EP0378800A2 - Method for the alkaline cleaning of cellulosic textile materials - Google Patents

Method for the alkaline cleaning of cellulosic textile materials Download PDF

Info

Publication number
EP0378800A2
EP0378800A2 EP89122694A EP89122694A EP0378800A2 EP 0378800 A2 EP0378800 A2 EP 0378800A2 EP 89122694 A EP89122694 A EP 89122694A EP 89122694 A EP89122694 A EP 89122694A EP 0378800 A2 EP0378800 A2 EP 0378800A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
phase transfer
transfer catalysts
alkenyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89122694A
Other languages
German (de)
French (fr)
Other versions
EP0378800B1 (en
EP0378800A3 (en
Inventor
Stefan Dr. Paasch
Dieter Dr. Nickel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT89122694T priority Critical patent/ATE91511T1/en
Publication of EP0378800A2 publication Critical patent/EP0378800A2/en
Publication of EP0378800A3 publication Critical patent/EP0378800A3/en
Application granted granted Critical
Publication of EP0378800B1 publication Critical patent/EP0378800B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
    • 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

  • the invention relates to a process for the alkaline cleaning of cellulose-containing fiber materials and the use of phase transfer catalysts in the alkali stage for cleaning cellulose-containing fiber materials.
  • Cotton contains natural impurities, for example waxes, wax-like substances, proteins, seed husks, fruit capsules and pectins, as well as impurities that were applied as foreign substances in the course of processing, for example sizing and harvesting aids. It is the task of the pretreatment to remove these substances as completely as possible from the fiber materials, to make the cellulose-containing fiber materials more hydrophilic for the subsequent finishing processes and to give them increased absorbency. The pretreatment process with which these effects are achieved is called the alkali stage.
  • the alkali stage is usually at temperatures between 90 and 140 ° C without pressure (boiling) or under pressure (humidification) with 1.5 to 12 percent by weight sodium hydroxide solution in the presence carried out by wetting and / or dispersing agents (Chwalla / Anger: “Handbuch der Textilosstoff", Chapter 3.9, Verlag Chemie Weinheim 1977).
  • wetting and / or dispersing agents Chwalla / Anger: "Handbuch der Textilosstoff", Chapter 3.9, Verlag Chemie Weinheim 1977.
  • the liquor: fabric weight ratio is pressed between, for example, 0.7 and 1.2 and with steam, optionally under pressure to 95 to 100 ° C. heated up. After lingering at this temperature for 1 to 3 hours, washing is carried out at 90 to 100 ° C. With the hot dwell process, the dwell temperature is between 40 and 60 ° C. However, in order to get well-boiled cotton goods, a longer treatment time of up to 10 hours and a higher amount of alkali are required compared to the pad roll process.
  • the object of the invention was therefore to develop a process which enables the alkaline treatment of cellulose-containing fiber materials to be carried out at low temperatures without lengthening the treatment time and without deteriorating the quality of the fiber materials.
  • the invention accordingly relates to a process for the alkaline cleaning of cellulose fibers, which thereby characterized in that cellulose-containing fiber materials with alkaline liquors containing 15 to 150 g of alkali, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atoms per liter of liquor, at temperatures between 30 and 70 ° C wetted, then squeezed and washed after 10 to 200 minutes at temperatures between 90 and 105 ° C at temperatures between 30 and 90 ° C.
  • the cellulose-containing fiber materials are preferably wetted with alkaline liquors which contain 2 to 7 g of active substance phase transfer catalysts and 0 to 2 g of alkyl and / or alkenyl alcohols having 6 to 12 carbon atoms per liter of liquor.
  • Another object of the invention is the use of 1 to 10 g of active substance phase transfer catalysts per liter of liquor and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 carbon atoms per liter of liquor in the alkali stage for cleaning cellulosic fiber materials.
  • Suitable phase transfer catalysts are quaternary ammonium compounds, planar macrocyclic polyethers, so-called crown ethers (Römpps Chemie-Lexikon, 8th edition, p. 2258, Franck'sche Verlags Stuttgart 1983) and / or cryptates (Römpps Chemielexikon, 8th edition, p. 2261 , Franck'sche Verlag Stuttgart 1983).
  • Quaternary ammonium compounds and in particular those of the general formula I are preferred in which the radicals R1 and R2 are methyl, R3 is a straight or branched chain, cyclic or noncyclic alkyl or alkenyl radical having 6 to 22 C atoms, R4 is a straight or branched chain alkyl or alkenyl radical having 1 to 14 C atoms or one Benzyl radical and X is a halogen, sulfate, lactate, acetate or citrate anion.
  • Quaternary ammonium compounds are produced by known industrial processes, for example by reacting tertiary amines with one or two long-chain alkyl and / or alkenyl radicals with alkylating reagents such as methyl chloride, methyl bromide, dimethyl sulfate or benzyl chloride (Winnacker / Küchler: "Chemical technology” 4th ed., Volume 7, pp. 126 to 128, Carl Hanser Verlag, Kunststoff 1986).
  • phase transfer catalysts together with alkyl and / or alkenyl alcohols with 1 to 18 carbon atoms, preferably with 6 to 12 carbon atoms.
  • Alkyl and / or alkenyl alcohols can be straight and / or branched, natural and / or synthetic in origin. Ethanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, hexadecanol, octadecanol and / or octadecenol are examples of alkyl and / or alkenyl alcohols to be used according to the invention.
  • Cellulose-containing fiber materials such as cotton and / or jute are first made with alkaline liquors, which are 15 to 150 g per liter Contain alkali, for example NaOH and / or KOH, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atoms, for example on a Benz laboratory continuous system at temperatures between 30 and 70 ° C wetted. After squeezing, the fiber materials, which are wound on, for example, chewing, are left to rotate for 10 to 200 minutes at temperatures between 90 and 105.degree. The fiber materials are then washed at temperatures between 30 and 90 ° C.
  • alkaline liquors which are 15 to 150 g per liter Contain alkali, for example NaOH and / or KOH, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atom
  • the temperature required for washing the cellulose-containing fiber materials can be significantly reduced and / or the total time of the alkali stage is significantly reduced.
  • waxes and / or wax-like substances can be largely removed from cellulose-containing fiber materials at temperatures between 30 and 90 ° C. by washing out. Fiber materials with good absorbency are obtained.
  • Penetration measurements were carried out to determine the saponification rate.
  • glass capillaries filled with cotton wax were immersed in sodium hydroxide solution containing quaternary ammonium compounds.
  • the solutions were each in a test tube which was immersed in a temperature-controlled water bath.
  • the penetration height in the capillaries which is characterized by a dark discoloration of the wax, was determined with the aid of a cathetometer to within 1/100 mm.
  • Tables 1 and 2 contain the results of the penetration measurements. Unless otherwise stated, solutions with 60 g / l NaOH and 5 g / l active substance quaternary ammonium compound were used.

