EP0632970A2 - Cellulose acetate based products, their use in the manufacture of filtertows for the production of tobacco smoke filters as well as filtertows and tobacco smoke filters - Google Patents

Cellulose acetate based products, their use in the manufacture of filtertows for the production of tobacco smoke filters as well as filtertows and tobacco smoke filters Download PDF

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Publication number
EP0632970A2
EP0632970A2 EP94107825A EP94107825A EP0632970A2 EP 0632970 A2 EP0632970 A2 EP 0632970A2 EP 94107825 A EP94107825 A EP 94107825A EP 94107825 A EP94107825 A EP 94107825A EP 0632970 A2 EP0632970 A2 EP 0632970A2
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EP
European Patent Office
Prior art keywords
cellulose acetate
tobacco smoke
filter tow
filaments
filter
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
EP94107825A
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German (de)
French (fr)
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EP0632970A3 (en
EP0632970B1 (en
Inventor
Eberhard Dipl.-Chem. Teufel
Rolf Dipl.Biol.-Dr. Habil. Willmund
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Cerdia Produktions GmbH
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Rhone Poulenc Rhodia AG
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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068—Biodegradable or disintegrable
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive

Definitions

  • the invention relates to structures formed from cellulose acetate, in which or on the surface of which an additive is present.
  • the invention further relates to the use of structures formed from cellulose acetate in the form of filaments and / or staple fibers for the production of filter tow.
  • the invention also relates to a filter tow.
  • the invention also relates to the use of a filter tow for producing a tobacco smoke filter element.
  • the invention relates to a tobacco smoke filter element consisting of a section of a cross-axially compressed filter tow made of cellulose acetate filaments and / or cellulose acetate staple fibers hardened with the aid of a plasticizer for cellulose acetate or an adhesive.
  • Cigarette filters rot relatively slowly and are therefore a nuisance for large sections of the population in places where there is a lot of smoking.
  • Fibrous cellulose acetate with an acetyl number between 53% and 57% is used for the majority of cigarette filters today (cf., for example, US Pat. No. 2,953,837.
  • the numerical values given in this step namely 38% to 41%, correspond to the acetyl content previously mentioned values 53% to 57% for the acetyl number).
  • such a cellulose acetate is readily biodegradable, but the periods after which cigarette filters made of such a material are in Fibrous form has at least optically disappeared under the influence of environmental influences, too long from today's point of view.
  • cigarette filters for other structures made of cellulose acetate such as films, foils, plates or other objects made of cellulose acetate, for example by injection molding, extrusion or blow molding: when storing such structures in landfills, for example, it takes too long until these structures are completely biological are degraded.
  • US Pat. No. 5,141,006 describes filter tow and tobacco smoke filter elements made of cellulose acetate fibers in which an additive is present. According to the US Pat. No. 5,141,006, the additive contained in the cellulose acetate fibers is said in particular to improve the filter effectiveness for nicotine. However, US Pat. No. 5,141,006 also gives no indication of the possibility of accelerating the biodegradability of the filter tow and the tobacco smoke filter elements.
  • the invention is therefore based on the object of providing structures formed from cellulose acetate, in particular those which are suitable for mass production and / or are subject to food law and the tobacco regulation, and which have improved biodegradation under the influence of environmental influences.
  • the invention is also based on the object of using structures formed from cellulose acetate in the form of filaments and / or staple fibers for the production of filter tow with improved biodegradation under the influence of environmental influences, and the use of such a filter tow for producing a tobacco smoke filter element also with one propose improved biodegradation under the influence of environmental influences.
  • the invention is also based on the object of providing a filter tow based on structures formed from cellulose acetate in the form of filaments and / or staple fibers, and a tobacco smoke filter element formed from such a filter tow, which improve biodegradation under the action of Have environmental influences.
  • the object is achieved with regard to the structures formed from cellulose acetate by structures formed from cellulose acetate in which or on the surface of which an additive is present, which are characterized in that the additive consists of a nitrogen-containing organic compound, during the degradation of which by microorganisms basic decomposition products, in particular ammonia and / or - basic - compounds which have an NH group or NH groups and / or an NH2 group or NH2 groups.
  • the nitrogen-containing organic compound is preferably urea or a urea derivative. These substances are preferred because they are safe under food law and are available in large quantities and at an acceptable price.
  • the nitrogen-containing organic compound preferably also consists of a protein, beta-lactoglobulin being very particularly preferred. Proteins are also safe under food law, and beta-lactoglobulin applies to the fact that it is produced in large quantities as a by-product of little use in industry.
  • the nitrogen-containing organic compound is a condensation product of an aldehyde with ammonia or with an amine, this condensation product being very particularly preferably hexamethylenetetramine.
  • a further, biodegradable additive is preferably present in the structures formed from cellulose acetate.
  • the structures formed from cellulose acetate consist of an acetone-soluble cellulose acetate with an acetyl number of less than 53%, preferably an acetylene number between 50% and 52%. This feature means that the hydrolysis of the cellulose acetate preceding the biodegradation takes place in a shorter time.
  • the structures formed from cellulose acetate have the form of filaments, staple fibers, films, foils, rats or other objects obtained by injection molding, extrusion or blow molding; Of course, the structures formed from cellulose acetate can also have been obtained using other shaping methods.
  • the object is achieved according to the invention by a filter tow which has the features specified in the characterizing part of claim 10.
  • the breaking strength of the filter tow is preferably at most preferably at most This feature facilitates mechanical comminution prior to biodegradation.
  • the object is achieved according to the invention by a tobacco smoke filter element with the features specified in claim 13.
  • the tobacco smoke filter element contains the plasticizer for cellulose acetate in an amount of at most 6% by mass based on the mass of the cellulose acetate filaments and / or on the mass of the cellulose acetate staple fibers.
  • the tobacco smoke filter element according to the invention that less than half the surface of the cellulose acetate filaments and the cellulose acetate staple fibers is provided with the plasticizer for cellulose acetate or the adhesive. This also facilitates the mechanical comminution of the tobacco smoke filter element preceding the biodegradation.
  • triacetin is preferably used as the plasticizer for cellulose acetate, but other plasticizers, such as triethylene glycol diacetate, can also be used.
  • the nitrogen-containing organic compound is either soluble in acetone or dispersible in acetone in such a way that it is used in the manufacture of the filaments also spun out and thus not separated to any appreciable extent in the filtration upstream of the spinning process.
  • the additive consists of a nitrogen-containing organic compound.
  • the additive can consist of several nitrogen-containing organic compounds, ie a mixture of several nitrogen-containing organic compounds in the sense of the invention.
  • the invention is based on the principle that, due to the biodegradation of the nitrogen-containing organic compound and the resulting basic decomposition products, a basic (alkaline) environment is generated on the surface of the structures formed from cellulose acetate, which causes a partial hydrolysis of the cellulose acetate (for the decomposition of nitrogenous natural products see Hans G. Schlegel, Med Mikrobiologie, 6th, revised edition with the collaboration of Karin Schmidt, 1985, Georg Thieme Verlag Stuttgart - New York, pages 430 ff).
  • a filter tow in the sense of the invention is to be understood to mean a band of a large number of cellulose acetate filaments and / or cellulose acetate staple fibers (see also the definition of the term "filter tow” in, for example, German Offenlegungsschrift 41 09 603).
  • the filter tow according to the invention is preferably a band of a large number of cellulose acetate filaments, these filaments being able to be crimped, in particular crimped in the stuffer box.
  • a filament is to be understood as a practically endless fiber, and the term “spinning fiber” means a fiber of limited length (compare to these two definitions "Römpps Chemie-Lexikon", eighth, revised and extended edition, Franckh'sche Verlags Stuttgart, W. Keller & Co., Stuttgart / 1987, respectively volume 2, page 1283, and volume 5, page 3925 - with reference to DIN 60 001 T2 from December 1974).
  • the tobacco smoke filter element according to the invention is preferably a cigarette filter, but it can also be a filter for cigars, cigarillos or tobacco pipes.
  • acetyl number means the proportion of bound acetic acid in cellulose acetate, expressed in% by mass (see also Ullmann's Encyclopedia of Industrial Chemistry, Fifth, Completely Revised Edition, Volume A 5, pages 444 and 445 - VCH Verlagsgesellschaft mbH, D-6940 Weinheim, Federal Republic of Germany, 1986).
  • the structures according to the invention are also suitable for use as mass articles and as structures which are subject to food law and / or the tobacco regulation.
  • the structures formed from cellulose acetate according to the invention are cheaper than the known structures formed from cellulose acetate.
  • the filter tow and the tobacco smoke filter element according to the invention that, compared to known filter tow and known tobacco smoke filter elements made of cellulose acetate fiber material, they show an acceleration of the rotting rate under environmental influences; nevertheless, the storage of the filter tow and the tobacco smoke filter element according to the invention is readily possible under the conditions customary today without the risk of microbiological degradation.
  • the invention not only accelerates the mechanical comminution of the structures formed from cellulose acetate - by the microbiological degradation of the additive - but also accelerates the microbiological degradation of the cellulose acetate itself.
  • this additive can be introduced into the aforementioned solution of cellulose acetate in acetone, after which it is spun.
  • the tobacco smoke filter element according to the invention is essentially produced by providing the filter tow, consisting of cellulose acetate filaments and / or cellulose acetate staple fibers, with a plasticizer for cellulose acetate or an adhesive, subsequent transverse axial compression and optionally wrapping this filter tow with a wrapping strip, cutting the thus compressed and, if appropriate encased filter tows into individual tobacco smoke filter rods and finally cutting these tobacco smoke filter rods into individual tobacco smoke filter elements.
  • a cellulose acetate spinning solution with a solids content of 28% by mass of cellulose acetate and 0.5% by mass of titanium dioxide in acetone was prepared.
  • the water content of this spinning solution was adjusted to 3% by mass.
  • the cellulose acetate used had an acetyl number of 55.4% and a degree of polymerization (DP) of 220.
  • This spinning solution was filtered and spun by dry spinning on a conventional Filtertow spinning system.
  • the cellulose acetate filaments formed were combined into a tape, crimped using a stuffer box crimping machine and dried.
  • the resulting filter tow of cellulose acetate filaments crimped in the stuffer box was first placed loosely with the aid of a packing machine and then pressed into a bale; the bale had a residual moisture of 5.5% by mass.
  • the specification of the filter tow thus produced was 3 Y 35 HK.
  • This specification designation means Filament titre: 3.3 dtex Total titer: 38,500 dtex
  • the filter tow mentioned above was processed on a filter rod machine of the KDF 2 / AF 2 type from Körber AG, Hamburg, Federal Republic of Germany, at a line speed of 400 m / min to filter rods of the following specification: Length: 126 mm Diameter: 7.85 mm Draw resistance: 390 da Pa Weight of cellulose acetate: 690 mg
  • the smoked cigarette filters were carefully freed from tobacco residues and the various papers (cigarette paper, filter wrapping paper, tipping), weighed and individually sewn into a fine-mesh nylon net (polyamide net).
  • the samples prepared in this way were introduced into the aeration tank (clarification tank) of the biological purification stage of a sewage treatment plant for a period of 20 days. After taking the samples from the clarifier, the cigarette filters were carefully washed with deionized water, dried and weighed.
  • the average weight loss of the samples based on the amount of cellulose acetate was 8% (independent tests have found that both the smoke deposited in the cigarette filters and the triacetin are completely degraded within 20 days under the aforementioned conditions; this was at the calculation of the weight loss of cellulose acetate is taken into account). There was no significant difference in weight loss between the smoked cigarette filter and the un-smoked.
  • a spinning solution was prepared as in the comparative example, with the difference that 1.5 mass% of a finely sieved (pore size of the sieve: 20 ⁇ m) beta-lactoglobulin powder, manufactured by Bridel, France, was dispersed into the acetone beforehand.
  • this spinning solution was made into 50 kg filter tow with a tensile strength based on its total titer of spun, the cellulose acetate filaments being crimped and dried again in the stuffer box, and filter sticks, and again cigarette filters, were produced from the filter tow, as in the comparative example;
  • filter cigarettes were manufactured and smoked.
  • the smoking results were as follows: Condensate: 18.1 mg Nicotine: 1.25 mg Condensate retention: 42.0%
  • the weight loss based on the amount of cellulose acetate was on average 15% for both the smoked and the un-smoked cigarette filters (in independent tests it was found that beta-lactoglobulin degrades completely under the test conditions mentioned; this fact was additionally increased according to the procedure in the comparative example correction due to the complete elimination of the smoke and triacetin separated in the cigarette filters).
  • a spinning solution was prepared as in the comparative example, but with the difference that 1.5% by mass of urea had previously been introduced into the acetone and dissolved with heating at 60.degree.
  • the degradation test was carried out on the smoked and un-smoked cigarette filters in the clarifier of the sewage treatment plant.
  • the weight loss based on the amount of cellulose acetate was 10.5% on average in the case of the smoked and un-smoked cigarette filters (in independent studies it was found that urea is completely biologically complete under the test conditions mentioned degrades; This was taken into account, in accordance with the procedure in the comparative example and in Example 1, when calculating the weight loss of cellulose acetate - plus the correction due to the complete breakdown of the smoke and triacetin separated in the cigarette filters).
  • a spinning solution was prepared as in the comparative example, but with the difference that 1.5% by mass of hexamethylenetetramine had previously been introduced into the acetone and dissolved.
  • the degradation test was carried out on the smoked and un-smoked cigarette filters in the clarifier of the sewage treatment plant.
  • the weight loss in relation to the amount of cellulose acetate in the smoked and un-smoked cigarette filters averaged 25% (in independent tests it was found that hexamethylenetetramine degrades completely under the test conditions mentioned; this was, in accordance with the procedure in the comparative example, in Example 1 and in example 2, when calculating the weight loss of cellulose acetate - plus the correction because of the complete breakdown of the smoke and triacetin separated in the cigarette filters - again taken into account).
  • a film A with a thickness of 0.05 mm was cast from the spinning solution according to the comparative example.
  • a film B likewise with a thickness of 0.05 mm, was cast using the spinning solution according to Example 1.
  • a film C likewise with a thickness of 0.05 mm, was cast using the spinning solution according to Example 3.
  • the three films A, B and C were carefully washed with deionized water to remove any remaining acetone.
  • a modified test method for water-insoluble samples was developed based on the degradation test for water-soluble substances described in DIN 38 409 H52.
  • the microbiological degradation is measured by measuring the oxygen consumption of the microorganisms determined during the mining process.
  • the oxygen consumption is determined manometrically.
  • the carbon dioxide formed by the metabolism of the microorganisms is bound by sodium hydroxide and does not affect the pressure measurement.

