effective date: 20160602 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SWISS KRONO TEC AG |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 837933 Country of ref document: AT Kind code of ref document: T Effective date: 20161115 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502009013238 Country of ref document: DE |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: SWISS KRONO TEC AG |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: BRAUNPAT BRAUN EDER AG, CH |
|
| REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR Ref country code: PT Ref legal event code: SC4A Ref document number: 2272644 Country of ref document: PT Date of ref document: 20170110 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20161230 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170119 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2611080 Country of ref document: ES Kind code of ref document: T3 Effective date: 20170504 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170219 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| REG | Reference to a national code |
Ref country code: SK Ref legal event code: T3 Ref document number: E 22822 Country of ref document: SK |
|
| REG | Reference to a national code |
Ref country code: HU Ref legal event code: HC9C Owner name: SWISS KRONO TEC AG, CH Free format text: FORMER OWNER(S): SWISS KRONO TEC AG, CH |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 Ref country code: DE Ref legal event code: R097 Ref document number: 502009013238 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 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: 20161019 |
|
| 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 |
|
| REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E031829 Country of ref document: HU |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170119 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| 26N | No opposition filed |
Effective date: 20170720 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| 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: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170706 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PCAR Free format text: NEW ADDRESS: HOLEESTRASSE 87, 4054 BASEL (CH) |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20180620 Year of fee payment: 19 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CZ Payment date: 20190627 Year of fee payment: 11 Ref country code: PL Payment date: 20190625 Year of fee payment: 11 Ref country code: PT Payment date: 20190627 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20190722 Year of fee payment: 11 Ref country code: LU Payment date: 20190722 Year of fee payment: 11 Ref country code: RO Payment date: 20190626 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SK Payment date: 20190626 Year of fee payment: 11 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161019 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20190822 Year of fee payment: 11 Ref country code: SE Payment date: 20190725 Year of fee payment: 11 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161019 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: HU Payment date: 20190621 Year of fee payment: 11 Ref country code: BE Payment date: 20190722 Year of fee payment: 11 |
|
| 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: 20161019 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20200801 |
|
| REG | Reference to a national code |
Ref country code: SK Ref legal event code: MM4A Ref document number: E 22822 Country of ref document: SK Effective date: 20200706 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200801 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210208 Ref country code: HU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200707 |
|
| 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: 20200707 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20211229 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20200707 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200706 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220725 Year of fee payment: 14 Ref country code: AT Payment date: 20220718 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220725 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20220727 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230629 Year of fee payment: 15 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 837933 Country of ref document: AT Kind code of ref document: T Effective date: 20230706 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230706 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230706 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230706 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230706 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230731 |