Abstract

A process for the alkaline cleaning of cellulosic fibre materials and the use of phase-transfer catalysts in the alkali stage for the cleaning of cellulosic fibre materials are described.

Description

Die Erfindung betrifft ein Verfahren zur alkalischen Reinigung von cellulosehaltigen Fasermaterialien sowie die Verwendung von Pha­sentransferkatalysatoren in der Alkalistufe zur Reinigung von cellulosehaltigen Fasermaterialien.The invention relates to a process for the alkaline cleaning of cellulose-containing fiber materials and the use of phase transfer catalysts in the alkali stage for cleaning cellulose-containing fiber materials.

Baumwolle enthält natürliche Verunreinigungen, beispielsweise Wachse, wachsartige Substanzen, Proteine, Samenschalen, Fruchtkap­sein und Pektine, sowie Verunreinigungen, die im Zuge der Verar­beitung als Fremdsubstanzen aufgebracht wurden, beispielsweise Schlichten und Erntehilfen. Es ist die Aufgabe der Vorbehandlung, diese Stoffe möglichst vollständig von den Fasermaterialien zu entfernen, die cellulosehaltigen Fasermaterialien für die nachfol­genden Veredlungsprozesse hydrophiler zu machen und ihnen eine er­höhte Saugfähigkeit zu verleihen. Der Vorbehandlungsprozeß, mit dem diese Effekte erzielt werden, wird als Alkalistufe bezeichnet. Da der Schmelzbereich der Wachse, insbesondere des Baumwollwachses zwischen 75 und 85 °C liegt, wird die Alkalistufe üblicherweise bei Temperaturen zwischen 90 und 140 °C ohne Druck (Abkochen) oder un­ter Druck (Beuchen) mit 1,5 bis 12 gewichtsprozentiger Natronlauge in Gegenwart von Netz- und/oder Dispergiermitteln durchgeführt (Chwalla/Anger: "Handbuch der Textilhilfsmittel", Kapitel 3.9, Verlag Chemie Weinheim 1977) ). Durch Variation von Temperatur, Zeit und Alkalikonzentration ist es möglich, die Alkalistufe dem vorliegenden Material und dem Maschinentyp anzupassen. Beim Pad Roll-Verfahren wird nach dem Tränken mit den Flotten bei Tempera­turen zwischen 30 und 70 °C zwischen Rollenpressen auf ein Ge­wichtsverhältnis Flotte : Gewebe zwischen beispielsweise 0,7 und 1,2 abgepreßt und mit Wasserdampf, gegebenenfalls unter Druck auf 95 bis 100 °C aufgeheizt. Nach 1- bis 3stündigem Verweilen bei dieser Temperatur wird bei 90 bis 100 °C ausgewaschen. Beim Warm­verweilverfahren liegt die Verweiltemperatur zwischen 40 und 60 °C. Um jedoch gut abgekochte Baumwollware zu bekommen, ist im Vergleich zum Pad Roll-Verfahren eine längere Behandlungsdauer von bis zu 10 Stunden und eine höhere Einsatzmenge an Alkali erforder­lich.Cotton contains natural impurities, for example waxes, wax-like substances, proteins, seed husks, fruit capsules and pectins, as well as impurities that were applied as foreign substances in the course of processing, for example sizing and harvesting aids. It is the task of the pretreatment to remove these substances as completely as possible from the fiber materials, to make the cellulose-containing fiber materials more hydrophilic for the subsequent finishing processes and to give them increased absorbency. The pretreatment process with which these effects are achieved is called the alkali stage. Since the melting range of the waxes, in particular the cotton wax, is between 75 and 85 ° C, the alkali stage is usually at temperatures between 90 and 140 ° C without pressure (boiling) or under pressure (humidification) with 1.5 to 12 percent by weight sodium hydroxide solution in the presence carried out by wetting and / or dispersing agents (Chwalla / Anger: "Handbuch der Textilhilfsmittel", Chapter 3.9, Verlag Chemie Weinheim 1977). By varying temperature, Time and alkali concentration make it possible to adapt the alkali level to the material and machine type. In the pad roll process, after soaking with the liquors at temperatures between 30 and 70 ° C. between roller presses, the liquor: fabric weight ratio is pressed between, for example, 0.7 and 1.2 and with steam, optionally under pressure to 95 to 100 ° C. heated up. After lingering at this temperature for 1 to 3 hours, washing is carried out at 90 to 100 ° C. With the hot dwell process, the dwell temperature is between 40 and 60 ° C. However, in order to get well-boiled cotton goods, a longer treatment time of up to 10 hours and a higher amount of alkali are required compared to the pad roll process.