Abstract

Described are shaped cellulose acetate articles within which or on whose surface is present an additive, said additive consisting of a nitrogen-containing organic compound whose degradation through microorganisms gives rise to basic decomposition products, in particular ammonia and/or basic compounds having an NH group or NH groups and/or an NH2 group or NH2 groups. The articles can have the shape of filaments, fibres, films, sheets, plates or other structures. The invention also relates to the use of the articles in the form of filaments and/or fibres for the manufacture of filter tow, to such a filter tow and to the use of such a filter tow for manufacturing a tobacco smoke filter element and to such a tobacco smoke filter element. The articles, the filter tow and the tobacco smoke filter element of the invention show improved biodegradation under the action of environmental influences, but the filter tow and the tobacco smoke filter element can be stored under the conditions customary today without risk of microbiological degradation.

Description

Die Erfindung betrifft aus Celluloseacetat geformte Gebilde, in denen oder auf deren Oberfläche ein Zusatzstoff vorhanden ist.
Die Erfindung betrifft ferner die Verwendung von aus Celluloseacetat geformten Gebilden in Form von Filamenten und/oder Spinnfasern zur Herstellung von Filtertow.
Die Erfindung betrifft auch ein Filtertow.
Außerdem betrifft die Erfindung die Verwendung eines Filtertows zur Herstellung eines Tabakrauchfilterelements.
Schließlich betrifft die Erfindung ein Tabakrauchfilterelement, bestehend aus einem Abschnitt eines queraxial verdichteten, mit Hilfe eines Weichmachers für Celluloseacetat oder eines Klebstoffes gehärteten Filtertows aus Celluloseacetatfilamenten und/oder Celluloseacetatspinnfasern.The invention relates to structures formed from cellulose acetate, in which or on the surface of which an additive is present.
The invention further relates to the use of structures formed from cellulose acetate in the form of filaments and / or staple fibers for the production of filter tow.
The invention also relates to a filter tow.
The invention also relates to the use of a filter tow for producing a tobacco smoke filter element.
Finally, the invention relates to a tobacco smoke filter element consisting of a section of a cross-axially compressed filter tow made of cellulose acetate filaments and / or cellulose acetate staple fibers hardened with the aid of a plasticizer for cellulose acetate or an adhesive.

Zigarettenfilter verrotten vergleichsweise langsam und sind deshalb an Plätzen, an denen viel geraucht wird, für weite Teile der Bevölkerung ein Ärgernis.Cigarette filters rot relatively slowly and are therefore a nuisance for large sections of the population in places where there is a lot of smoking.

Für die überwiegende Zahl der Zigarettenfilter wird heute faserförmiges Celluloseacetat mit einer Acetylzahl zwischen 53 % und 57 % eingesetzt (vgl. dazu beispielsweise die US-Patentschrift 2,953,837. Die in dieser Schritt angegebenen Zahlenwerte, nämlich 38 % bis 41 %, für den Acetylgehalt entsprechen den zuvor erwähnten Werten 53 % bis 57 % für die Acetylzahl).
Im Vergleich mit anderen, insbesondere synthetischen Polymeren ist ein solches Celluloseacetat zwar gut biologisch abbaubar, jedoch sind die Zeiträume, nach denen Zigarettenfilter aus einem solchen Material in Faserform unter der Einwirkung von Umgebungseinflüssen zumindest optisch verschwunden sind, unter heutigen Gesichtspunkten zu lang.Fibrous cellulose acetate with an acetyl number between 53% and 57% is used for the majority of cigarette filters today (cf., for example, US Pat. No. 2,953,837. The numerical values given in this step, namely 38% to 41%, correspond to the acetyl content previously mentioned values 53% to 57% for the acetyl number).
In comparison with other, in particular synthetic polymers, such a cellulose acetate is readily biodegradable, but the periods after which cigarette filters made of such a material are in Fibrous form has at least optically disappeared under the influence of environmental influences, too long from today's point of view.

Ähnliches wie für Zigarettenfilter gilt auch für andere Gebilde aus Celluloseacetat, wie Filme, Folien, Platten oder andere durch beispielsweise Spritzgießen, Extrudieren oder Blasformen erhaltene Gegenstände aus Celluloseacetat: bei der Lagerung solcher Gebilde auf beispielsweise Deponien dauert es zu lang, bis diese Gebilde vollständig biologisch abgebaut sind.The same applies as for cigarette filters for other structures made of cellulose acetate, such as films, foils, plates or other objects made of cellulose acetate, for example by injection molding, extrusion or blow molding: when storing such structures in landfills, for example, it takes too long until these structures are completely biological are degraded.

Filtertow und Tabakrauchfilterelemente aus Celluloseacetatfasern, auf deren Oberfläche ein Zusatzstoff vorhanden ist, sind beispielsweise aus der deutschen Patentschritt 1 079 521 bekannt. Gemäß der deutschen Patentschritt 1 079 521 dient der auf die Oberfläche der Celluloseacetatfasern aufgebrachte Zusatzstoff dazu, die Rauhheit dieser Fasern zu verbessern. Der deutschen Patentschrift 1 079 521 ist jedoch keinerlei Anregung zu entnehmen, die biologische Abbaubarkeit des Filtertows und der Tabakrauchfilterelemente zu beschleunigen.Filter tow and tobacco smoke filter elements made of cellulose acetate fibers, on the surface of which an additive is present, are known, for example, from German patent step 1 079 521. According to German patent step 1 079 521, the additive applied to the surface of the cellulose acetate fibers serves to improve the roughness of these fibers. However, no suggestion can be found in German patent specification 1 079 521 to accelerate the biodegradability of the filter tow and the tobacco smoke filter elements.

Ferner beschreibt die US-Patentschritt 5,141,006 Filtertow und Tabakrauchfilterelemente aus Celluloseacetatfasern, in denen ein Zusatzstoff vorhanden ist. Mit dem in den Celluloseacetatfasern befindlichen Zusatzstoff soll gemäß der US-Patentschrift 5,141,006 insbesondere die Filterwirksamkeit für Nikotin verbessert werden. Die US-Patentschrift 5,141,006 gibt jedoch ebenfalls keinen Hinweis auf die Möglichkeit zur Beschleunigung der biologischen Abbaubarkeit des Filtertows und der Tabakrauchfilterelemente.Furthermore, US Pat. No. 5,141,006 describes filter tow and tobacco smoke filter elements made of cellulose acetate fibers in which an additive is present. According to the US Pat. No. 5,141,006, the additive contained in the cellulose acetate fibers is said in particular to improve the filter effectiveness for nicotine. However, US Pat. No. 5,141,006 also gives no indication of the possibility of accelerating the biodegradability of the filter tow and the tobacco smoke filter elements.

