EP0090351B1 - Liquid oxidant desizing agent, and process for oxidative desizing - Google Patents
Liquid oxidant desizing agent, and process for oxidative desizing Download PDFInfo
- Publication number
- EP0090351B1 EP0090351B1 EP83102909A EP83102909A EP0090351B1 EP 0090351 B1 EP0090351 B1 EP 0090351B1 EP 83102909 A EP83102909 A EP 83102909A EP 83102909 A EP83102909 A EP 83102909A EP 0090351 B1 EP0090351 B1 EP 0090351B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- desizing
- oxidative
- impregnated
- treated
- persulfate
- 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
Links
- 239000003795 chemical substances by application Substances 0.000 title claims description 9
- 238000010012 oxidative desizing Methods 0.000 title claims description 6
- 238000009990 desizing Methods 0.000 title description 18
- 238000000034 method Methods 0.000 title description 5
- 239000007788 liquid Substances 0.000 title description 4
- 239000007800 oxidant agent Substances 0.000 title 1
- 230000001590 oxidative effect Effects 0.000 title 1
- 239000004094 surface-active agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000203 mixture Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 6
- 239000010695 polyglycol Substances 0.000 description 6
- 241000219422 Urtica Species 0.000 description 5
- 235000009108 Urtica dioica Nutrition 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- -1 rice starch Polymers 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
- D06L1/14—De-sizing
Definitions
- persulfates and peroxodiphosphates for the oxidative desizing of tissues from cellulose fibers and their blends with synthetic fibers, since persulfates and peroxodiphosphates are starches such as. B. potato starch, rice starch, corn starch and tapioca, which are used for the sizing of tissues, excellent in the presence of alkali.
- a disadvantage of desizing with persulfates is that damage to the cellulosic fibers can easily occur, which is expressed in a sharp drop in the average degree of polymerization.
- the invention relates to a new oxidative desizing agent consisting of 5 to 20 wt.% Sodium or ammonium persulfate, potassium, sodium, ammonium or calcium peroxodiphosphate, 20 to 50 wt.% Of one or more surfactants from the group C B -C 2o -sec.alkanesulfonates, C4-C12-alkylphenol oxyethylates with 6-12 units of ethylene oxide and C1crC18-fatty alcohol oxyethylates with 3 to 8 units of ethylene oxide as well as water according to the balance to 100%.
- a new oxidative desizing agent consisting of 5 to 20 wt.% Sodium or ammonium persulfate, potassium, sodium, ammonium or calcium peroxodiphosphate, 20 to 50 wt.% Of one or more surfactants from the group C B -C 2o -sec.alkanesulfonates, C4-C12-alkylphenol
- the groups of surfactants mentioned above can be taken alone or in combination with one another. Mixtures of an alkanesulfonate and one of the two nonionic surfactants in a weight ratio of 1: 6 or 6: 1 are preferred.
- the desizing agent according to the invention is obtained by dissolving the persulfate or peroxodiphosphate in the surfactant or surfactants at about 50 ° C. for 1-2 hours, allowing it to cool and then diluting it with the required amount of water.
- This surfactant-persulfate or peroxodiphosphate mixture is suitable for the oxidative desizing of fabrics which contain cellulose fibers alone or in a mixture with synthetic fibers.
- the fabric is impregnated with an aqueous solution of this desizing agent with the simultaneous addition of alkali, preferably sodium hydroxide solution.
- alkali preferably sodium hydroxide solution.
- the material impregnated in this way is squeezed to a moisture content of approximately 100% and then treated at 20-160 ° C for a period of between 30 seconds and 24 hours.
- the length of the treatment time depends on the respective process-specific temperature and type of dwelling unit.
- the content of the desizing agent described above in the aqueous liquor is 0.5 to 3, preferably 0.8 to 2% by weight, assuming a squeezing effect of 100%.
- the amount of alkali to be added is chosen so that the pH of the liquor is always above 10. This generally requires 0.1 to 10, preferably 0.3 to 4,% by weight of solid sodium hydrox
- the fabric is expediently washed out with hot water at approx. 85-95 ° C for 10-60 seconds and then rinsed cold.
- alkali and detergent are expediently added to the wash water.
- This desizing process can also be combined with a conventional bleaching process.
- the fabric is impregnated with an aqueous liquor which, in addition to the desizing agent and alkali in the amount and composition specified above, also contains 30 to 60 ml of H 2 O 2 (35%) in one liter of liquor and sodium silicate as stabilizer.
- the impregnated fabric is again squeezed to approx. 100% and stored for 6 to 24 hours at room temperature or briefly steamed at approx. 100%.
- the fabric is then washed out, with alkali and detergent being added to the wash water to improve the size degradation.