Mit den hohen Arbeitstemperaturen der Alkalistufe ist jedoch ein erheblicher Energieverbrauch verbunden. Die Aufgabe der Erfindung bestand daher in der Entwicklung eines Verfahrens, das die Durch­führung der alkalischen Behandlung cellulosehaltiger Fasermateria­lien bei niedrigen Temperaturen ohne Verlängerung der Behandlungs­dauer und ohne Verschlechterung der Qualität der Fasermaterialien ermöglicht.However, the high working temperatures of the alkali stage involve considerable energy consumption. The object of the invention was therefore to develop a process which enables the alkaline treatment of cellulose-containing fiber materials to be carried out at low temperatures without lengthening the treatment time and without deteriorating the quality of the fiber materials.

Überraschenderweise wurde gefunden, daß die Verseifung von Baum­wollwachs, dessen Solubilisierung sowie die Solubilisierung anhaf­tender Begleitstoffe wie Schlichten in Gegenwart von Phasentrans­ferkatalysatoren beschleunigt wird, wodurch das Auswaschen cellulosehaltiger Fasermaterialien bei niedrigeren Temperaturen durchgeführt werden kann, ohne die Behandlungsdauer zu verlängern und ohne Verschlechterung der Qualität der Fasermaterialien.Surprisingly, it was found that the saponification of cotton wax, its solubilization and the solubilization of accompanying substances such as sizing is accelerated in the presence of phase transfer catalysts, as a result of which the washing out of cellulose-containing fiber materials can be carried out at lower temperatures without prolonging the treatment time and without deteriorating the quality of the fiber materials .

Gegenstand der Erfindung ist dementsprechend ein Verfahren zur al­kalischen Reinigung von Cellulosefasern, welches dadurch gekennzeichnet ist, daß man cellulosehaltige Fasermaterialien mit alkalischen Flotten, die pro Liter Flotte 15 bis 150 g Alkali, 1 bis 10 g Aktivsubstanz Phasentransferkatalysatoren und 0 bis 5 g Alkyl- und/oder Alkenylalkohole mit 1 bis 18 CAtomen enthalten, bei Temperaturen zwischen 30 und 70 °C benetzt, anschließend abge­quetscht und nach 10 bis 200 minütigem Verweilen bei Temperaturen zwischen 90 und 105 °C bei Temperaturen zwischen 30 und 90 °C wäscht.The invention accordingly relates to a process for the alkaline cleaning of cellulose fibers, which thereby characterized in that cellulose-containing fiber materials with alkaline liquors containing 15 to 150 g of alkali, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atoms per liter of liquor, at temperatures between 30 and 70 ° C wetted, then squeezed and washed after 10 to 200 minutes at temperatures between 90 and 105 ° C at temperatures between 30 and 90 ° C.

Vorzugsweise werden die cellulosehaltigen Fasermaterialien mit al­kalischen Flotten, die pro Liter Flotte 2 bis 7 g Aktivsubstanz Phasentransferkatalysatoren und 0 bis 2 g Alkyl- und/oder Alkenyl­alkohole mit 6 bis 12 C-Atomen enthalten, benetzt.The cellulose-containing fiber materials are preferably wetted with alkaline liquors which contain 2 to 7 g of active substance phase transfer catalysts and 0 to 2 g of alkyl and / or alkenyl alcohols having 6 to 12 carbon atoms per liter of liquor.

Weiterer Erfindungsgegenstand ist die Verwendung von 1 bis 10 g Aktivsubstanz Phasentransferkatalysatoren pro Liter Flotte und 0 bis 5 g Alkyl- und/oder Alkenylalkohole mit 1 bis 18 C-Atomen pro Liter Flotte in der Alkalistufe zur Reinigung von cellulosehaltigen Fasermaterialien.Another object of the invention is the use of 1 to 10 g of active substance phase transfer catalysts per liter of liquor and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 carbon atoms per liter of liquor in the alkali stage for cleaning cellulosic fiber materials.