Die deutsche Offenlegungsschrift 40 13 293 und die deutsche Offenlegungsschrift 40 13 304 beschreiben zwar Zigarettenfilter, die unter Einwirkung von Umgebungseinflüssen relativ schnell zersetzbar sind, jedoch bestehen diese Zigarettenfilter aus einem Abschnitt eines queraxial verdichteten Faserstrangs aus Fasern aus gesponnenem PHB (Polyhydroxybuttersäure) oder einem Copolymer aus PHB und PHV (Polyhydroxyvaleriansäure). Solche Polymere werden jedoch derzeit nicht, zumindest nicht in nennenswertem Umfang, zur Herstellung von Filtertow und Tabakrauchfilterelementen verwendet, was sich möglicherweise

  • mit der zu geringen industriellen Verfügbarkeit dieser Polymere,
  • mit der gegenüber Celluloseacetat unterschiedlichen Geschmacksbeeinflussung des Rauches
und
  • mit noch ungeklärten verfahrenstechnischen Problemen bei der Verarbeitung solcher Polymere zu Filtertow und Tabakrauchfilterelementen (beispielsweise in Zusammenhang mit der Härtung solcher Tabakrauchfilterelemente oder in Zusammenhang mit der Verwendung von problematischen Lösungsmitteln beim Erspinnen von Fäden aus diesen Polymeren)
erklären läßt.German Offenlegungsschrift 40 13 293 and German Offenlegungsschrift 40 13 304 describe cigarette filters which can be decomposed relatively quickly under the influence of environmental influences, but these cigarette filters consist of a section of a cross-axially compressed fiber strand made of fibers of spun PHB (polyhydroxybutyric acid) or a copolymer PHB and PHV (polyhydroxyvaleric acid). However, such polymers are currently being used not, at least not to a significant extent, used for the manufacture of filter tow and tobacco smoke filter elements, which may be
  • with the insufficient industrial availability of these polymers,
  • with the different taste influence of the smoke compared to cellulose acetate
and
  • with still unsettled procedural problems in the processing of such polymers into filter tow and tobacco smoke filter elements (for example in connection with the hardening of such tobacco smoke filter elements or in connection with the use of problematic solvents when spinning threads from these polymers)
can be explained.

Schließlich sind aus der deutschen Offenlegungsschrift 39 14 022 neue, biologisch durch Kompostieren leicht abbaubare Kunststoffmaterialien und ihre Verwendung zur Herstellung von Hüllen/Behältern für Öllichte, Ewiglichtölkerzen, Kompositionsöllichte, anderer Grablichtausführungen, Opferlichten und Folien bekannt. Als Kunststoffmaterial wird in der deutschen Offenlegungsschrift 39 14 022 ein solches auf der Basis von z.B. Celluloseacetat mit Zusätzen, wie Zitronensäureestern, Polyester, Phosphorsäureestern und organischen Eisenverbindungen, genannt. Als organische Eisenverbindungen können beispielsweise Ferrocene, d.h., Derivate von Bis-(zyklopentadienyl)-Eisen oder Eisen (II)-acetylacetonat, eingesetzt werden.
Die in der deutschen Offenlegungsschritt 39 14 022 beschriebenen Kunststoffmaterialien sind jedoch für die Anwendung zur Herstellung von Massenartikeln kaum oder nicht geeignet, da

  • die erforderliche Menge an den genannten Additiven sehr hoch ist, was im übrigen auch die Einsatzmöglichkeiten solcher Kunststoffmaterialien erheblich einschränkt,
und
  • die erwähnten Additive aufgrund ihres hohen Preises auch die aus den beschriebenen Kunststoffmaterialien hergestellten Gegenstände erheblich verteuern.
Finally, German published patent application 39 14 022 discloses new plastic materials that are easily biodegradable by composting and their use for the production of casings / containers for oil lights, eternal light candles, composition oil lights, other types of grave lights, sacrificial objects and foils. As a plastic material in German Offenlegungsschrift 39 14 022, one based on, for example, cellulose acetate with additives such as citric acid esters, polyester, phosphoric acid esters and organic iron compounds is mentioned. Ferrocenes, ie derivatives of bis (cyclopentadienyl) iron or iron (II) acetylacetonate, can be used as organic iron compounds, for example.
The plastic materials described in the German disclosure step 39 14 022 are, however, hardly or not suitable for use in the production of mass articles, since
  • the required amount of the additives mentioned is very high, which also considerably limits the possible uses of such plastic materials,
and
  • because of their high price, the additives mentioned also make the articles made from the plastic materials described considerably more expensive.

Hinzu kommt, daß für manche der in der deutschen Offenlegungsschrift 39 14 022 beschriebenen Additive eine lebensmittelrechtliche Zulassung oder eine Zulassung gemäß TVO (Tabakverordnung) sowohl wegen der erforderlichen Mengen als auch wegen deren Toxizität kaum oder nicht möglich ist, was der Einsatz der in der deutschen Offenlegungsschrift 30 14 022 beschriebenen Kunststoffmaterialien für beispielsweise Filtertow und Tabakrauchtilterelemente, wie Zigarettenfilter, unmöglich macht. Im übrigen ist der deutschen Offenlegungsschrift 39 14 022 keinerlei Hinweis auf die Möglichkeit zur Beschleunigung des biologischen Abbaus von Filtertow und Tabakrauchfilterelementen zu entnehmen; die in der deutschen Offenlegungsschrift 39 14 022 beschriebene Rezeptur wäre zur Herstellung von Filtertow und Tabakrauchfilterelementen wegen des zu hohen Weichmacheranteils im Celluloseacetat auch nicht geeignet.In addition, for some of the additives described in German Offenlegungsschrift 39 14 022, approval under food law or approval under the TVO (Tobacco Ordinance) is hardly possible or not possible, both because of the quantities required and because of their toxicity, which is what the use of in German Laid-open specification 30 14 022 plastic materials described for example filter tow and tobacco smoke filter elements, such as cigarette filters, makes impossible. For the rest, there is no reference to the possibility of accelerating the biodegradation of filter tow and tobacco smoke filter elements from German laid-open specification 39 14 022; the recipe described in German Offenlegungsschrift 39 14 022 would also not be suitable for the production of filter tow and tobacco smoke filter elements because of the excessive plasticizer content in the cellulose acetate.

Eine Zusammenschau des Standes der Technik zeigt also, daß

  • für Massenartikel aus Celluloseacetat immer noch ein Bedürfnis besteht, sie besser biologisch abbaubar zu machen,
und
  • auch für Gebilde aus Celluloseacetat, die dem Lebensmittelrecht und/oder der Tabakverordnung unterliegen, wie aus Celluloseacetatfasermaterial bestehendes Filtertow sowie Tabakrauchfilterelemente, die aus einem solchen Filtertow hergestellt sind, noch keine Lösung bekannt ist, deren biologischer Abbau zu beschleunigen.
A review of the prior art shows that
  • for bulk articles made from cellulose acetate there is still a need to make them more biodegradable,
and
  • also for structures made of cellulose acetate, which are subject to food law and / or the tobacco regulation Cellulose acetate fiber material existing filter tow and tobacco smoke filter elements that are made from such a filter tow, no solution is known to accelerate their biodegradation.

Der Erfindung liegt somit die Aufgabe zugrunde, aus Celluloseacetat geformte Gebilde, insbesondere solche, die als Massenartikel geeignet sind und/oder dem Lebensmittelrecht und der Tabakverordnung unterliegen, zur Verfügung zu stellen, die einen verbesserten biologischen Abbau unter der Einwirkung von Umgebungseinflüssen aufweisen.
Der Erfindung liegt auch die Aufgabe zugrunde, die Verwendung von aus Celluloseacetat geformten Gebilden in Form von Filamenten und/oder Spinnfasern zur Herstellung von Filtertow mit einem verbesserten biologischen Abbau unter der Einwirkung von Umgebungseinflüssen sowie die Verwendung eines solchen Filtertows zur Herstellung eines Tabakrauchfilterelements mit ebenfalls einem verbesserten biologischen Abbau unter der Einwirkung von Umgebungseinflüssen vorzuschlagen.
Schließlich liegt der Erfindung auch noch die Aufgabe zugrunde, ein Filtertow auf der Basis von aus Celluloseacetat geformten Gebilden in Form von Filamenten und/oder Spinnfasern sowie ein aus einem solchen Filtertow gebildetes Tabakrauchfilterelement zur Verfügung zu stellen, die einen verbesserten biologischen Abbau unter der Einwirkung von Umgebungseinflüssen aufweisen.The invention is therefore based on the object of providing structures formed from cellulose acetate, in particular those which are suitable for mass production and / or are subject to food law and the tobacco regulation, and which have improved biodegradation under the influence of environmental influences.
The invention is also based on the object of using structures formed from cellulose acetate in the form of filaments and / or staple fibers for the production of filter tow with improved biodegradation under the influence of environmental influences, and the use of such a filter tow for producing a tobacco smoke filter element also with one propose improved biodegradation under the influence of environmental influences.
Finally, the invention is also based on the object of providing a filter tow based on structures formed from cellulose acetate in the form of filaments and / or staple fibers, and a tobacco smoke filter element formed from such a filter tow, which improve biodegradation under the action of Have environmental influences.

Die Aufgabe wird bezüglich der aus Celluloseacetat geformten Gebilde gelöst durch aus Celluloseacetat geformte Gebilde, in denen oder auf deren Oberfläche ein Zusatzstoff vorhanden ist, die dadurch gekennzeichnet sind, daß der Zusatzstoff aus einer stickstoffhaltigen organischen Verbindung besteht, bei deren Abbau durch Mikroorganismen basische Zersetzungsprodukte, insbesondere Ammoniak und/oder - basische - Verbindungen, die eine NH-Gruppe oder NH-Gruppen und/oder eine NH₂-Gruppe oder NH₂-Gruppen aufweisen, entstehen.The object is achieved with regard to the structures formed from cellulose acetate by structures formed from cellulose acetate in which or on the surface of which an additive is present, which are characterized in that the additive consists of a nitrogen-containing organic compound, during the degradation of which by microorganisms basic decomposition products, in particular ammonia and / or - basic - compounds which have an NH group or NH groups and / or an NH₂ group or NH₂ groups.

Bevorzugt ist die stickstoffhaltige organische Verbindung Harnstoff oder ein Harnstoffderivat.
Diese Substanzen sind deshalb bevorzugt, da sie lebensmittelrechtlich unbedenklich und in großen Mengen und zu einem akzeptablen Preis verfügbar sind.The nitrogen-containing organic compound is preferably urea or a urea derivative.
These substances are preferred because they are safe under food law and are available in large quantities and at an acceptable price.