- the advantage of the desizing agent according to the invention is that it is liquid and therefore easy to dose. In addition, it is very stable in storage and remains stable for up to 6 months at 30 ° C. In addition, when using this combination, the amount of per-compound required for desizing can be reduced to approx. 25% of the amount of per-compound that would be necessary with desizing alone with a per-compound. This reduction results in a substantial reduction in fiber damage. In order to achieve these advantages, it is crucial that, according to this invention, the per compound and the surfactant are not added separately to the impregnation liquor, but rather that the mixture of the per compound and surfactant is used first and this mixture is then added to the fleet.
- the impregnated material is squeezed to 100% residual moisture content and treated with steam on a steamer at 103-105 ° C.
- the goods are then washed free of alkali with hot water.
- the goods treated in this way have a whiteness of 66.7%.
- the degree of desizing measured according to the violet scale TEGEWA, is 8-9.
- the average degree of polymerization (DP) of the treated material is 2550.
- the impregnated material is squeezed to a residual moisture content of 100%, wound up and rests in a steam atmosphere with 100% relative humidity at 95 ° C. for 1 hour. The material is then treated as in Example 1.
- the goods treated in this way have a whiteness of 67.2%.
- the degree of desizing, measured according to the violet scale TEGEWA, is 8-9.
- the DP value of the treated material is 2500.
- the impregnated material is squeezed to a residual moisture content of 100%, wrapped on a pillow and wrapped with plastic wrap to prevent it from drying out.
- the lump is then left for 16-20 hours at room temperature.
- the goods are then washed out in the first wash baths with the addition of alkali.
- the goods treated in this way have a whiteness of 85%.
- the DP value of the treated material is 2450.
- the impregnated material is squeezed to 100% residual moisture content and treated with steam on a steamer at 100-102 ° C.
- the goods are then washed out in the first wash baths with the addition of alkali.
- the goods treated in this way have a whiteness of 84%.
- the DP value of the treated material is 2400.
- the impregnated material is squeezed to a residual moisture content of 100% and treated with steam on a steamer at 103-105 ° C. The goods must then be washed free of alkali.
- the goods treated in this way have a whiteness of 68.6%.
- the degree of desizing, measured according to the violet scale TEGEWA, is 8.
- the average degree of polymerization (DP) of the treated material is 2400.
- the impregnated material is squeezed to a residual moisture content of 100%, wrapped on a pillow and wrapped with plastic wrap to prevent it from drying out.
- the lump is then left for 16-20 hours at room temperature.
- the goods are then washed out with the addition of alkali in the first wash baths.
- the goods treated in this way have a whiteness of 84%.
- the DP value of the treated material is 2300.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Removal Of Specific Substances (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Paints Or Removers (AREA)
Description
Es ist bekannt, Persulfate und Peroxodiphosphate zur oxidativen Entschlichtung von Geweben aus Cellulosefasern und deren Mischungen mit Synthesefasern zu verwenden, da Persulfate und Peroxodiphosphate Stärken wie z. B. Kartoffelstärke, Reis-, Maisstärke und Tapioca, die zur Beschlichtung von Geweben verwendet werden, in Gegenwart von Alkali hervorragend abbauen. Als Nachteil der Entschlichtung mit Persulfaten ist zu werten, dass leicht eine Schädigung der cellulosischen Fasern eintreten kann, die sich in einem starken Abfall des Durchschnittspolymerisations-Grades ausdrückt.It is known to use persulfates and peroxodiphosphates for the oxidative desizing of tissues from cellulose fibers and their blends with synthetic fibers, since persulfates and peroxodiphosphates are starches such as. B. potato starch, rice starch, corn starch and tapioca, which are used for the sizing of tissues, excellent in the presence of alkali. A disadvantage of desizing with persulfates is that damage to the cellulosic fibers can easily occur, which is expressed in a sharp drop in the average degree of polymerization.
Weiterhin ist aus der DE-OS 2 913 177 bekannt, dass es durch geeignete Kaliumpersulfat-Tensid-Kombination möglich ist, den gleichen Entschlichtungseffekt mit einer wesentlich niedrigeren Persulfatkonzentration zu erreichen. Solche Tensid/Kaliumpersulfat-Kombinationen werden vor dem Gebrauch als fertige Zubereitungen hergestellt und sind zum Zwecke einer ausreichenden Lagerstabilität hochviskos bzw. pastös. Sie sind deshalb vor dem Gebrauch separat zu lösen. Dies ist für deren praktischen Einsatz ein schwerwiegender Nachteil, da ein Vorlösen zusätzlichen Arbeitsaufwand bedeutet und andererseits nicht einwandrei gelöste Persulfatteilchen auf dem Textilmaterial örtlich zu Faserschädigungen führen. Ausserdem ist bei Grossverbrauchern der Zusatz der Einzelkomponenten zu den Entschlichtungs-, Abkoch- und Bleichflotten über Dosierpumpen üblich, so dass die Verwendung von pump- und dosierfähigen Produkten unerlässlich ist. Solche dosierfähigen, flüssigen Kaliumpersulfat/Tensid-Kombinationen konnten bisher in der von den Textilbetrieben geforderten Konzentration nicht hergestellt werden.Furthermore, it is known from DE-OS 2 913 177 that a suitable combination of potassium persulfate and surfactant makes it possible to achieve the same desizing effect with a substantially lower persulfate concentration. Such surfactant / potassium persulfate combinations are prepared before use as finished preparations and are highly viscous or pasty for the purpose of sufficient storage stability. They must therefore be solved separately before use. This is a serious disadvantage for their practical use, since pre-loosening means additional workload and, on the other hand, persulfate particles on the textile material which are not correctly dissolved locally lead to fiber damage. In addition, it is common for large consumers to add the individual components to the desizing, decoction and bleaching liquors via metering pumps, so that the use of pumpable and meterable products is essential. Such meterable, liquid potassium persulfate / surfactant combinations have so far not been able to be produced in the concentration required by the textile companies.