Als Phasentransferkatalysatoren eignen sich quartäre Ammoniumver­bindungen, planar gebaute makrocyclische Polyether, sogenannte Kronenether (Römpps Chemie-Lexikon, 8. Auflage, S. 2258, Franck'sche Verlagshandlung Stuttgart 1983) und/oder Kryptate (Römpps Chemielexikon, 8. Auflage, S. 2261, Franck'sche Verlags­handlung Stuttgart 1983). Vorzugsweise werden quartäre Ammonium­verbindungen und insbesondere solche der allgemeinen Formel I in der die Reste R¹ und R² Methyl, R³ einen gerad- oder verzweigtkettigen, cyclischen oder nichtcyclischen Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, R⁴ einen gerad- oder verzweigtkettigen Alkyl- oder Alkenylrest mit 1 bis 14 C-Atomen oder einen Benzylrest und X ein Halogen-, Sulfat-, Lactat-, Acetat- oder Citratanion bedeutet, eingesetzt. Quartäre Ammoniumverbindun­gen werden nach bekannten großtechnischen Verfahren hergestellt, indem beispielsweise tertiäre Amine mit einem oder zwei langket­tigen Alkyl- und/oder Alkenylresten mit Alkylierungsreagentien wie Methylchlorid, Methylbromid, Dimethylsulfat oder Benzylchlorid um­gesetzt werden (Winnacker/Küchler: "Chemische Technologie" 4. Aufl., Band 7, S. 126 bis 128, Carl Hanser Verlag, München 1986).Suitable phase transfer catalysts are quaternary ammonium compounds, planar macrocyclic polyethers, so-called crown ethers (Römpps Chemie-Lexikon, 8th edition, p. 2258, Franck'sche Verlagshandlung Stuttgart 1983) and / or cryptates (Römpps Chemielexikon, 8th edition, p. 2261 , Franck'sche Verlaghandlung Stuttgart 1983). Quaternary ammonium compounds and in particular those of the general formula I are preferred in which the radicals R¹ and R² are methyl, R³ is a straight or branched chain, cyclic or noncyclic alkyl or alkenyl radical having 6 to 22 C atoms, R⁴ is a straight or branched chain alkyl or alkenyl radical having 1 to 14 C atoms or one Benzyl radical and X is a halogen, sulfate, lactate, acetate or citrate anion. Quaternary ammonium compounds are produced by known industrial processes, for example by reacting tertiary amines with one or two long-chain alkyl and / or alkenyl radicals with alkylating reagents such as methyl chloride, methyl bromide, dimethyl sulfate or benzyl chloride (Winnacker / Küchler: "Chemical technology" 4th ed., Volume 7, pp. 126 to 128, Carl Hanser Verlag, Munich 1986).

Es kann vorteilhaft sein, die phasentransferkatalysatoren zusammen mit Alkyl- und/oder Alkenylalkoholen mit 1 bis 18 C-Atomen, vor­zugsweise mit 6 bis 12 C-Atomen einzusetzen. Alkyl- und/oder Alkenylalkohole können gerad- und/oder verzweigtkettig, natürlichen und/oder synthetischen Ursprungs sein. Ethanol, Butanol, Pentanol, Hexanol, Octanol, Decanol, Dodecanol, Hexadecanol, Octadecanol und/oder Octadecenol sind Beispiele für erfindungsgemäß einzuset­zende Alkyl- und/oder Alkenylalkohole.It may be advantageous to use the phase transfer catalysts together with alkyl and / or alkenyl alcohols with 1 to 18 carbon atoms, preferably with 6 to 12 carbon atoms. Alkyl and / or alkenyl alcohols can be straight and / or branched, natural and / or synthetic in origin. Ethanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, hexadecanol, octadecanol and / or octadecenol are examples of alkyl and / or alkenyl alcohols to be used according to the invention.

Cellulosehaltige Fasermaterialien wie Baumwolle und/oder Jute, werden zunächst mit alkalischen Flotten, die pro Liter 15 bis 150 g Alkali, beispielsweise NaOH und/oder KOH, 1 bis 10 g Aktivsubstanz Phasentransferkatalysatoren und 0 bis 5 g Alkyl- und/oder Alkenylalkohole mit 1 bis 18 C-Atomen enthalten, auf beispielsweise einer Benz Labor-Kontinueanlage bei Temperaturen zwischen 30 und 70 °C benetzt. Nach dem Abquetschen läßt man die auf beispielsweise Kaulen gewickelten Fasermaterialien 10 bis 200 Minuten bei Tempe­raturen zwischen 90 und 105 °C rotierend verweilen. Anschließend werden die Fasermaterialien bei Temperaturen zwischen 30 und 90 °C gewaschen.Cellulose-containing fiber materials such as cotton and / or jute are first made with alkaline liquors, which are 15 to 150 g per liter Contain alkali, for example NaOH and / or KOH, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atoms, for example on a Benz laboratory continuous system at temperatures between 30 and 70 ° C wetted. After squeezing, the fiber materials, which are wound on, for example, chewing, are left to rotate for 10 to 200 minutes at temperatures between 90 and 105.degree. The fiber materials are then washed at temperatures between 30 and 90 ° C.