Bevorzugt besteht die stickstoffhaltige organische Verbindung auch aus einem Protein, wobei ganz besonders bevorzugt das Betalactoglobulin ist. Auch Proteine sind lebensmittelrechtlich unbedenklich, und für das Betalactoglobulin gilt, daß es bei der Käseherstellung in großen Mengen als industriell wenig genutztes Nebenprodukt anfällt.The nitrogen-containing organic compound preferably also consists of a protein, beta-lactoglobulin being very particularly preferred. Proteins are also safe under food law, and beta-lactoglobulin applies to the fact that it is produced in large quantities as a by-product of little use in industry.

Ferner ist es bevorzugt, daß die stickstoffhaltige organische Verbindung ein Kondensationsprodukt aus einem Aldehyd mit Ammoniak oder mit einem Amin ist, wobei dieses Kondensationsprodukt ganz besonders bevorzugt Hexamethylentetramin ist.It is further preferred that the nitrogen-containing organic compound is a condensation product of an aldehyde with ammonia or with an amine, this condensation product being very particularly preferably hexamethylenetetramine.

Schließlich ist es bevorzugt, daß die stickstoffhaltige organische Verbindung eine cyclische Verbindung, insbesondere Carbazol (= Dibenzopyrrol, Diphenylenimid), ist.Finally, it is preferred that the nitrogen-containing organic compound is a cyclic compound, in particular carbazole (= dibenzopyrrole, diphenylene imide).

Selbstverständlich können jedoch auch andere stickstoffhaltige organische Verbindungen eingesetzt werden, wobei man jedoch darauf achten sollte, daß diese möglichst nicht toxisch sind.Of course, however, other nitrogen-containing organic compounds can also be used, although care should be taken to ensure that these are as non-toxic as possible.

Vorzugsweise ist in den aus Celluloseacetat geformten Gebilden noch ein weiter, biologisch abbaubarer Zusatzstoff vorhanden.A further, biodegradable additive is preferably present in the structures formed from cellulose acetate.

Ferner ist es bevorzugt, daß die aus Celluloseacetat geformten Gebilde aus einem acetonlöslichen Celluloseacetat mit einer Acetylzahl von weniger als 53 %, vorzugsweise einer Acetyzahl zwischen 50 % und 52 %, bestehen.
Dieses Merkmal bewirkt, daß die dem biologischen Abbau vorausgehende Hydrolyse des Celluloseacetats in kürzerer Zeit vonstatten geht.It is further preferred that the structures formed from cellulose acetate consist of an acetone-soluble cellulose acetate with an acetyl number of less than 53%, preferably an acetylene number between 50% and 52%.
This feature means that the hydrolysis of the cellulose acetate preceding the biodegradation takes place in a shorter time.

Außerdem ist es bevorzugt, daß die aus Celluloseacetat geformten Gebilde die Form von Filamenten, Spinnfasern, Filmen, Folien, Ratten oder anderen durch Spritzgießen, Extrudieren oder Blasformen erhaltenen Gegenständen aufweisen; selbstverständlich können die aus Celluloseacetat geformten Gebilde auch mit Hilfe von anderen Formgebungsmethoden erhalten worden sein.It is also preferred that the structures formed from cellulose acetate have the form of filaments, staple fibers, films, foils, rats or other objects obtained by injection molding, extrusion or blow molding; Of course, the structures formed from cellulose acetate can also have been obtained using other shaping methods.

Bezüglich der Verwendung der aus Celluloseacetat geformten Gebilde in Form von Filamenten und/oder Spinnfasern zur Herstellung von Filtertow wird die Aufgabe durch die im Anspruch 9 angegebenen Merkmale gelöst.With regard to the use of the structures formed from cellulose acetate in the form of filaments and / or staple fibers for the production of filter tow, the object is achieved by the features specified in claim 9.

Bezüglich des Filtertows wird die gestellte Aufgabe erfindungsgemäß gelöst durch ein Filtertow, das die im Kennzeichen des Anspruchs 10 angegebenen Merkmale aufweist.With regard to the filter tow, the object is achieved according to the invention by a filter tow which has the features specified in the characterizing part of claim 10.

Bevorzugt beträgt die auf den Gesamttiter bezogene Reißkraft des Filtertows höchstens

Figure imgb0001

vorzugsweise höchstens
Figure imgb0002

Durch dieses Merkmal wird die dem biologischen Abbau vorausgehende mechanische Zerkleinerung erleichtert.The breaking strength of the filter tow, based on the total titer, is preferably at most
Figure imgb0001

preferably at most
Figure imgb0002

This feature facilitates mechanical comminution prior to biodegradation.

Bezüglich der Verwendung des Filtertows zur Herstellung eines Tabakrauchfilterelements wird die gestellte Aufgabe erfindungsgemäß gelöst durch die im Anspruch 12 angegebenen Merkmale.With regard to the use of the filter tow for producing a tobacco smoke filter element, the object is achieved according to the invention by the features specified in claim 12.

Bezüglich des Tabakrauchfilterelements wird die gestellte Aufgabe erfindungsgemäß gelöst durch ein Tabakrauchfilterelement mit den im Anspruch 13 angegebenen Merkmalen.With regard to the tobacco smoke filter element, the object is achieved according to the invention by a tobacco smoke filter element with the features specified in claim 13.

Beim erfindungsgemäßen Tabakrauchfilterelement ist es bevorzugt, daß

  • der Weichmacher für Celluloseacetat biologisch abbaubar ist und/oder den mikrobiologischen Bewuchs der Celluloseacetatfilamente und der Celluloseacetatspinnfasern beschleunigt
oder
  • der Klebstoff wasserlöslich und/oder biologisch abbaubar ist,
wobei es ganz besonders bevorzugt ist, daß der Klebstoff ein Stärkeleim oder ein Polyvinylacetatleim ist.
Durch Einsatz eines wasserlöslichen und/oder biologisch abbaubaren Klebstoffes wird erreicht, daß die dem biologischen Abbau vorausgehende mechanische Zerkleinerung des Tabakrauchfilterelements erleichtert wird.In the tobacco smoke filter element according to the invention, it is preferred that
  • the plasticizer for cellulose acetate is biodegradable and / or accelerates the microbiological growth of the cellulose acetate filaments and the cellulose acetate staple fibers
or
  • the adhesive is water-soluble and / or biodegradable,
it being most preferred that the adhesive be a starch glue or a polyvinyl acetate glue.
The use of a water-soluble and / or biodegradable adhesive ensures that the mechanical comminution of the tobacco smoke filter element preceding the biodegradation is facilitated.

Ferner ist es bevorzugt, daß das Tabakrauchfilterelement den Weichmacher für Celluloseacetat in einer Menge von höchstens 6 Masse-% bezogen auf die Masse der Celluloseacetatfilamente und/oder auf die Masse der Celluloseacetatspinnfasern enthält.
Obwohl mit diesem Merkmal eine gewisse Reduzierung der Härte des Tabakrauchfilterelements in Kauf genommen wird, erreicht man damit wiederum eine Erleichterung der dem biologischen Abbau vorausgehenden mechanischen Zerkleinerung des Tabakrauchfilterelements.It is further preferred that the tobacco smoke filter element contains the plasticizer for cellulose acetate in an amount of at most 6% by mass based on the mass of the cellulose acetate filaments and / or on the mass of the cellulose acetate staple fibers.
Although a certain reduction in the hardness of the tobacco smoke filter element is accepted with this feature, the mechanical comminution of the tobacco smoke filter element preceding the biodegradation is again facilitated.

Schließlich ist es beim erfindungsgemäßen Tabakrauchfilterelement noch bevorzugt, daß weniger als die Hälfte der Oberfläche der Celluloseactatfilamente und der Celluloseacetatspinnfasern mit dem Weichmacher für Celluloseacetat oder dem Klebstoff versehen ist. Auch hiermit wird die dem biologischen Abbau vorausgehende mechanische Zerkleinerung des Tabakrauchfilterelements erleichtert.Finally, it is still preferred in the tobacco smoke filter element according to the invention that less than half the surface of the cellulose acetate filaments and the cellulose acetate staple fibers is provided with the plasticizer for cellulose acetate or the adhesive. This also facilitates the mechanical comminution of the tobacco smoke filter element preceding the biodegradation.

Als Weichmacher für Celluloseacetat wird gemäß der Erfindung bevorzugt Triacetin eingesetzt, jedoch können auch andere Weichmacher, wie Triethylenglykoldiacetat, verwendet werden.According to the invention, triacetin is preferably used as the plasticizer for cellulose acetate, but other plasticizers, such as triethylene glycol diacetate, can also be used.

Soweit die erfindungsgemäßen Gebilde in Form von Filamenten oder Fasern vorliegen, ist es bevorzugt, daß die stickstoffhaltige organische Verbindung entweder in Aceton löslich oder in der Weise in Aceton dispergierbar ist, daß sie bei der Herstellung der Filamente mitausgesponnen und somit bei der dem Spinnprozeß vorgeschalteten Filtration nicht in nennenswertem Umfang abgeschieden wird.If the structures according to the invention are in the form of filaments or fibers, it is preferred that the nitrogen-containing organic compound is either soluble in acetone or dispersible in acetone in such a way that it is used in the manufacture of the filaments also spun out and thus not separated to any appreciable extent in the filtration upstream of the spinning process.

Gemäß der Erfindung besteht der Zusatzstoff aus einer stickstoffhaltigen organischen Verbindung. Selbstverständlich beinhaltet dieses auch, daß der Zusatzstoff aus mehreren stickstoffhaltigen organischen Verbindungen, also aus einem Gemisch aus mehreren stickstoffhaltigen organischen Verbindungen im Sinne der Erfindung bestehen kann.According to the invention, the additive consists of a nitrogen-containing organic compound. Of course, this also means that the additive can consist of several nitrogen-containing organic compounds, ie a mixture of several nitrogen-containing organic compounds in the sense of the invention.