Es wurde nun überraschend gefunden, dass solche flüssigen, lagerstabilen Persulfat/Tensidkombinationen erhalten werden, wenn man ausgewählte anionische und nichtionische Tenside verwendet und anstelle von Kaliumpersulfat das Natrium-, Ammoniumpersulfat oder Peroxodiphosphate einarbeitet.It has now surprisingly been found that such liquid, storage-stable persulfate / surfactant combinations are obtained if selected anionic and nonionic surfactants are used and sodium, ammonium persulfate or peroxodiphosphate are incorporated instead of potassium persulfate.
Gegenstand der Erfindung ist ein neues oxidatives Entschlichtungsmittel bestehend aus 5 bis 20 Gew.% Natrium- oder Ammoniumpersulfat, Kalium-, Natrium-, Ammonium- oder Calciumperoxodiphosphat, 20 bis 50 Gew.% eines oder mehrerer Tenside aus der Gruppe CB-C2o-sek.Alkansulfonate, C4-C12-Alkylphenoloxethylate mit 6-12 Einheiten Ethylenoxid und C1crC18-Fettalkoholoxethylate mit 3 bis 8 Einheiten Ethylenoxid sowie Wasser entsprechend dem Ausgleich zu 100%.The invention relates to a new oxidative desizing agent consisting of 5 to 20 wt.% Sodium or ammonium persulfate, potassium, sodium, ammonium or calcium peroxodiphosphate, 20 to 50 wt.% Of one or more surfactants from the group C B -C 2o -sec.alkanesulfonates, C4-C12-alkylphenol oxyethylates with 6-12 units of ethylene oxide and C1crC18-fatty alcohol oxyethylates with 3 to 8 units of ethylene oxide as well as water according to the balance to 100%.
Man kann die oben genannten Gruppen von Tensiden jeweils allein nehmen oder in Kombination miteinander. Bevorzugt werden Mischungen aus einem Alkansulfonat und einem der beiden nichtionischen Tenside im Gewichtsverhältnis von 1 : 6 bzw. 6 : 1.The groups of surfactants mentioned above can be taken alone or in combination with one another. Mixtures of an alkanesulfonate and one of the two nonionic surfactants in a weight ratio of 1: 6 or 6: 1 are preferred.
Man erhält das erfindungsgemässe Entschlichtungsmittel, indem man bei ca. 50°C während 1-2 Stunden das Persulfat bzw. Peroxodiphosphat in dem Tensid bzw. den Tensiden löst, abkühlen lässst und dann mit der erforderlichen Menge Wasser verdünnt.The desizing agent according to the invention is obtained by dissolving the persulfate or peroxodiphosphate in the surfactant or surfactants at about 50 ° C. for 1-2 hours, allowing it to cool and then diluting it with the required amount of water.
Diese Tensid-Persulfat bzw. Peroxodiphosphat-Mischung ist zur oxidativen Entschlichtung von Geweben, die Cellulosefasern alleine oder in Mischung mit Synthesefasern enthalten, geeignet. Man imprägniert das Gewebe mit einer wässrigen Lösung dieses Entschlichtungsmittels bei gleichzeitigem Zusatz von Alkali, vorzugsweise Natronlauge. Das so imprägnierte Material wird durch Abquetschen auf einen Feuchtigkeitsgehalt von ca. 100% gebracht und nachfolgend bei 20-160 °C über einen Zeitraum zwischen 30 Sekunden und 24 Stunden behandelt. Die Länge der Behandlungszeit richtet sich nach der jeweiligen verfahrensspezifischen Temperatur und Art des Verweilaggregates. Der Gehalt des oben beschriebenen Entschlichtungsmittels in der wässrigen Flotte beträgt 0,5 bis 3, vorzugsweise 0,8 bis 2 Gew.% unter Annahme eines Abquetscheffekts von 100%. Die Menge an zuzugebendem Alkali wird wie üblich so gewählt, dass der pH-Wert der Flotte immer über 10 liegt. Hierzu sind im allgemeinen 0,1 bis 10, vorzugsweise 0,3 bis 4 Gew.% an festem Natriumhydroxid erforderlich.This surfactant-persulfate or peroxodiphosphate mixture is suitable for the oxidative desizing of fabrics which contain cellulose fibers alone or in a mixture with synthetic fibers. The fabric is impregnated with an aqueous solution of this desizing agent with the simultaneous addition of alkali, preferably sodium hydroxide solution. The material impregnated in this way is squeezed to a moisture content of approximately 100% and then treated at 20-160 ° C for a period of between 30 seconds and 24 hours. The length of the treatment time depends on the respective process-specific temperature and type of dwelling unit. The content of the desizing agent described above in the aqueous liquor is 0.5 to 3, preferably 0.8 to 2% by weight, assuming a squeezing effect of 100%. As usual, the amount of alkali to be added is chosen so that the pH of the liquor is always above 10. This generally requires 0.1 to 10, preferably 0.3 to 4,% by weight of solid sodium hydroxide.