Aufgrund der hohen Penetrationsgeschwindigkeiten, d.h. der hohen Verseifungsraten, die beim Einsatz phasentransferkatalysator­haltiger Alkaliflotten erzielt werden, kann die zum Waschen der cellulosehaltigen Fasermaterialien benötigte Temperatur deutlich gesenkt werden und/oder wird die Gesamtzeit der Alkalistufe deut­lich reduziert. Mit dem erfindungsgemäßen Verfahren lassen sich Wachse und/oder wachsartige Substanzen aus cellulosehaltigen Fa­sermaterialien bei Temperaturen zwischen 30 und 90 °C weitgehend durch Auswaschen entfernen. Es werden Fasermaterialien mit guter Saugfähigkeit erhalten.Due to the high penetration rates, ie the high saponification rates that are achieved when using alkali liquors containing phase transfer catalysts, the temperature required for washing the cellulose-containing fiber materials can be significantly reduced and / or the total time of the alkali stage is significantly reduced. With the method according to the invention, waxes and / or wax-like substances can be largely removed from cellulose-containing fiber materials at temperatures between 30 and 90 ° C. by washing out. Fiber materials with good absorbency are obtained.

BeispieleExamples Bestimmung der Verseifungsgeschwindigkeit von BaumwollwachsDetermination of the saponification rate of cotton wax

Zur Bestimmung der Verseifungsgeschwindigkeit wurden Penetrations­messungen durchgeführt. Hierzu wurden mit Baumwollwachs gefüllte Glaskapillare in Natronlauge, die quartäre Ammoniumverbindungen enthielt, getaucht. Die Lösungen befanden sich jeweils in einem Reagenzglas, welches in ein temperierbares Wasserbad eintauchte. Die Penetrationshöhe in den Kapillaren, die durch eine dunkle Ver­färbung des Wachses gekennzeichnet ist, wurde mit Hilfe eines Ka­thetometers auf 1/100 mm genau bestimmt. Die Tabellen 1 und 2 ent­halten die Ergebnisse der Penetrationsmessungen. Wenn nicht anders angegeben, wurden Lösungen mit 60 g/l NaOH und 5 g/l Aktivsubstanz quartäre Ammoniumverbindung eingesetzt. Tabelle 1 Relative Penetration (NaOH ohne Zusätze = 1), gemessen bei 70 °C Phasentransferkatalysator Zusatz relative Penetration Bardac 201) 2,4 Dimethyldidecylammoniumchlorid 1,75 Dimethyldioctylammoniumchlorid 2,2 Cyclododecyl-dimethyl-n-hexylammoniumchlorid 1,9 Cyclododecyl-dimethyl-n-octylammoniumchlorid 2,4 Dodigen 16112) 1,5 Dodigen 1611 Octanol 2 g/l 2 Dehyquart LDB3) 1,4 1) 25 Gew.-% Dimethyldidecylammoniumchlorid, 25 Gew.-% Dimethyldioctylammoniumchlorid, 50 Gew.-% Dimethyloctyldecylammoniumchlorid, Hersteller: Lonza 2) Alkyldimethylbenzylammoniumchlorid (70 Gew.-% C₁₂, 30 Gew.-% C₁₄), Hersteller: Hoechst AG 3) Dimethyl-C₁₂₋₁₄-alkylbenzylammoniumchlorid, Hersteller: Henkel-KGaA Tabelle 2 Penetration nach 24 Stunden, gemessen bei 50 °C Phasentransferkatalysator Penetration in mm - 0 Bardac 20 1) 0,95 Dimethyldidecylammoniumchlorid 1,6 Dimethyldioctylammoniumchlorid 1,8 Cyclododecyl-dimethyl-n-hexylammoniumchlorid 1,2 Cyclododecyl-dimethyl-n-octylammoniumchlorid 1,1 1) 25 Gew.-% Dimethyldidecylammoniumchlorid, 25 Gew.-% Dimethyldioctylammoniumchlorid, 50 Gew.-% Dimethyloctyldecylammoniumchlorid, Hersteller: Lonza Penetration measurements were carried out to determine the saponification rate. For this purpose, glass capillaries filled with cotton wax were immersed in sodium hydroxide solution containing quaternary ammonium compounds. The solutions were each in a test tube which was immersed in a temperature-controlled water bath. The penetration height in the capillaries, which is characterized by a dark discoloration of the wax, was determined with the aid of a cathetometer to within 1/100 mm. Tables 1 and 2 contain the results of the penetration measurements. Unless otherwise stated, solutions with 60 g / l NaOH and 5 g / l active substance quaternary ammonium compound were used. Table 1 Relative penetration (NaOH without additives = 1), measured at 70 ° C Phase transfer catalyst additive relative penetration Bardac 20 1) 2.4 Dimethyldidecylammonium chloride 1.75 Dimethyldioctylammonium chloride 2.2 Cyclododecyl-dimethyl-n-hexylammonium chloride 1.9 Cyclododecyldimethyl-n-octylammonium chloride 2.4 Dodigen 1611 2) 1.5 Dodigen 1611 Octanol 2 g / l 2nd Dehyquart LDB 3) 1.4 1) 25% by weight of dimethyldidecylammonium chloride, 25% by weight of dimethyldioctylammonium chloride, 50% by weight of dimethyloctyldecylammonium chloride, manufacturer: Lonza 2) Alkyldimethylbenzylammoniumchlorid (70 wt .-% C₁₂, 30 wt .-% C₁₄), manufacturer: Hoechst AG 3) Dimethyl-C₁₂₋₁₄-alkylbenzylammonium chloride, manufacturer: Henkel-KGaA Penetration after 24 hours, measured at 50 ° C Phase transfer catalyst Penetration in mm - 0 Bardac 20 1) 0.95 Dimethyldidecylammonium chloride 1.6 Dimethyldioctylammonium chloride 1.8 Cyclododecyldimethyl-n-hexylammonium chloride 1.2 Cyclododecyldimethyl-n-octylammonium chloride 1.1 1) 25% by weight of dimethyldidecylammonium chloride, 25% by weight of dimethyldioctylammonium chloride, 50% by weight of dimethyloctyldecylammonium chloride, manufacturer: Lonza