Der Erfindung liegt das Prinzip zugrunde, daß, bedingt durch den biologischen Abbau der stickstoffhaltigen organischen Verbindung und die dabei entstehenden basischen Zersetzungsprodukte, auf der Oberfläche der aus Celluloseacetat geformten Gebilde ein basisches (alkalisches) Milieu erzeugt wird, das eine partielle Hydrolyse des Celluloseacetats bewirkt (zum Abbau von stickstoffhaltigen Naturstoffen vgl. Hans G. Schlegel, Allgemeine Mikrobiologie, 6., überarbeitete Auflage unter Mitarbeit von Karin Schmidt, 1985, Georg Thieme Verlag Stuttgart - New York, Seiten 430 ff).The invention is based on the principle that, due to the biodegradation of the nitrogen-containing organic compound and the resulting basic decomposition products, a basic (alkaline) environment is generated on the surface of the structures formed from cellulose acetate, which causes a partial hydrolysis of the cellulose acetate ( for the decomposition of nitrogenous natural products see Hans G. Schlegel, Allgemeine Mikrobiologie, 6th, revised edition with the collaboration of Karin Schmidt, 1985, Georg Thieme Verlag Stuttgart - New York, pages 430 ff).

Unter einem Filtertow im Sinne der Erfindung soll ein Band aus einer Vielzahl von Celluloseacetatfilamenten und/oder Celluloseacetatspinnfasern verstanden werden (vergleiche dazu auch die Definition des Begriffes "Filtertow" in beispielsweise der deutschen Offenlegungsschrift 41 09 603). Vorzugsweise ist das erfindungsgemäße Filtertow ein Band aus einer Vielzahl von Celluloseacetatfilamenten, wobei diese Filamente gekräuselt, insbesondere stauchkammergekräuselt sein können.
Unter einem Filament ist eine praktisch endlose Faser zu verstehen, und der Ausdruck "Spinnfaser" bedeutet eine Faser begrenzter Länge (vergleiche zu diesen beiden Definitionen "Römpps Chemie-Lexikon", achte, neubearbeitete und erweiterte Auflage, Franckh'sche Verlagshandlung, W. Keller & Co., Stuttgart/1987, resp. Band 2, Seite 1283, und Band 5, Seite 3925 - unter Hinweis auf DIN 60 001 T2 vom Dezember 1974).A filter tow in the sense of the invention is to be understood to mean a band of a large number of cellulose acetate filaments and / or cellulose acetate staple fibers (see also the definition of the term "filter tow" in, for example, German Offenlegungsschrift 41 09 603). The filter tow according to the invention is preferably a band of a large number of cellulose acetate filaments, these filaments being able to be crimped, in particular crimped in the stuffer box.
A filament is to be understood as a practically endless fiber, and the term "spinning fiber" means a fiber of limited length (compare to these two definitions "Römpps Chemie-Lexikon", eighth, revised and extended edition, Franckh'sche Verlagshandlung, W. Keller & Co., Stuttgart / 1987, respectively volume 2, page 1283, and volume 5, page 3925 - with reference to DIN 60 001 T2 from December 1974).

Das Tabakrauchfilterelement gemäß der Erfindung ist vorzugsweise ein Zigarettenfilter, es kann jedoch auch ein Filter für Zigarren, Zigarillos oder Tabakpfeifen sein.
Unter Acetylzahl versteht man im Sinne der Erfindung den Anteil an gebundener Essigsäure im Celluloseacetat, ausgedrückt in Masse-% (vergleiche dazu auch Ullmann's Encyclopedia of Industrial Chemistry, Fifth, Completely Revised Edition, Volume A 5, Seiten 444 und 445 - VCH Verlagsgesellschaft mbH, D-6940 Weinheim, Federal Republic of Germany, 1986).The tobacco smoke filter element according to the invention is preferably a cigarette filter, but it can also be a filter for cigars, cigarillos or tobacco pipes.
For the purposes of the invention, acetyl number means the proportion of bound acetic acid in cellulose acetate, expressed in% by mass (see also Ullmann's Encyclopedia of Industrial Chemistry, Fifth, Completely Revised Edition, Volume A 5, pages 444 and 445 - VCH Verlagsgesellschaft mbH, D-6940 Weinheim, Federal Republic of Germany, 1986).

Mit der Erfindung werden folgende Vorteile erreicht:
Die erfindungsgemäßen, aus Celluloseacetat geformten Gebilde eignen sich auch für die Anwendung als Massenartikel sowie als Gebilde, die dem Lebensmittelrecht und/oder der Tabakverordnung unterliegen. Außerdem sind die erfindungsgemäßen, aus Celluloseacetat geformten Gebilde preiswerter als die bekannten, aus Celluloseacetat geformten Gebilde.The following advantages are achieved with the invention:
The structures according to the invention, formed from cellulose acetate, are also suitable for use as mass articles and as structures which are subject to food law and / or the tobacco regulation. In addition, the structures formed from cellulose acetate according to the invention are cheaper than the known structures formed from cellulose acetate.

Für das Filtertow und das Tabakrauchfilterelement gemäß der Erfindung gilt, daß sie gegenüber bekanntem Filtertow und bekannten Tabakrauchfilterelementen aus Celluloseacetatfasermaterial eine Beschleunigung der Verrottungsgeschwindigkeit unter Umgebungseinflüssen zeigen; dennoch ist die Lagerung des Filtertows und des Tabakrauchfilterelements gemäß der Erfindung unter den heute üblichen Bedingungen ohne die Gefahr des mikrobiologischen Abbaus ohne weiteres möglich.It applies to the filter tow and the tobacco smoke filter element according to the invention that, compared to known filter tow and known tobacco smoke filter elements made of cellulose acetate fiber material, they show an acceleration of the rotting rate under environmental influences; nevertheless, the storage of the filter tow and the tobacco smoke filter element according to the invention is readily possible under the conditions customary today without the risk of microbiological degradation.

Mit der Erfindung wird nicht nur eine Beschleunigung der mechanischen Zerkleinerung der aus Celluloseacetat geformten Gebilde - durch den mikrobiologischen Abbau des Zusatzstoffes - erreicht, sondern auch eine Beschleunigung des mikrobiologischen Abbaus des Celluloseacetats selbst.The invention not only accelerates the mechanical comminution of the structures formed from cellulose acetate - by the microbiological degradation of the additive - but also accelerates the microbiological degradation of the cellulose acetate itself.

Die Herstellung des Filtertows gemäß der Erfindung erfolgt durch im wesentlichen

  • Erspinnen von Celluloseacetatfilamenten durch Pressen einer Lösung von Celluloseacetat in Aceton durch eine Spinndüse mit mehreren Öffnungen und gegebenenfalls anschließendes Zerschneiden der Celluloseacetatfilamente zu Celluloseacetatspinnfasern
und
  • Zusammenfassen einer Vielzahl der so erhaltenen Celluloseacetatfilamente und/oder Celluloseacetatspinnfasern zu einem Filtertow.
The filter tow according to the invention is essentially produced by
  • Spinning of cellulose acetate filaments by pressing a solution of cellulose acetate in acetone through a spinneret with several openings and optionally subsequently cutting the cellulose acetate filaments into cellulose acetate staple fibers
and
  • Combining a large number of the cellulose acetate filaments and / or cellulose acetate staple fibers thus obtained to form a filter tow.

Um zu erreichen, daß der Zusatzstoff (die stickstoffhaltige organische Verbindung oder mehrere dieser Verbindungen) in den Celluloseacetatfilamenten und in den Celluloseacetatspinnfasern vorhanden ist, kann dieser Zusatzstoff in die zuvor erwähnte Lösung von Celluloseacetat in Aceton eingegeben werden, wonach diese versponnen wird.In order to ensure that the additive (the nitrogen-containing organic compound or several of these compounds) is present in the cellulose acetate filaments and in the cellulose acetate staple fibers, this additive can be introduced into the aforementioned solution of cellulose acetate in acetone, after which it is spun.

Die Herstellung des Tabakrauchfilterelements gemäß der Erfindung erfolgt im wesentlichen durch Versehen des Filtertows, bestehend aus Celluloseacetatfilamenten und/oder Celluloseacetatspinnfasern, mit einem Weichmacher für Celluloseacetat oder einem Klebstoff, anschließendes queraxiales Verdichten und gegebenenfalls Umhüllen dieses Filtertows mit einem Umhüllungsstreifen, Zerschneiden des so verdichteten und gegebenenfalls umhüllten Filtertows in einzelne Tabakrauchfilterstäbe und schließlich Zerschneiden dieser Tabakrauchfilterstäbe in einzelne Tabakrauchfilterelemente.The tobacco smoke filter element according to the invention is essentially produced by providing the filter tow, consisting of cellulose acetate filaments and / or cellulose acetate staple fibers, with a plasticizer for cellulose acetate or an adhesive, subsequent transverse axial compression and optionally wrapping this filter tow with a wrapping strip, cutting the thus compressed and, if appropriate encased filter tows into individual tobacco smoke filter rods and finally cutting these tobacco smoke filter rods into individual tobacco smoke filter elements.

Um zu erreichen, daß der Zusatzstoff (die stickstoffhaltige organische Verbindung oder mehrere dieser Verbindungen) auf der Oberfläche der Celluloseacetatfilamente und der Celluloseacetatspinnfasern vorhanden ist, kann dieser Zusatzstoff

  • während der Herstellung des Filtertows, aber nach der Bildung der Celluloseacetatfilamente auf diese Filamente oder auf die daraus gebildeten Celluloseacetatspinnfasern aufgebracht werden (beispielsweise kann der Zusatzstoff unmittelbar vor dem Zerschneiden der Celluloseacetatfilamente zu Celluloseacetatspinnfasern auf die Filamente aufgebracht werden, oder der Zusatzstoff kann auf das fertige Filtertow, also nach dem Zusammenfassen der Celluloseacetatfilamente und/oder Celluloseacetatspinnfasern zu einem Filtertow auf die Filamente und/oder Spinnfasern aufgebracht werden)
oder
  • während der Herstellung des Tabakrauchfilterelements, aber vor dem queraxialen Verdichten des Filtertows auf die Celluloseacetatfilamente und/oder Celluloseacetatspinnfasern aufgebracht werden (bevorzugt wird der Zusatzstoff unmittelbar nach dem Versehen des Filtertows mit einem Weichmacher oder einem Klebstoff auf die Celluloseacetatfilamente und/oder Celluloseacetatspinnfasern aufgebracht).
In order to ensure that the additive (the nitrogen-containing organic compound or more of these compounds) is present on the surface of the cellulose acetate filaments and the cellulose acetate staple fibers, this additive can
  • during the manufacture of the filter tow, but after the formation of the cellulose acetate filaments are applied to these filaments or to the cellulose acetate staple fibers formed therefrom (for example, the additive can be applied to the filaments immediately before the cellulose acetate filaments are cut into cellulose acetate staple fibers, or the additive can be applied to the finished filter tow after combining the cellulose acetate filaments and / or cellulose acetate staple fibers to form a filter tow onto which the filaments and / or staple fibers are applied)
or
  • be applied to the cellulose acetate filaments and / or cellulose acetate staple fibers during the manufacture of the tobacco smoke filter element, but before the filter tow is compressed axially (the additive is preferably applied to the cellulose acetate filaments and / or cellulose acetate staple fibers immediately after the filter tow has been provided with a plasticizer or an adhesive).