Nach der Behandlung wird das Gewebe zweckmässig mit heissem Wasser von ca. 85-95 °C während 10-60 Sekunden ausgewaschen und nachfolgend kalt gespült.Dem Waschwasser wird zur Erhöhung des Auswaschgrades noch zweckmässigerweise Alkali und Waschmittel zugesetzt.After the treatment, the fabric is expediently washed out with hot water at approx. 85-95 ° C for 10-60 seconds and then rinsed cold. To increase the degree of washout, alkali and detergent are expediently added to the wash water.
Dieses Entschlichtungsverfahren kann man auch mit einem üblichen Bleichverfahren kombinieren. In diesem Fall wird das Gewebe mit einer wässrigen Flotte imprägniert, die neben dem Entschlichtungsmittel und Alkali in der oben angegebenen Menge und Zusammensetzung noch 30 bis 60 ml H202 (35%ig) in einem Liter Flotte sowie Natriumsilikat als Stabilisator enthält. Das imprägnierte Gewebe wird wiederum auf ca. 100% abgequetscht und 6 bis 24 Stunden bei Raumtemperatur gelagert oder kurzzeitig bei etwa 100% gedämpft. Dann wird das Gewebe ausgewaschen, wobei dem Waschwasser zur Verbesserung des Schlichteabbaus Alkali und Waschmittel zugesetzt wird.This desizing process can also be combined with a conventional bleaching process. In this case, the fabric is impregnated with an aqueous liquor which, in addition to the desizing agent and alkali in the amount and composition specified above, also contains 30 to 60 ml of H 2 O 2 (35%) in one liter of liquor and sodium silicate as stabilizer. The impregnated fabric is again squeezed to approx. 100% and stored for 6 to 24 hours at room temperature or briefly steamed at approx. 100%. The fabric is then washed out, with alkali and detergent being added to the wash water to improve the size degradation.
Der Vorteil des erfindungsgemässen Entschlichtungsmittel besteht darin, dass es flüssig ist und damit leicht dosiert werden kann. Ausserdem ist es sehr gut lagerstabil und bleibt bis zu 6 Monaten bei 30°C lagerstabil. Darüber hinaus lässt sich bei Verwendung dieser Kombination die zur Entschlichtung erforderliche Menge an Perverbindung auf ca. 25% der Menge an Perverbindung senken, die beim Entschlichten allein mit einer Perverbindung nötig wäre. Durch diese Reduzierung erreicht man eine weitgehende Verminderung der Faserschädigung. Um diese Vorteile zu erreichen, ist es ausschlaggebend, dass gemäss dieser Erfindung die Perverbindung und das Tensid nicht separat in die Imprägnierflotte gegeben werden, sondern dass zunächst die Mischung aus der Perverbindung und Tensid hergestellt und diese Mischung dann in die Flotte gegeben wird.The advantage of the desizing agent according to the invention is that it is liquid and therefore easy to dose. In addition, it is very stable in storage and remains stable for up to 6 months at 30 ° C. In addition, when using this combination, the amount of per-compound required for desizing can be reduced to approx. 25% of the amount of per-compound that would be necessary with desizing alone with a per-compound. This reduction results in a substantial reduction in fiber damage. In order to achieve these advantages, it is crucial that, according to this invention, the per compound and the surfactant are not added separately to the impregnation liquor, but rather that the mixture of the per compound and surfactant is used first and this mixture is then added to the fleet.
Die nachfolgenden Beispiele sollen das erfindungsgemässe Verfahren erläutern, aber nicht einschränken. Die Prozentangaben sind Gewichtsprozente.The following examples are intended to explain, but not to limit, the process according to the invention. The percentages are percentages by weight.