AnwendungsbeispielApplication example

Entschlichtetes Baumwollnesselgewebe wurde auf einer Benzlabor-­Kontinueanlage mit verschiedenen alkalihaltigen Flotten bei 70 °C imprägniert. Der Abquetscheffekt lag in allen Fällen bei 90 %. Nach einer Verweilzeit von 50 Minuten bei 102 °C in gesättigter Wasser­dampfatmosphäre wurden die Gewebe bei 50, 70 oder 90 °C gewaschen. In Tabelle 3 sind die prozentualen Abnahmen der Baumwollwachsan­schmutzungen nach dem Waschen angegeben. Tabelle 3 Prozentuale Abnahmen der Baumwollwachsanschmutzung von Baumwollnessel mit 0,26 Gew.-% Wachsanteil Flotte enthaltend pro 1 prozentuale Abnahme der Baumwollwachsanschmutzung nach dem Waschen bei 50 °C 70 °C 90 °C 30 g NaOH 23 % 31 % 38 % 30 g NaOH + 5 g Dimethyldioctylammoniumchlorid 50 % 54 % 58 % Desized cotton nettle fabric was impregnated on a Benzlabor continuous system with various alkaline liquors at 70 ° C. The squeezing effect was 90% in all cases. After a dwell time of 50 minutes at 102 ° C. in a saturated steam atmosphere, the fabrics were washed at 50, 70 or 90 ° C. Table 3 shows the percentage decreases in cotton wax stains after washing. Table 3 Percentage decrease in cotton wax contamination from cotton nettle with 0.26% by weight wax Fleet containing per 1 percentage decrease in cotton wax soiling after washing 50 ° C 70 ° C 90 ° C 30 g NaOH 23% 31% 38% 30 g NaOH + 5 g dimethyldioctylammonium chloride 50% 54% 58%

Claims (8)