Die Erfindung wird nachstehend anhand von Beispielen noch näher erläutert.The invention is explained in more detail below with the aid of examples.

VergleichsbeispielComparative example

Es wurde eine Celluloseacetat-Spinnlösung mit einem Feststoffgehalt von 28 Masse-% Celluloseacetat und 0,5 Masse-% Titandioxid in Aceton hergestellt. Der Wassergehalt dieser Spinnlösung wurde auf 3 Masse-% eingestellt.
Das eingesetzte Celluloseacetat hatte eine Acetylzahl von 55,4 % und einen Polymerisationsgrad (DP) von 220. Diese Spinnlösung wurde filtriert und durch Trockenspinnen auf einer herkömmlichen Filtertow-Spinnanlage versponnen. Die gebildeten Celluloseacetatfilamente wurden zu einem Band zusammengefaßt, mit Hilfe einer Stauchkammerkräuselmaschine gekräuselt und getrocknet. Das so entstandene Filtertow aus stauchkammergekräuselten Celluloseacetatfilamenten wurde mit Hilfe einer Packmaschine zunächst lose abgelegt und anschließend zu einem Ballen verpresst; der Ballen hatte eine Restfeuchte von 5,5 Masse-%.
Die Spezifikation des so hergestellten Filtertows war 3 Y 35 HK. Diese Spezifikationsbezeichnung bedeutet Filamenttiter: 3,3 dtex Gesamttiter: 38.500 dtex Querschnittsform der Celluloseacetatfilamente: Y. A cellulose acetate spinning solution with a solids content of 28% by mass of cellulose acetate and 0.5% by mass of titanium dioxide in acetone was prepared. The water content of this spinning solution was adjusted to 3% by mass.
The cellulose acetate used had an acetyl number of 55.4% and a degree of polymerization (DP) of 220. This spinning solution was filtered and spun by dry spinning on a conventional Filtertow spinning system. The cellulose acetate filaments formed were combined into a tape, crimped using a stuffer box crimping machine and dried. The resulting filter tow of cellulose acetate filaments crimped in the stuffer box was first placed loosely with the aid of a packing machine and then pressed into a bale; the bale had a residual moisture of 5.5% by mass.
The specification of the filter tow thus produced was 3 Y 35 HK. This specification designation means Filament titre: 3.3 dtex Total titer: 38,500 dtex Cross-sectional shape of the cellulose acetate filaments: Y.

Die Reißkraft des Filtertows bezogen auf den Gesamttiter dieses Filtertows betrug

Figure imgb0003
The tear strength of the filter tow based on the total titer of this filter tow was
Figure imgb0003

Das zuvor erwähnte Filtertow wurde auf einer Filterstabmaschine des Typs KDF 2/AF 2 der Firma Körber AG, Hamburg, Bundesrepublik Deutschland, mit einer Stranggeschwindigkeit von 400 m/min zu Filterstäben folgender Spezifikation verarbeitet: Länge: 126 mm Durchmesser: 7,85 mm Zugwiderstand: 390 da Pa Gewicht an Celluloseacetat: 690 mg The filter tow mentioned above was processed on a filter rod machine of the KDF 2 / AF 2 type from Körber AG, Hamburg, Federal Republic of Germany, at a line speed of 400 m / min to filter rods of the following specification: Length: 126 mm Diameter: 7.85 mm Draw resistance: 390 da Pa Weight of cellulose acetate: 690 mg

Bei der Produktion dieser Filterstäbe wurde als Weichmacher für das Celluloseacetat Triacetin aufgebracht, und zwar so, daß die fertigen Filterstäbe 55 mg Triacetin pro Filterstab enthielten.In the production of these filter rods, triacetin was applied as a plasticizer for the cellulose acetate, in such a way that the finished filter rods contained 55 mg of triacetin per filter rod.

Diese Filterstäbe wurden auf einer Laborfilteransetzmaschine des Typs Lab Max der zuvor erwähnten Firma Körber AG auf eine Länge von zunächst 84 mm gekürzt und anschließend nach dem üblichen Filteransetzverfahren auf der zuvor erwähnten Lab Max genannten Vorrichtung mit einem Tabakstrang des Typs "American Blend" gekoppelt, wodurch schließlich Filterzigaretten mit einer Filterlänge von 21 mm entstanden.These filter rods were first shortened to a length of 84 mm on a laboratory filter attachment machine of the type Lab Max from the aforementioned company Körber AG and then using the conventional filter attachment method on the device named Lab Max with a tobacco rod of the "American Blend" type. coupled, which ultimately resulted in filter cigarettes with a filter length of 21 mm.

Von den so hergestellten Filterzigaretten wurden danach in 10 Rauchgängen je 20 Stück auf einer Standardrauchmaschine des Typs RM 20 der Firma Borgwaldt, Hamburg, Bundesrepublik Deutschland, nach CORESTA-Norm (Methode No. 23) mit folgendem Resultat abgeraucht: Kondensat: 18,4 mg Nikotin: 1,23 mg Kondensatretention: 42,5 %. The filter cigarettes produced in this way were then smoked in 10 smoke ducts each on a standard RM 20 smoke machine from Borgwaldt, Hamburg, Federal Republic of Germany, according to the CORESTA standard (method No. 23) with the following result: Condensate: 18.4 mg Nicotine: 1.23 mg Condensate retention: 42.5%.

Die berauchten Zigarettenfilter wurden sorgfältig von Tabakresten und den diversen Papieren (Zigarettenpapier, Filterumhüllungspapier, Tipping) befreit, gewogen und einzeln in ein feinmaschiges Nylonnetz (Polyamidnetz) eingenäht.The smoked cigarette filters were carefully freed from tobacco residues and the various papers (cigarette paper, filter wrapping paper, tipping), weighed and individually sewn into a fine-mesh nylon net (polyamide net).

Die gleiche Menge an unberauchten Zigarettenfiltern mit ebenfalls einer Länge von 21 mm wurde auch von Papier befreit, gewogen und genauso in ein feinmaschiges Nylonsäckchen eingenäht.The same amount of unsmoked cigarette filters, also 21 mm long, was also freed from paper, weighed and sewn into a fine-mesh nylon bag.

Die so präparierten Proben wurden für einen Zeitraum von 20 Tagen in das Belebungsbecken (Klärbecken) der biologischen Reinigungsstufe einer Kläranlage eingebracht.
Nach Entnahme der Proben aus dem Klärbecken wurden die Zigarettenfilter sorgfältig mit entionisiertem Wasser gewaschen, getrocknet und gewogen.The samples prepared in this way were introduced into the aeration tank (clarification tank) of the biological purification stage of a sewage treatment plant for a period of 20 days.
After taking the samples from the clarifier, the cigarette filters were carefully washed with deionized water, dried and weighed.

Der durchschnittliche Gewichtsverlust der Proben bezogen auf die Menge an Celluloseacetat betrug 8 % (durch unabhängige Tests wurde festgestellt, daß sowohl der in den Zigarettenfiltern abgeschiedene Rauch als auch das Triacetin innerhalb von 20 Tagen unter den zuvor erwähnten Bedingungen vollständig abgebaut wird; dieses wurde bei der Berechnung des Gewichtsverlustes an Celluloseacetat berücksichtigt).
Es war kein signifikanter Unterschied an Gewichtsverlust zwischen den berauchten Zigarettenfilter und den unberauchten feststellbar.The average weight loss of the samples based on the amount of cellulose acetate was 8% (independent tests have found that both the smoke deposited in the cigarette filters and the triacetin are completely degraded within 20 days under the aforementioned conditions; this was at the calculation of the weight loss of cellulose acetate is taken into account).
There was no significant difference in weight loss between the smoked cigarette filter and the un-smoked.

Beispiel 1example 1

Es wurde eine Spinnlosung wie im Vergleichsbeispiel hergestellt, jedoch mit dem Unterschied, daß in das Aceton zuvor 1,5 Masse-% eines feingesiebten (Porengröße des Siebes: 20 µm) Betalactoglobulin-Pulvers, hergestellt von der Firma Bridel, Frankreich, eindispergiert wurde.
Diese Spinnlösung wurde wie im Vergleichsbeispiel zu 50 kg Filtertow mit einer Reißkraft bezogen auf dessen Gesamttiter von

Figure imgb0004

versponnen, wobei die Celluloseacetatfilamente auch wieder stauchkammergekräuselt und getrocknet wurden, und aus dem Filtertow wurden, wie im Vergleichsbeispiel, Filterstäbe und daraus wiederum Zigarettenfilter hergestellt; wie im Vergleichsbeispiel wurden Filterzigaretten gefertigt und abgeraucht. Die Abrauchergebnisse waren wie folgt: Kondensat: 18,1 mg Nikotin: 1,25 mg Kondensatretention: 42,0 % A spinning solution was prepared as in the comparative example, with the difference that 1.5 mass% of a finely sieved (pore size of the sieve: 20 μm) beta-lactoglobulin powder, manufactured by Bridel, France, was dispersed into the acetone beforehand.
As in the comparative example, this spinning solution was made into 50 kg filter tow with a tensile strength based on its total titer of
Figure imgb0004

spun, the cellulose acetate filaments being crimped and dried again in the stuffer box, and filter sticks, and again cigarette filters, were produced from the filter tow, as in the comparative example; As in the comparative example, filter cigarettes were manufactured and smoked. The smoking results were as follows: Condensate: 18.1 mg Nicotine: 1.25 mg Condensate retention: 42.0%

Wie im Vergleichsbeispiel beschrieben, wurde die biologische Abbaubarkeit der berauchten und unberauchten Zigarettenfilter im Klärbecken der Kläranlage untersucht. In einem solchen Klärbecken sind immer genügend Mikroorganismen der Art vorhanden, die in der Lage sind, den Stickstoff aus Betalactoglobulin derart umzusetzen, daß basische Zersetzungsprodukte entstehen und somit auf der Oberfläche der Celluloseacetatfilamente ein basisches (alkalisches) Milieu erzeugt wird.As described in the comparative example, the biodegradability of the smoked and un-smoked cigarette filters in the clarifier of the sewage plant was examined. In such a clarifier, there are always enough microorganisms of the type which are able to convert the nitrogen from beta-lactoglobulin in such a way that basic decomposition products are formed and thus a basic (alkaline) medium is generated on the surface of the cellulose acetate filaments.