Mit Stärke geschlichteter Baumwollnessel wurde mit einer Lösung folgender Zusammensetzung imprägniert:
- 6,0% Natriumhydroxid
- 1,5% Persulfat-Tensid-Mischung folgender Zusammensetzung:
- 5,0% Nonylphenolpolyglykolether + 8 Mol AeO
- 30,0% sekundäres Alkansulfonat (C11-C17)
- 7,0% Peroxidisulfat (Na-Salz)
- 6.0% sodium hydroxide
- 1.5% persulfate surfactant mixture of the following composition:
- 5.0% nonylphenol polyglycol ether + 8 mol AeO
- 30.0% secondary alkanesulfonate (C 11 -C 17 )
- 7.0% peroxydisulfate (Na salt)
Das imprägnierte Material wird auf 100% Restfeuchtegehalt abgequetscht und auf einem Dämpfer bei 103-105°C mit Dampf behandelt. Anschliessend wird die Ware mit heissem Wasser alkalifrei gewaschen.The impregnated material is squeezed to 100% residual moisture content and treated with steam on a steamer at 103-105 ° C. The goods are then washed free of alkali with hot water.
Die so behandelte Ware weist einen Weissgrad von 66,7% auf. Der Entschlichtungsgrad, gemessen nach Violettskala TEGEWA, ist 8-9. Der Durchschnittspolymerisationsgrad (DP) des behandelten Materials beträgt 2550.The goods treated in this way have a whiteness of 66.7%. The degree of desizing, measured according to the violet scale TEGEWA, is 8-9. The average degree of polymerization (DP) of the treated material is 2550.
Baumwollgewebe wie im Beispiel 1 wird mit einer Lösung folgender Zusammensetzung imprägniert:
- 3,0% Natriumhydroxid
- 1,5% Persulfat-Tensid-Kombination folgender Zusammensetzung:
- 10,0% C1o-C14-Fettalkoholpolyglykolether + 6 Mol AeO
- 10,0% sekundäres Alkansulfonat (C11-C17)
- 7,0% Peroxidisulfat (NH4-Salz)
- 3.0% sodium hydroxide
- 1.5% persulfate-surfactant combination of the following composition:
- 10.0% C1o-C14 fatty alcohol polyglycol ether + 6 mol AeO
- 10.0% secondary alkanesulfonate (C 11 -C 17 )
- 7.0% peroxydisulfate (NH 4 salt)
Das imprägnierte Material wird auf 100% Restfeuchtegehalt abgequetscht, aufgewickelt und verweilt in Dampfatmosphäre mit 100% relativer Feuchtigkeit bei 95°C 1 Stunde. Anschliessend wird das Material wie im Beispiel 1 behandelt.The impregnated material is squeezed to a residual moisture content of 100%, wound up and rests in a steam atmosphere with 100% relative humidity at 95 ° C. for 1 hour. The material is then treated as in Example 1.
Die so behandelte Ware weist einen Weissgrad von 67,2% auf. Der Entschlichtungsgrad, gemessen nach Violettskala TEGEWA, ist 8-9. Der DP-Wert des behandelten Materials ist 2500.The goods treated in this way have a whiteness of 67.2%. The degree of desizing, measured according to the violet scale TEGEWA, is 8-9. The DP value of the treated material is 2500.
Baumwollnessel wie im Beispiel 1 wird mit einer Lösung folgender Zusammensetzung imprägniert:
- 4,0% Wasserstoffperoxid 35%ig
- 2,0% Natriumsilikat 36-38°Be
- 1,0% Natriumhydroxid
- 1,0% Persulfat-Tensid-Kombination folgender Zusammensetzung:
- 30,0% Nonylphenolpolyglykolether + 6 Mol AeO
- 5,0% sekundäres Alkansulfonat (C11-C17)
- 17,0% Peroxidisulfat (NH4-Salz)
- 4.0% hydrogen peroxide 35%
- 2.0% sodium silicate 36-38 ° Be
- 1.0% sodium hydroxide
- 1.0% persulfate-surfactant combination with the following composition:
- 30.0% nonylphenol polyglycol ether + 6 mol AeO
- 5.0% secondary alkanesulfonate (C 11 -C 17 )
- 17.0% peroxydisulfate (NH 4 salt)
Das imprägnierte Material wird auf 100% Restfeuchtegehalt abgequetscht, auf eine Kaule gewickelt und mit Plastikfolie umwickelt, um ein Antrocknen zu vermeiden. Die Kaule wird anschliessend 16-20 Stunden bei Raumtemperatur verweilen lassen. Anschliessend wird die Ware unter Alkalizusatz in den ersten Waschbädern ausgewaschen.The impregnated material is squeezed to a residual moisture content of 100%, wrapped on a pillow and wrapped with plastic wrap to prevent it from drying out. The lump is then left for 16-20 hours at room temperature. The goods are then washed out in the first wash baths with the addition of alkali.