1. Verfahren zur alkalischen Reinigung von cellulosehaltigen Fa­sermaterialien, dadurch gekennzeichnet, daß man cellulosehaltige Fasermaterialien mit alkalischen Flotten, enthaltend pro Liter Flotte 15 bis 150 g Alkali, 1 bis 10 g Aktivsubstanz phasentransferkatalysatoren und 0 bis 5 g Alkyl- und/oder Alkenylalkohole mit 1 bis 18 C-Atomen, bei Tempera­turen zwischen 30 und 70 °C benetzt, anschließend abquetscht und nach 10 bis 200 minütigem Verweilen bei Temperaturen zwi­schen 90 und 105 °C bei Temperaturen zwischen 30 und 90 °C wäscht.1. A process for the alkaline cleaning of cellulose-containing fiber materials, characterized in that cellulose-containing fiber materials with alkaline liquors containing 15 to 150 g of alkali per liter of liquor, 1 to 10 g of active substance phase transfer catalysts and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 C atoms, wetted at temperatures between 30 and 70 ° C, then squeezed and washed after 10 to 200 minutes at temperatures between 90 and 105 ° C at temperatures between 30 and 90 ° C. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die al­kalischen Flotten pro Liter 2 bis 7 g Aktivsubstanz Phasen­transferkatalysatoren und 0 bis 2 g Alkyl- und/oder Alkenylalkohole mit 6 bis 12 C-Atomen enthalten.2. The method according to claim 1, characterized in that the alkaline liquors contain 2 to 7 g of active substance phase transfer catalysts per liter and 0 to 2 g of alkyl and / or alkenyl alcohols having 6 to 12 carbon atoms per liter. 3. Verfahren nach einem oder beiden der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß als Phasentransferkatalysatoren quartäre Ammoniumverbindungen eingesetzt werden.3. The method according to one or both of claims 1 to 2, characterized in that quaternary ammonium compounds are used as phase transfer catalysts. 4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, da­durch gekennzeichnet, daß quartäre Ammoniumverbindungen der allgemeinen Formel I
Figure imgb0001
 in der die Reste R¹ und R² Methyl, R³ einen gerad- oder verzweigtkettigen, cyclischen oder nichtcyclischen Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, R⁴ einen gerad- oder verzweigtkettigen Alkyl- oder Alkenylrest mit 1 bis 14 C-Atomen oder einen Benzylrest und X ein Halogen-, Sulfat-, Lactat-, Acetat- oder Citratanion bedeuten, eingesetzt werden.4. The method according to one or more of claims 1 to 3, characterized in that quaternary ammonium compounds of the general formula I.
Figure imgb0001
 in which the radicals R¹ and R² are methyl, R³ is a straight or branched chain, cyclic or noncyclic alkyl or alkenyl radical having 6 to 22 C atoms, R⁴ is a straight or branched chain alkyl or alkenyl radical having 1 to 14 C atoms or one Benzyl radical and X is a halogen, sulfate, lactate, acetate or citrate anion can be used. 5. Verwendung von 1 bis 10 g Aktivsubstanz Phasentransfernkata­lysatoren pro 1 Flotte und 0 bis 5 g Alkyl- und/oder Alkenylalkohole mit 1 bis 18 C-Atomen pro 1 Flotte in der Al­kalistufe zur Reinigung von cellulosehaltigen Fasermaterialien.5. Use of 1 to 10 g of active substance phase transfer catalysts per 1 liquor and 0 to 5 g of alkyl and / or alkenyl alcohols with 1 to 18 carbon atoms per 1 liquor in the alkali stage for cleaning cellulosic fiber materials. 6. Verwendung nach Anspruch 5, dadurch gekennzeichnet, daß pro 1 Flotte 2 bis 7 g Aktivsubstanz Phasentransferkatalysatoren und 0 bis 2 g Alkyl- und/oder Alkenylalkohole mit 6 bis 12 C-Atomen verwendet werden.6. Use according to claim 5, characterized in that 2 to 7 g of active substance phase transfer catalysts and 0 to 2 g of alkyl and / or alkenyl alcohols having 6 to 12 carbon atoms are used per 1 liquor. 7. Verwendung nach einem oder beiden der Ansprüche 5 bis 6, da­durch gekennzeichnet, daß quartäre Ammoniumverbindungen als Phasentransferkatalysatoren verwendet werden.7. Use according to one or both of claims 5 to 6, characterized in that quaternary ammonium compounds are used as phase transfer catalysts. 8. Verwendung nach einem oder mehreren der Ansprüche 5 bis 7, da­durch gekennzeichnet, daß quartäre Ammoniumverbindungen der allgemeinen Formel I
Figure imgb0002
 in der die beste R¹ und R² Methyl, R³ einen gerad- oder verzweigtkettigen, cyclischen oder nichtcyclischen Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, R⁴ einen gerad- oder verzweigtkettigen Alkyl- oder Alkenylrest mit 1 bis 14 C-Atomen oder einen Benzylrest und X ein Halogen-, Sulfat-, Lactat-, Acetat- oder Citratanion bedeuten, verwendet werden.8. Use according to one or more of claims 5 to 7, characterized in that quaternary ammonium compounds of the general formula I.
Figure imgb0002
 in which the best R¹ and R² methyl, R³ is a straight or branched chain, cyclic or noncyclic alkyl or alkenyl radical having 6 to 22 carbon atoms, R⁴ is a straight or branched chain alkyl or alkenyl radical having 1 to 14 carbon atoms or one Benzyl radical and X is a halogen, sulfate, lactate, acetate or citrate anion can be used.
EP89122694A 1988-12-16 1989-12-08 Method for the alkaline cleaning of cellulosic textile materials Expired - Lifetime EP0378800B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89122694T ATE91511T1 (en) 1988-12-16 1989-12-08 PROCESS FOR THE ALKALINE CLEANING OF CELLULOSIC FIBER MATERIALS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3842342 1988-12-16
DE3842342A DE3842342A1 (en) 1988-12-16 1988-12-16 METHOD FOR ALKALINE CLEANING OF FIBER MATERIALS CONTAINING CELLULOSE

Publications (3)

Publication Number Publication Date
EP0378800A2 true EP0378800A2 (en) 1990-07-25
EP0378800A3 EP0378800A3 (en) 1991-08-14
EP0378800B1 EP0378800B1 (en) 1993-07-14

Family

ID=6369293

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89122694A Expired - Lifetime EP0378800B1 (en) 1988-12-16 1989-12-08 Method for the alkaline cleaning of cellulosic textile materials

Country Status (4)

Country Link
EP (1) EP0378800B1 (en)
AT (1) ATE91511T1 (en)
DE (2) DE3842342A1 (en)
ES (1) ES2057079T3 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2320036A (en) * 1996-12-03 1998-06-10 Hall Edward Ltd Increasing absorbency of cotton
WO2009003606A1 (en) * 2007-07-02 2009-01-08 Flasin Faser Gmbh High-strength fibrous material consisting of natural fibres, method for the production thereof, and use of same for producing composite materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE204817T1 (en) 1999-09-20 2001-09-15 Alain Faymonville LOAD SECURING SYSTEM FOR GLASS PANEL PACKAGES