Der auf die Menge an Celluloseacetat bezogene Gewichtsverlust betrug sowohl für die berauchten als auch für die unberauchten Zigarettenfilter im Mittel 15 % (in unabhängigen Versuchen wurde festgestellt, daß Betalactoglobulin sich unter den genannten Versuchsbedingungen vollständig abbaut; diese Tatsache wurde entsprechend der Vorgehensweise im Vergleichsbeispiel zuzüglich zu der Korrektur wegen des vollständigen Abbaus des in den Zigarettenfiltern abgeschiedenen Rauches und Triacetins berücksichtigt).The weight loss based on the amount of cellulose acetate was on average 15% for both the smoked and the un-smoked cigarette filters (in independent tests it was found that beta-lactoglobulin degrades completely under the test conditions mentioned; this fact was additionally increased according to the procedure in the comparative example correction due to the complete elimination of the smoke and triacetin separated in the cigarette filters).

Beispiel 2Example 2

Es wurde eine Spinnlösung wie im Vergleichsbeispiel hergestellt, jedoch mit dem Unterschied, daß zuvor in das Aceton 1,5 Masse-% Harnstoff eingebracht und unter Erwärmung bei 60°C gelöst wurde.A spinning solution was prepared as in the comparative example, but with the difference that 1.5% by mass of urea had previously been introduced into the acetone and dissolved with heating at 60.degree.

Mit Hilfe dieser Spinnlösung wurde, wie im Vergleichsbeispiel, 200 kg Filtertow aus stauchkammergekräuselten Celluloseacetatfilamenten hergestellt, das wiederum zu Filterstäben und schließlich zu Zigarettenfiltern verarbeitet wurde. Das Filtertow hatte eine Reißkraft bezogen auf den Gesamttiter von

Figure imgb0005

Die Abrauchung der mit diesen Filtern versehenen Filterzigaretten (siehe Vergleichsbeispiel) ergab folgende Ergebnisse: Kondensat: 18,7 mg Nikotin: 1,20 mg Kondensatretention: 42,1 %. With the aid of this spinning solution, as in the comparative example, 200 kg of filter tow were produced from cellulose acetate filaments crimped in the stuffer box, which in turn was processed into filter rods and finally into cigarette filters. The filter tow had a tensile strength based on the total titer of
Figure imgb0005

The smoking of the filter cigarettes provided with these filters (see comparative example) gave the following results: Condensate: 18.7 mg Nicotine: 1.20 mg Condensate retention: 42.1%.

Wie im Vergleichsbeispiel und im Beispiel 1 geschildert, wurde der Abbautest an den berauchten und unberauchten Zigarettenfiltern im Klärbecken der Kläranlage durchgeführt.
Der auf die Menge an Celluloseacetat bezogene Gewichtsverlust lag bei den berauchten und unberauchten Zigarettenfilter im Mittel bei 10,5 % (in unabhängigen Untersuchungen wurde festgestellt, daß Harnstoff sich unter den genannten Versuchsbedingungen biologisch vollständig abbaut; dieses wurde, entsprechend der Vorgehensweise im Vergleichsbeispiel und im Beispiel 1, bei der Errechnung des Gewichtsverlustes an Celluloseacetat - zuzüglich zu der Korrektur wegen des vollständigen Abbaus des in den Zigarettenfiltern abgeschiedenen Rauches und Triacetins - wiederum berücksichtigt).As described in the comparative example and in example 1, the degradation test was carried out on the smoked and un-smoked cigarette filters in the clarifier of the sewage treatment plant.
The weight loss based on the amount of cellulose acetate was 10.5% on average in the case of the smoked and un-smoked cigarette filters (in independent studies it was found that urea is completely biologically complete under the test conditions mentioned degrades; This was taken into account, in accordance with the procedure in the comparative example and in Example 1, when calculating the weight loss of cellulose acetate - plus the correction due to the complete breakdown of the smoke and triacetin separated in the cigarette filters).

Beispiel 3Example 3

Es wurde eine Spinnlösung wie im Vergleichsbeispiel hergestellt, jedoch mit dem Unterschied, daß zuvor in das Aceton 1,5 Masse-% Hexamethylentetramin eingebracht und gelöst wurde.A spinning solution was prepared as in the comparative example, but with the difference that 1.5% by mass of hexamethylenetetramine had previously been introduced into the acetone and dissolved.

Mit Hilfe dieser Spinnlösung wurde, wie im Vergleichsbeispiel, 200 kg Filtertow aus stauchkammergekräuselten Celluloseacetatfilamenten hergestellt, das wiederum zu Filterstäben und schließlich zu Zigarettenfiltern verarbeitet wurde. Das Filtertow hatte eine Reißkratt bezogen auf den Gesamttiter von

Figure imgb0006

Die Abrauchung der mit diesen Filtern versehenen Filterzigaretten (siehe Vergleichsbeispiel) ergab folgende Ergebnisse: Kondensat: 18,3 mg Nikotin: 1,18 mg Kondensatretention: 41,5 %. With the aid of this spinning solution, as in the comparative example, 200 kg of filter tow were produced from cellulose acetate filaments crimped in the stuffer box, which in turn was processed into filter rods and finally into cigarette filters. The filter tow had a tearing scratch based on the total titer of
Figure imgb0006

The smoking of the filter cigarettes provided with these filters (see comparative example) gave the following results: Condensate: 18.3 mg Nicotine: 1.18 mg Condensate retention: 41.5%.

Wie im Vergleichsbeispiel und im Beispiel 1 geschildert, wurde der Abbautest an den berauchten und unberauchten Zigarettenfiltern im Klärbecken der Kläranlage durchgeführt.
Der auf die Menge an Celluloseacetat bezogene Gewichtsverlust lag bei den berauchten und unberauchten Zigarettenfiltern im Mittel bei 25 % (in unabhängigen Untersuchungen wurde festgestellt, daß Hexamethylentetramin sich unter den genannten Versuchsbedingungen vollständig abbaut; dieses wurde, entsprechend der Vorgehensweise im Vergleichsbeispiel, im Beispiel 1 und im Beispiel 2, bei der Errechnung des Gewichtsverlustes an Celluloseacetat - zuzüglich zu der Korrektur wegen des vollständigen Abbaus des in den Zigarettenfiltern abgeschiedenen Rauches und Triacetins - wiederum berücksichtigt).As described in the comparative example and in example 1, the degradation test was carried out on the smoked and un-smoked cigarette filters in the clarifier of the sewage treatment plant.
The weight loss in relation to the amount of cellulose acetate in the smoked and un-smoked cigarette filters averaged 25% (in independent tests it was found that hexamethylenetetramine degrades completely under the test conditions mentioned; this was, in accordance with the procedure in the comparative example, in Example 1 and in example 2, when calculating the weight loss of cellulose acetate - plus the correction because of the complete breakdown of the smoke and triacetin separated in the cigarette filters - again taken into account).

Beispiel 4Example 4

Aus der Spinnlösung gemäß Vergleichsbeispiel wurde eine Folie A mit einer Dicke von 0,05 mm gegossen.A film A with a thickness of 0.05 mm was cast from the spinning solution according to the comparative example.

Mit Hilfe der Spinnlösung gemäß Beispiel 1 wurde eine Folie B, ebenfalls mit einer Dicke von 0,05 mm gegossen.A film B, likewise with a thickness of 0.05 mm, was cast using the spinning solution according to Example 1.

Mit Hilfe der Spinnlösung gemäß Beispiel 3 wurde eine Folie C, ebenfalls mit einer Dicke von 0,05 mm gegossen.A film C, likewise with a thickness of 0.05 mm, was cast using the spinning solution according to Example 3.

Die drei Folien A, B und C wurden zur Entfernung von eventuell noch vorhandenem Restaceton sorgfältig mit entionisiertem Wasser gewaschen.The three films A, B and C were carefully washed with deionized water to remove any remaining acetone.

Die Untersuchung der biologischen Abbaubarkeit der Folien A, B und C wurde wie im Kontrollbeispiel beschrieben unter kontrollierten mikrobiologischen Bedingungen durchgeführt.The biodegradability of films A, B and C was investigated as described in the control example under controlled microbiological conditions.

Untersuchung der biologischen Abbaubarkeit unter kontrollierten mikrobiologischen Bedingungen (Kontrollbeispiel)Investigation of the biodegradability under controlled microbiological conditions (control example)

Um die aufgrund der erfindungsgemäßen Merkmale bedingte Beschleunigung des biologischen Abbaus unter definierten mikrobiologischen Bedingungen zu veritizieren, wurde in Anlehnung an dem in der DIN 38 409 H52 beschriebenen Abbautest für wasserlösliche Substanzen eine modifizierte Testmethode für wasserunlösliche Proben entwickelt.
Nach diesem modifizierten Testverfahren wird der mikrobiologische Abbau durch Messung des Sauerstoffverbrauchs der Mikroorganismen während des Abbauvorgangs bestimmt. Der Sauerstoffverbrauch wird manometrisch bestimmt. Das durch den Stoffwechsel der Mikroorganismen gebildete Kohlendioxid wird durch Natriumhydroxid gebunden und beeinflußt dadurch die Druckmessung nicht.In order to verify the acceleration of the biological degradation due to the features according to the invention under defined microbiological conditions, a modified test method for water-insoluble samples was developed based on the degradation test for water-soluble substances described in DIN 38 409 H52.
According to this modified test method, the microbiological degradation is measured by measuring the oxygen consumption of the microorganisms determined during the mining process. The oxygen consumption is determined manometrically. The carbon dioxide formed by the metabolism of the microorganisms is bound by sodium hydroxide and does not affect the pressure measurement.

Pro Test wurden jeweils 200 mg Filtertow gemäß Vergleichsbeispiel, Beispiel 1, Beispiel 2 und Beispiel 3 sowie jeweils 200 mg der Folien A, B und C gemäß Beispiel 4 in eine mineralische Nährlösung eingebracht. Die für den mikrobiologischen Abbau benötigten Bodenbakterien wurden aus Erdfiltrat gewonnen; die Nährlösungen wurden mit je 2 ml dieser Erdfiltratlösung angeimpft.
Der aus dem Sauerstoffverbrauch errechnete prozentuale Massenverlust der Proben ist in der nachfolgenden Tabelle aufgelistet. % Gewichtsverlust nach Tagen 20 40 60 Filtertow nach Vergleichsbeispiel 0,5 1,3 2,5 Filtertow nach Beispiel 1 7 13 21 Filtertow nach Beispiel 2 7 9 12 Filtertow nach Beispiel 3 9 25 48 Folie A nach Beispiel 4 0,3 1,0 1,9 Folie B nach Beispiel 4 4 8 12 Folie C nach Beispiel 4 5 12 24 For each test, 200 mg of filter tow in accordance with comparative example, example 1, example 2 and example 3 and in each case 200 mg of films A, B and C in accordance with example 4 were introduced into a mineral nutrient solution. The soil bacteria required for microbiological degradation were obtained from earth filtrate; the nutrient solutions were inoculated with 2 ml of this earth filtrate solution.
The percentage mass loss of the samples calculated from the oxygen consumption is listed in the table below. % Weight loss after days 20th 40 60 Filter tow according to comparative example 0.5 1.3 2.5 Filter tow according to example 1 7 13 21 Filter tow according to example 2 7 9 12th Filter tow according to example 3 9 25th 48 Film A according to Example 4 0.3 1.0 1.9 Film B according to Example 4 4th 8th 12th Film C according to Example 4 5 12th 24th

Bei der Berechnung dieser Meßergebnisse wurde im Unterschied zum Vorgehen gemäß Vergleichsbeispiel, Beispiel 1, Beispiel 2 und Beispiel 3 keine Korrektur für den biologischen Abbau des jeweiligen Zusatrstoffes durchgeführt.In contrast to the procedure according to comparative example, example 1, example 2 and example 3, no correction for the biodegradation of the respective additive was carried out when calculating these measurement results.