Die so behandelte Ware weist einen Weissgrad von 85% auf. Der Entschlichtungsgrad, gemessen nach Violettskala TEGEWA, ist 9. Der DP-Wert des behandelten Materials ist 2450.The goods treated in this way have a whiteness of 85%. The degree of desizing, measured according to the violet scale TEGEWA, is 9. The DP value of the treated material is 2450.
Baumwollnessel wie im Beispiel 1, wird mit einer Lösung folgender Zusammensetzung imprägniert:
- 3,0% Wasserstoffperoxid 35%ig
- 1,0% Natriumsilikat 36-38°Be
- 0,6% Natriumhydroxid
- 3,0% Persulfat-Tensid-Kombination folgender Zusammensetzung:
- 5,0% C10-C14-Fettalkoholpolyglykolether + 5 MoI AeO
- 30,0% sekundäres Alkansulfonat (Cii-C17)
- 7,0% Peroxidisulfat (Na- oder NH4-Salz)
- 3.0% hydrogen peroxide 35%
- 1.0% sodium silicate 36-38 ° Be
- 0.6% sodium hydroxide
- 3.0% persulfate-surfactant combination of the following composition:
- 5.0% C 10 -C 14 fatty alcohol polyglycol ether + 5 MoI AeO
- 30.0% secondary alkanesulfonate (C ii -C 17 )
- 7.0% peroxydisulfate (Na or NH 4 salt)
Das imprägnierte Material wird auf 100% Restfeuchtegehalt abgequetscht und auf einem Dämpfer bei 100-102°C mit Dampf behandelt. Anschliessend wird die Ware unter Alkalizusatz in den ersten Waschbädern ausgewaschen.The impregnated material is squeezed to 100% residual moisture content and treated with steam on a steamer at 100-102 ° C. The goods are then washed out in the first wash baths with the addition of alkali.
Die so behandelte Ware weist einen Weissgrad von 84% auf. Der Entschlichtungsgrad, gemessen nach Violettskala TEGEWA, ist 8-9. Der DP-Wert des behandelten Materials ist 2400.The goods treated in this way have a whiteness of 84%. The degree of desizing, measured according to the violet scale TEGEWA, is 8-9. The DP value of the treated material is 2400.
Mit Stärke geschlichteter Baumwollnessel wurde mit einer Lösung folgender Zusammensetzung imprägniert:
- 6,0% Natriumhydroxid
- 1,5% Peroxodiphosphat-Tensid-Mischung folgender Zusammensetzung:
- 5,0% Nonylphenolpolyglykolether + 8-10 Mol AeO
- 30,0% sekundäres Alkansulfonat (C11-C17)
- 8,0% Peroxodiphosphat (Natriumsalz)
- 6.0% sodium hydroxide
- 1.5% peroxodiphosphate surfactant mixture of the following composition:
- 5.0% nonylphenol polyglycol ether + 8-10 mol AeO
- 30.0% secondary alkanesulfonate (C 11 -C 17 )
- 8.0% peroxodiphosphate (sodium salt)
Das so imprägnierte Material wird auf 100%igen Restfeuchtegehalt abgequetscht und auf einem Dämpfer bei 103-105°C mit Dampf behandelt. Anschliessend ist die Ware alkalifrei zu waschen.The impregnated material is squeezed to a residual moisture content of 100% and treated with steam on a steamer at 103-105 ° C. The goods must then be washed free of alkali.
Die so behandelte Ware weist einen Weissgrad von 68,6% auf. Der Entschlichtungsgrad, gemessen nach Violettskala TEGEWA, ist 8.The goods treated in this way have a whiteness of 68.6%. The degree of desizing, measured according to the violet scale TEGEWA, is 8.
Der Durchschnittspolymerisationsgrad (DP) des behandelten Materials beträgt 2400.The average degree of polymerization (DP) of the treated material is 2400.
Baumwollnessel wie im vorstehenden Beispiel wird mit einer Lösung folgender Zusammensetzung imprägniert:
- 5,0% Wasserstoffperoxid 35%ig
- 2,0% Natriumsilikat 36-38°Be.
- 1,0% Natriumhydroxid
- 1,5% Peroxodiphosphat-Tensid-Mischung folgender Zusammensetzung:
- 30,0% Nonylphenolpolyglykolether + 10 Mol AeO
- 5,0% sekundäres Alkansulfonat (C11-C17)
- 15,0% Peroxodiphosphat (Ammoniumsalz)
- 5.0% hydrogen peroxide 35%
- 2.0% sodium silicate 36-38 ° Be.