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008839A1 (en) * 1978-09-08 1980-03-19 Akzo N.V. Process for preparing compositions containing quaternary ammonium compounds
EP0279138A1 (en) * 1987-01-13 1988-08-24 Rhovyl Fibres, yarns, textile articles based on polyvinyl chloride with an improved thermal resistance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008839A1 (en) * 1978-09-08 1980-03-19 Akzo N.V. Process for preparing compositions containing quaternary ammonium compounds
EP0279138A1 (en) * 1987-01-13 1988-08-24 Rhovyl Fibres, yarns, textile articles based on polyvinyl chloride with an improved thermal resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 96, no. 18, 03 Mai 82 Columbus, Ohio, USA JI,GUISUN ET AL: "STUDY ON A MECHANISM AND TECHNOLOGY OF THE ALKALINE SCOURING OF POLYESTERFIBERS" Seite 83; linke Spalte; ref. no. 144374 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2320036A (en) * 1996-12-03 1998-06-10 Hall Edward Ltd Increasing absorbency of cotton
WO2009003606A1 (en) * 2007-07-02 2009-01-08 Flasin Faser Gmbh High-strength fibrous material consisting of natural fibres, method for the production thereof, and use of same for producing composite materials
RU2471904C2 (en) * 2007-07-02 2013-01-10 Флазин Фазер Гмбх High-strength fiber material from natural fibers, method of its obtaining and its use for obtaining composite materials
US8784503B2 (en) 2007-07-02 2014-07-22 Flasin Faser Gmbh High-strength fibrous material consisting of natural fibres, method for the production thereof, and use of same for producing composite materials

Also Published As

Publication number Publication date
EP0378800B1 (en) 1993-07-14
ATE91511T1 (en) 1993-07-15
EP0378800A3 (en) 1991-08-14
DE58904917D1 (en) 1993-08-19
ES2057079T3 (en) 1994-10-16
DE3842342A1 (en) 1990-06-21

Similar Documents

Publication Publication Date Title
DE1961451C3 (en) Fabric softener and its use in a built-up fabric detergent
EP1194434B1 (en) Antimicrobial siloxane quat formulations and the production and use thereof
DE3046352A1 (en) Boundary-active quaternary ammonium compounds and their use for the treatment of textile and cellulose materials
EP0230565A1 (en) Laundry aftertreating agent
DE1195265B (en) Process for the antistatic, softening and bactericidal finishing of fabrics
EP0420802B1 (en) Aqueous, storage stable, low foaming wetting agent
DE2210087A1 (en) TEXTILE SOFTENERS
DE3730444C2 (en)
EP0378800B1 (en) Method for the alkaline cleaning of cellulosic textile materials
EP0151936A2 (en) Washing agent having laundry softening properties and process for its production
DE2641286A1 (en) Quat. ammonium derivs. useful as cellulose fibre softeners - derived from prod. of fatty acids and aminopropyl-diethanolamine
EP0589978B1 (en) Use of special alkyl glycosides as auxiliaries in the pretreatment of textiles
DE2949212C2 (en)
DE1619182B2 (en) PROCESS FOR SOFTENING TEXTILES
DE3111149C2 (en) Triammonium salts of citric or tricarballylic acid and processes for reducing the graying of textiles during washing or dry cleaning
DE1769447A1 (en) Process for softening water-absorbing, cellulose-containing textile fabrics
DE1904424B2 (en) PROCESS FOR OPTICAL LIGHTENING OF FIBER MATERIALS MADE OF POLYACRYLNITRILE
DE1469383A1 (en) Process for softening textiles
EP0415279B1 (en) Use of ethoxylated fatty acid amides as textil softeners
DE2155941C3 (en) Process for the production of quaternary cation-active starch ethers and liquid laundry care products containing them
EP0102930B1 (en) Wetting agent and its use as mercerising aid
WO2000066820A1 (en) Method for reducing the fibrillation tendency of cellulose fibres spun from solvents
DE1619081B2 (en) AVIVAGE AGENTS FOR TEXTILES
DE1769525A1 (en) Process for softening textile materials
DE1928814A1 (en) Process for the permanent finishing of textile materials containing cellulose fibers

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

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19920117

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL

17Q First examination report despatched

Effective date: 19920903

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 ES FR GB IT LI LU NL

REF Corresponds to:

Ref document number: 91511

Country of ref document: AT

Date of ref document: 19930715

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58904917

Country of ref document: DE

Date of ref document: 19930819

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931022

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

Ref country code: AT

Effective date: 19931208

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

Ref country code: LU

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

Effective date: 19931231

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
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2057079

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: FR

Payment date: 19961211

Year of fee payment: 8

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

Ref country code: DE

Payment date: 19961216

Year of fee payment: 8

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

Ref country code: CH

Payment date: 19961219

Year of fee payment: 8

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

Ref country code: ES

Payment date: 19961228

Year of fee payment: 8

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

Ref country code: NL

Payment date: 19961231

Year of fee payment: 8

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

Ref country code: BE

Payment date: 19970214

Year of fee payment: 8

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

Ref country code: GB

Payment date: 19971201

Year of fee payment: 9

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19971209

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

Ref country code: LI

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

Effective date: 19971231

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19971231

Ref country code: CH

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

Effective date: 19971231

Ref country code: BE

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

Effective date: 19971231

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19971231

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

Ref country code: NL

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

Effective date: 19980701

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980701

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

Ref country code: DE

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

Effective date: 19980901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: GB

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

Effective date: 19981208

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981208

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010301

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051208