Claims (17)

Aus Celluloseacetat geformte Gebilde, in denen oder auf deren Oberfläche ein Zusatzstoff vorhanden ist, dadurch gekennzeichnet, daß der Zusatzstoff aus einer stickstoffhaltigen organischen Verbindung besteht, bei deren Abbau durch Mikroorganismen basische Zersetzungsprodukte, insbesondere Ammoniak und/oder - basische - Verbindungen, die eine NH-Gruppe oder NH-Gruppen und/oder eine NH₂-Gruppe oder NH₂-Gruppen aufweisen, entstehen.Formed from cellulose acetate, in which or on the surface of which there is an additive, characterized in that the additive consists of a nitrogen-containing organic compound, during the breakdown of which by microorganisms basic decomposition products, in particular ammonia and / or - basic - compounds which contain an NH - Group or NH groups and / or an NH₂ group or NH₂ groups arise. Gebilde nach Anspruch 1, dadurch gekennzeichnet, daß die stickstoffhaltige organische Verbindung Harnstoff oder ein Harnstoffderivat ist.Structure according to claim 1, characterized in that the nitrogen-containing organic compound is urea or a urea derivative. Gebilde nach Anspruch 1, dadurch gekennzeichnet, daß die stickstoffhaltige organische Verbindung aus einem Protein, insbesondere aus Betalactoglobulin, besteht.Structure according to claim 1, characterized in that the nitrogen-containing organic compound consists of a protein, in particular beta-lactoglobulin. Gebilde nach Anspruch 1, dadurch gekennzeichnet, daß die stickstoffhaltige organische Verbindung ein Kondensationsprodukt aus einem Aldehyd mit Ammoniak oder mit einem Amin ist, wobei dieses Kondensationsprodukt insbesondere Hexamethylentetramin ist.Structure according to claim 1, characterized in that the nitrogen-containing organic compound is a condensation product of an aldehyde with ammonia or with an amine, this condensation product being in particular hexamethylenetetramine. Gebilde nach Anspruch 1, dadurch gekennzeichnet, daß die stickstoffhaltige organische Verbindung eine cyclische Verbindung, insbesondere Carbazol, ist.Structure according to claim 1, characterized in that the nitrogen-containing organic compound is a cyclic compound, in particular carbazole. Gebilde nach mindestens einem der vorhergehenden Ansprüche 1 bis 5, dadurch gekennzeichnet, daß in ihnen ein weiterer, biologisch abbaubarer Zusatzstoff vorhanden ist.Structure according to at least one of the preceding claims 1 to 5, characterized in that a further, biodegradable additive is present in them. Gebilde nach mindestens einem der vorhergehenden Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Celluloseacetat ein acetonlösliches Celluloseacetat mit einer Acetylzahl von weniger als 53 %, vorzugsweise einer Acetylzahl zwischen 50 % und 52 %, ist.Structure according to at least one of the preceding claims 1 to 6, characterized in that the cellulose acetate is an acetone-soluble cellulose acetate with an acetyl number of less than 53%, preferably an acetyl number between 50% and 52%. Gebilde nach mindestens einem der vorhergehenden Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie die Form von Filamenten, Spinnfasern, Filmen, Folien, Platten oder anderen durch Spritzgießen, Extrudieren oder Blasformen erhaltenen Gegenständen aufweisen.A structure according to at least one of the preceding claims 1 to 7, characterized in that it has the form of filaments, staple fibers, films, foils, plates or other objects obtained by injection molding, extrusion or blow molding. Verwendung der Gebilde in Form von Filamenten und/oder Spinnfasern nach Anspruch 8 zur Herstellung von Filtertow durch Zusammenfassen einer Vielzahl dieser Filamente und/oder Spinnfasern zu einem solchen Filtertow.Use of the structures in the form of filaments and / or staple fibers according to claim 8 for the production of filter tow by combining a plurality of these filaments and / or staple fibers to form such a filter tow. Filtertow, dadurch gekennzeichnet, daß es aus einer Vielzahl der Gebilde in Form von Filamenten und/oder Spinnfasern gemäß Anspruch 8 besteht.Filter tow, characterized in that it consists of a plurality of the structures in the form of filaments and / or staple fibers according to claim 8. Filtertow nach Anspruch 10, dadurch gekennzeichnet, daß die Reißkratt dieses Filtertows bezogen auf dessen Gesamttiter höchstens
Figure imgb0007
vorzugsweise höchstens
Figure imgb0008
beträgt.Filter tow according to claim 10, characterized in that the tearing scratch of this filter tow is at most based on its total titer
Figure imgb0007
preferably at most
Figure imgb0008
is. Verwendung des Filtertows nach Anspruch 10 oder 11 zur Herstellung eines Tabakrauchfilterelements durch im wesentlichen Versehen dieses Filtertows mit einem Weichmacher für Celluloseacetat oder einem Klebstoff, anschließendes queraxiales Verdichten und gegebenenfalls Umhüllen dieses Filtertows mit einem Umhüllungsstreifen, Zerschneiden des so verdichteten und gegebenenfalls umhüllten Filtertows in einzelne Tabakrauchfilterstäbe und schließlich Zerschneiden dieser Tabakrauchfilterstäbe in einzelne Tabakrauchfilterelemente.Use of the filter tow according to claim 10 or 11 for the production of a tobacco smoke filter element by essentially providing this filter tow with a plasticizer for cellulose acetate or an adhesive, then compressing it axially and optionally enveloping this filter tow with a wrapping strip, cutting the filter tow thus compressed and optionally wrapped into individual tobacco smoke filter rods and finally cutting these tobacco smoke filter bars into individual tobacco smoke filter elements. Tabakrauchfilterelement, bestehend aus einem Abschnitt eines queraxial verdichteten, mit Hilfe eines Weichmachers für Celluloseacetat oder eines Klebstoffes gehärteten Filtertows aus Celluloseacetatfilamenten und/oder Celluloseacetatspinnfasern, dadurch gekennzeichnet, daß das Filtertow ein solches nach Anspruch 10 oder 11 ist.Tobacco smoke filter element consisting of a section of a cross-axially compressed filter tow made of cellulose acetate filaments and / or cellulose acetate staple fibers hardened with the aid of a plasticizer for cellulose acetate or an adhesive, characterized in that the filter tow is one according to claim 10 or 11. Tabakrauchfilterelement nach Anspruch 13, dadurch gekennzeichnet daß - der Weichmacher für Celluloseacetat biologisch abbaubar ist und/oder den mikrobiologischen Bewuchs der Celluloseacetatfilamente und der Celluloseacetatspinnfasern beschleunigt oder - der Klebstoff wasserlöslich und/oder biologisch abbaubar ist. Tobacco smoke filter element according to claim 13, characterized in that - The plasticizer for cellulose acetate is biodegradable and / or accelerates the microbiological growth of the cellulose acetate filaments and the cellulose acetate staple fibers or - The adhesive is water-soluble and / or biodegradable. Tabakrauchfilterelement nach Anspruch 14, dadurch gekennzeichnet, daß der Klebstoff ein Stärkeleim oder ein Polyvinylacetatleim ist.Tobacco smoke filter element according to claim 14, characterized in that the adhesive is a starch glue or a polyvinyl acetate glue. Tabakrauchfilterelement nach einem der Ansprüche 13 oder 14, dadurch gekennzeichnet, daß das Tabakrauchfilterelement den Weichmacher für Celluloseacetat in einer Menge von höchstens 6 Masse-% bezogen auf die Masse der Celluloseacetatfilamente und/oder auf die Masse der Celluloseacetatspinnfasern enthält.Tobacco smoke filter element according to one of claims 13 or 14, characterized in that the tobacco smoke filter element contains the plasticizer for cellulose acetate in an amount of at most 6 mass% based on the mass of the cellulose acetate filaments and / or on the mass of the cellulose acetate staple fibers. Tabakrauchfilterelement nach einem der Ansprüche 13, 14, 15 oder 16, dadurch gekennzeichnet, daß weniger als die Hälfte der Oberfläche der Celluloseacetatfilamente und der Celluloseacetatspinnfasern mit dem Weichmacher für Celluloseacetat oder dem Klebstoff versehen ist.Tobacco smoke filter element according to one of claims 13, 14, 15 or 16, characterized in that less than half of the surface of the cellulose acetate filaments and the cellulose acetate staple fibers is provided with the plasticizer for cellulose acetate or the adhesive.
EP94107825A 1993-07-09 1994-05-20 Cellulose acetate based products, their use in the manufacture of filtertows for the production of tobacco smoke filters as well as filtertows and tobacco smoke filters Expired - Lifetime EP0632970B1 (en)

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WO2009007851A2 (en) * 2007-06-04 2009-01-15 Philip Morris Products S.A. Cellulose acetate fiber modification
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DE4322966C2 (en) 1995-10-26
CA2124629A1 (en) 1995-01-10
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KR950002655A (en) 1995-02-16
DE4322966A1 (en) 1995-01-12
CN1097962A (en) 1995-02-01
US5495860A (en) 1996-03-05
LTIP1995A (en) 1995-02-27
CA2124629C (en) 2001-04-17
JP2838256B2 (en) 1998-12-16
RU2082302C1 (en) 1997-06-27
LT3712B (en) 1996-02-26
KR0144648B1 (en) 1998-07-01
RU94026291A (en) 1996-07-20
JPH0799959A (en) 1995-04-18
EE03200B1 (en) 1999-08-16
EP0632970A3 (en) 1995-04-19
EP0632970B1 (en) 2000-01-12

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