- 1.0% sodium hydroxide
- 1.5% peroxodiphosphate surfactant mixture of the following composition:
- 30.0% nonylphenol polyglycol ether + 10 mol AeO
- 5.0% secondary alkanesulfonate (C 11 -C 17 )
- 15.0% peroxodiphosphate (ammonium salt)
Das imprägnierte Material wird auf 100% Restfeuchtegehalt abgequetscht, auf eine Kaule gewickelt und mit Plastikfolie umwickelt, um ein Antrocknen zu vermeiden. Die Kaule wird anschliessend 16-20 Stunden bei Raumtemperatur verweilen lassen. Nachfolgend wird die Ware unter Alkalizusatz in den ersten Waschbädern ausgewaschen.The impregnated material is squeezed to a residual moisture content of 100%, wrapped on a pillow and wrapped with plastic wrap to prevent it from drying out. The lump is then left for 16-20 hours at room temperature. The goods are then washed out with the addition of alkali in the first wash baths.
Die so behandelte Ware weist einen Weissgrad von 84% auf. Der Entschlichtungsgrad, gemessen nach der Violettskala TEGEWA, ist 7-8. Der DP-Wert des behandelten Materials ist 2300.The goods treated in this way have a whiteness of 84%. The degree of desizing, measured according to the violet scale TEGEWA, is 7-8. The DP value of the treated material is 2300.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83102909T ATE27192T1 (en) | 1982-03-30 | 1983-03-24 | LIQUID OXIDATIVE DESIZING AGENT AND OXIDATIVE DESIZING PROCESS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823211677 DE3211677A1 (en) | 1982-03-30 | 1982-03-30 | LIQUID OXIDATIVE DETOXIFICANT AND METHOD FOR OXIDATIVE DECOXIFYING |
| DE3211677 | 1982-03-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0090351A2 EP0090351A2 (en) | 1983-10-05 |
| EP0090351A3 EP0090351A3 (en) | 1985-05-15 |
| EP0090351B1 true EP0090351B1 (en) | 1987-05-13 |
Family
ID=6159703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83102909A Expired EP0090351B1 (en) | 1982-03-30 | 1983-03-24 | Liquid oxidant desizing agent, and process for oxidative desizing |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4478737A (en) |
| EP (1) | EP0090351B1 (en) |
| JP (1) | JPS58174675A (en) |
| KR (1) | KR900007089B1 (en) |
| AR (1) | AR230299A1 (en) |
| AT (1) | ATE27192T1 (en) |
| BR (1) | BR8301618A (en) |
| CA (1) | CA1189657A (en) |
| DE (2) | DE3211677A1 (en) |
| ZA (1) | ZA832228B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180514A (en) * | 1985-06-17 | 1993-01-19 | The Clorox Company | Stabilizing system for liquid hydrogen peroxide compositions |
| US4900468A (en) * | 1985-06-17 | 1990-02-13 | The Clorox Company | Stabilized liquid hydrogen peroxide bleach compositions |
| DE8713542U1 (en) * | 1987-10-09 | 1987-12-17 | Schmitt, Horst, 4236 Hamminkeln | Wall hook |
| EP0360743A1 (en) * | 1988-09-19 | 1990-03-28 | Ciba-Geigy Ag | Mixtures of non-ionic surfactants and their use as textile finishing agents |
| DE3914827C2 (en) * | 1989-05-05 | 1995-06-14 | Schuelke & Mayr Gmbh | Liquid disinfectant concentrate |
| AT408987B (en) * | 2000-10-13 | 2002-04-25 | Thonhauser Gmbh Dipl Ing | Cleaner and disinfectant |
| CN108505318B (en) * | 2018-03-23 | 2020-07-07 | 多恩生物科技有限公司 | Desizing agent and preparation method thereof |
| CN110592925A (en) * | 2019-09-09 | 2019-12-20 | 苏州联胜化学有限公司 | Chemical fiber desizing agent and preparation method and use method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT151637B (en) * | 1936-03-23 | 1937-11-25 | Friedrich Ing Bohac | Process for the desizing of goods made of cotton or other cellulose-containing textile fibers. |
| BE787058A (en) * | 1971-08-02 | 1973-02-01 | Fmc Corp | COMBINED PROCESS FOR DECASTING, LAUNCHING AND BLEACHING OF TEXTILE FIBERS |
| US3740188A (en) * | 1971-08-02 | 1973-06-19 | Fmc Corp | Simultaneous desize-scour-bleach with activated hydrogen peroxide |
| AU472097B2 (en) * | 1974-01-31 | 1974-04-04 | Fmc Corporation | Desize-scouring of textiles |
| DE2913177A1 (en) * | 1979-04-02 | 1980-10-23 | Hoechst Ag | OXIDATIVE DETOXIFICATION AGENT AND METHOD FOR OXIDATIVE DECOMPOSITION |
| JPS5622988A (en) * | 1979-08-01 | 1981-03-04 | Hitachi Ltd | Device for supporting nuclear fusion device vaccum vessel |
| JPS6027338B2 (en) * | 1979-08-07 | 1985-06-28 | 明 山村 | Japanese-style and Western-style square tiles with locking protrusions |
-
1982
- 1982-03-30 DE DE19823211677 patent/DE3211677A1/en not_active Withdrawn
-
1983
- 1983-03-24 DE DE8383102909T patent/DE3371546D1/en not_active Expired
- 1983-03-24 US US06/478,245 patent/US4478737A/en not_active Expired - Lifetime
- 1983-03-24 AT AT83102909T patent/ATE27192T1/en not_active IP Right Cessation
- 1983-03-24 EP EP83102909A patent/EP0090351B1/en not_active Expired
- 1983-03-28 KR KR1019830001245A patent/KR900007089B1/en not_active IP Right Cessation
- 1983-03-29 JP JP58051737A patent/JPS58174675A/en active Granted
- 1983-03-29 AR AR292561A patent/AR230299A1/en active
- 1983-03-29 BR BR8301618A patent/BR8301618A/en not_active IP Right Cessation
- 1983-03-29 CA CA000424809A patent/CA1189657A/en not_active Expired
- 1983-03-29 ZA ZA832228A patent/ZA832228B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR900007089B1 (en) | 1990-09-28 |
| DE3371546D1 (en) | 1987-06-19 |
| AR230299A1 (en) | 1984-03-01 |
| US4478737A (en) | 1984-10-23 |
| JPS58174675A (en) | 1983-10-13 |
| KR840004201A (en) | 1984-10-10 |
| ATE27192T1 (en) | 1987-05-15 |
| EP0090351A3 (en) | 1985-05-15 |
| ZA832228B (en) | 1983-12-28 |
| DE3211677A1 (en) | 1983-10-06 |
| EP0090351A2 (en) | 1983-10-05 |
| JPH0375663B2 (en) | 1991-12-02 |
| BR8301618A (en) | 1983-12-06 |
| CA1189657A (en) | 1985-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0090351B1 (en) | Liquid oxidant desizing agent, and process for oxidative desizing | |
| DE1005923B (en) | Process for cleaning, in particular for boiling and boiling, cellulose fiber fibers | |
| DE3820160C2 (en) | Concentrated preparation and its use as a stabilizer for alkaline liquors containing peroxide | |
| EP0017190B1 (en) | Process for oxidative desizing | |
| DE1469473A1 (en) | Process for improving the absorption capacity of cellulose fibers | |
| LU82125A1 (en) | METHOD FOR WASHING TEXTILES AND THE DETERGENTS TO BE USED FOR THIS | |
| DE2721402C2 (en) | Process for bleaching pulp | |
| DE2140325C3 (en) | Bleaching process for cellulose textiles | |
| DE837917C (en) | Detergents, cleaning agents or soaking agents | |
| EP0705357B1 (en) | Use of carboxymethylated guargalactomannan as a sizing agent | |
| DE1034133B (en) | Process for reducing pilling of textile material based on polyesters containing six-membered carbocyclic rings | |
| AT156474B (en) | Process for pretreatment or desizing of yarns and fabrics before dyeing. | |
| DE739749C (en) | Process for treating textiles made from hydrate cellulose fibers or blended fabrics containing them | |
| DE1301792B (en) | Optical brightener | |
| DE2143969C3 (en) | Process for lightening raw bast fibers | |
| DE1619028A1 (en) | Process for making cellulose textiles flame resistant | |
| DE749266C (en) | Process for the production of artificial structures such as rayon and rayon from viscose with improved textile properties | |
| AT206857B (en) | Process for improving the whiteness of organic substances, in particular of fibers, such as textiles and paper, as well as foils | |
| DE2412175A1 (en) | PROCESS FOR APPRETING TEXTILES, IN PARTICULAR DURING CHEMICAL CLEANING | |
| DE668572C (en) | Process for finishing textile material made from cellulose or hydrate cellulose fibers | |
| DE1126353B (en) | Process for sizing and starching cellulose fabrics | |
| DE1419355A1 (en) | Process for bleaching bast fibers | |
| DE69103407T2 (en) | Process for hydrogen peroxide bleaching of high-yield pulps. | |
| DE1013253B (en) | Method of bleaching with chlorites | |
| CH300565A (en) | Laundry detergent. |
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 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19851105 |
|
| 17Q | First examination report despatched |
Effective date: 19860915 |
|
| 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 DE FR GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 27192 Country of ref document: AT Date of ref document: 19870515 Kind code of ref document: T |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| REF | Corresponds to: |
Ref document number: 3371546 Country of ref document: DE Date of ref document: 19870619 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19920214 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19920217 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19920221 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19920228 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19920311 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19920331 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19920513 Year of fee payment: 10 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19930324 Ref country code: AT Effective date: 19930324 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19930331 Ref country code: CH Effective date: 19930331 Ref country code: BE Effective date: 19930331 |
|
| BERE | Be: lapsed |
Owner name: HOECHST A.G. Effective date: 19930331 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19931001 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19930324 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19931130 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19931201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |