EP0608744A1 - Cellulose acetate filaments, an optically isotropic spinning solution therefor and its use for the production of the filaments - Google Patents
Cellulose acetate filaments, an optically isotropic spinning solution therefor and its use for the production of the filaments Download PDFInfo
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- EP0608744A1 EP0608744A1 EP94100584A EP94100584A EP0608744A1 EP 0608744 A1 EP0608744 A1 EP 0608744A1 EP 94100584 A EP94100584 A EP 94100584A EP 94100584 A EP94100584 A EP 94100584A EP 0608744 A1 EP0608744 A1 EP 0608744A1
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- Prior art keywords
- spinning solution
- filaments
- cellulose acetate
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
- D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2965—Cellulosic
Definitions
- the invention relates to filaments based on a cellulose acetate soluble in acetone, an optically isotropic spinning solution for the production of filaments, which contains a cellulose acetate dissolved in acetone and optionally further additives, and the use of this spinning solution for producing the designated filaments.
- DE-OS 27 05 382 describes an extensive group of cellulose derivatives, including also cellulose acetates. These are to be transferred to an anisotropic spinning solution in order to produce filaments using conventional spinning processes. According to Table I, the degree of substitution (DS) of the cellulose acetate should be between 1.89 and 2.45. Halogenated and phenolic compounds are predominantly specified as suitable solvents for this. In connection with the other cellulose derivatives specified in DE-OS 27 05 382, acetone is also listed in a large number of solvents. The cellulose derivatives should be present in the spinning solution in an amount of at least 15% by volume in order to meet the requirement for optical anisotropy.
- a cellulose acetate with a degree of substitution (DS) of 1.89 is not soluble in acetone.
- DS degree of substitution
- DE-OS 27 05 382 Cellulose derivatives with an average degree of polymerization (DP) of at least 100 anhydroglucose units have a sufficiently high molecular weight to be suitable for the production of filaments. Precise statements on the degree of polymerization of the cellulose acetate and the degree of substitution between 1.89 to 2.45 are not found in DE-OS 27 05 382.
- the invention is therefore based on the object of proposing filaments based on a cellulose acetate soluble in acetone and a spinning solution which is particularly suitable for their production and which remedy the disadvantages of the prior art described above, in particular the poor economy, without the properties of the filaments being eliminated , in particular the tensile strength and the elongation, are impaired in comparison to known products.
- filaments based on a cellulose acetate soluble in acetone which is characterized in that the degree of polymerization (DP) of the cellulose acetate is between about 110 and 210.
- the range of the degree of polymerization between about 150 and 180 and in particular between about 160 and 180 is particularly preferred.
- the degree of substitution (DS) is preferably set between about 2.2 and 2.7. It is particularly preferred if the degree of substitution (DS) is between approximately 2.4 and 2.6 and very particularly preferably between approximately 2.4 and 2.5.
- cellulose-2.5-acetate If the term "cellulose-2.5-acetate” is used below, then this term should be understood in an abstract manner. This means that the degree of substitution of 2.5 can be more or less greatly exceeded or undershot, with the only requirement being that a cellulose-2,5-acetate of this type is soluble in acetone at room temperature (about 20 ° C.) is. In any case, the number "2.5" in the chemical name "cellulose-2,5-acetate” should include the cellulose acetates previously designated with the preferred degree of substitution.
- the titer of the filaments according to the invention is not critical. It is preferably between about 1 and 14 dtex, in particular between about 1.5 and 9 dtex. It is the fineness designation for filaments, i.e. a weight per length, the unit of which is the dtex.
- the parameters of the filaments according to the invention are preferably set such that their tensile strength is between approximately 0.9 and 1.2 cN / dtex, in particular between approximately 1.0 and 1.2 cN / dtex, and the elongation is between approximately 10 and 30%. in particular between about 15 and 25%. They therefore meet the requirements placed on the known filaments of this type in order to make them suitable for the fields of application described below.
- this optically isotropic spinning solution is characterized in that the concentration of the cellulose-2,5-acetate in the spinning solution is about 35 to 47% by mass and the degree of polymerization (DP) of the cellulose-2,5-acetate between about 110 and 210 lies. It is preferred here that the cellulose-2,5-acetate has the degrees of polymerization and substitution already mentioned above in connection with the description of the filaments.
- the concentration (c) in the spinning solution is at most 8% by mass and in particular at most 6% by mass below the critical Concentration (c *), measured at room temperature (about 20 ° C), is. If this critical concentration of cellulose-2,5-acetate is exceeded to higher concentrations of the spinning solution without the action of external forces, such as shear forces (c> c *), the spinning solution is converted from the isotropic to the anisotropic state.
- optically isotropic spinning solution In order to further improve the optically isotropic spinning solution according to the invention, various additives such as pigments and water can be incorporated into it.
- the optically isotropic spinning solution according to the invention preferably contains up to about 6% by mass and in particular about 2 to 4% by mass of water.
- the incorporation of water has the advantage that the viscosity of the spinning solution is reduced with the result of improved spinnability.
- the spinning solution preferably contains a finely divided pigment, in particular a white pigment, such as preferably titanium dioxide.
- the particle size is expediently in the range from about 0.3 ⁇ m to 0.5 ⁇ m.
- the amount of finely divided pigment in the spinning solution is preferably about 0.4 to 0.8% by mass, based on the proportion of cellulose-2,5-acetate in the spinning solution.
- the mass percentage range from about 0.4 to 0.6 is very particularly preferred.
- an optically isotropic acetone spinning solution with a substantially higher content of cellulose-2,5-acetate can be produced and spun, in particular after the usual dry spinning.
- e.g. (Cigarettes) filtertow because of the high concentration of spinning solution, much less acetone has to be recovered per unit weight of filtertow than under the previous conditions. In this way, e.g. same filter tow production, which significantly reduces the costs associated with the recovery of acetone.
- a spinning solution can be produced and processed at a much higher concentration than before using the inventive spinning solution with the same viscosity.
- the advantages mentioned above are therefore achieved with an optically isotropic acetone spinning solution with a high concentration of cellulose-2,5-acetate.
- the anisotropy or isotropy can be determined by visual inspection. An anisotropic phase looks cloudy and / or "mother-of-pearl", while the isotropic phase is always clear.
- the respective isotropic or anisotropic state of a spinning solution can also be determined microscopically with crossed Nicols. If, for example, a sample of an anisotropic spinning solution is observed between the slide and the cover glass of a microscope after the cover glass has been pressed down between crossed Nicols, at least part of the solution is translucent.
- the temperature also plays a role here; if the temperature of an anisotropic cellulose acetate solution is raised from room temperature initially, then the anisotropic phase may gradually transition to the isotropic phase. If the temperature is increased further, the entire spinning solution is converted into an isotropic system.
- the temperature ranges at which these transitions take place vary depending on the type of cellulose derivative, its concentration in the spinning solution and its degree of substitution.
- filaments obtained according to the invention are not restricted in comparison with the known filaments of this type. They can be used for the production of filter tow (bundles of filaments combined into a band), for tobacco smoke filters, in particular cigarette filters, but also for example for the production of - textile - yarns for linings or of mixed fabrics with cotton.
- the present invention could be explained as follows: the starting point is an isotropic acetone solution of cellulose-2,5-acetate of the type described, the concentration of which can be raised to close to the critical concentration value (c *), from which an anisotropic phase arises. If such an isotropic solution is introduced into the spinneret channels (capillaries), then the shear forces in the spinneret channel caused by the flow forces cause predominantly orientation and thus anisotropy. In the area of the capillary and after exiting the capillary, the isotropic phase does not differ from a real anisotropic phase. For this reason, almost identical fiber strengths are obtained in both cases.
- the relaxation time of the oriented polymer chains is longer than the time within which the critical concentration (c *) is reached by the evaporation of the acetone.
- the rate of evaporation is higher than the rate of relaxation.
- the anisotropic state occurs, for example, at a concentration of cellulose-2,5-acetas of approximately 47 to 48% by mass in the acetone solution, if its DP value is approximately 150 and its DS value is approximately 2.45. This information is only an example.
- the acetone spinning solution of the cellulose-2,5-acetate should be transferred into a concentration range in which the system shows anisotropy by means of rapid evaporation.
- a sotropic spinning solution can be used in accordance with the invention and that filaments can be obtained in a highly economical manner, which previously could only be produced with anisotropic spinning solutions.
- a spinning solution with the following composition was used: Dimensions-% Cellulose acetate (DP: 150; DS: 2.45) 43.2 water 3rd acetone 53.8
- the spinning solution was spun in a conventional dry spinning system which had a nozzle plate with 125 nozzle channels.
- the nozzle channels were triangular in cross section. The triangle had an edge length of 45 ⁇ m.
- the nozzle temperature was 47 ° C and the nozzle pressure was 88 bar.
- the spinning speed was 340 m / min with a draw factor of 1.6.
- a temperature of 70 ° C prevailed in the spinning shaft with a total length of 4 m located under the spinneret. 10 m3 of acetone-air mixture were suctioned off per hour.
- the filaments obtained had the following physical properties: Titer: 3.1 dtex Tensile strenght: 1.0 cN / dtex Strain: 19.4%
- the 125 filaments obtained by the process according to this example were combined into a filament bundle. 80 such filament bundles were combined into a cigarette filter tow.
- a spinning solution with the following composition was used: Dimensions-% Cellulose acetate (DP: 170; DS: 2.47) 42.1 water 3rd acetone 54.9
- the spinning solution was spun on the same dry spinning system as in Example 1, but the nozzle plate had 240 nozzle channels.
- the nozzle channels would be triangular in cross section.
- the triangle had an edge length of 45 ⁇ m.
- the nozzle temperature was adjusted to 52 ° C and the nozzle pressure was 80 bar.
- the spinning speed was 310 m / min with a stretching factor of 1.3.
- the temperature in the spinning shaft located under the spinneret with a total length of 4 m was 70 ° C. 10 m3 of acetone-air mixture were suctioned off per hour.
- the filaments obtained had the following physical properties: Titer: 3.6 dtex Tensile strenght: 1.1 cN / dtex Strain: 20.5%
Abstract
Beschrieben werden Filamente auf der Basis eines in Aceton löslichen Celluloseacetats, wobei der Polymerisationsgrad (DP) des Celluloseacetats zwischen etwa 110 und 210 und der Substitutionsgrad (DS) vorzugsweise zwischen etwa 2,2 und 2,7 liegt. Es lassen sich optisch isotrope Spinnlösungen gewinnen, deren Konzentration an Celluloseacetat etwa 35 bis 47 Masse-% beträgt. Wird eine derartige optisch isotrope Spinnlösung versponnen, insbesondere nach dem Trockenspinnverfahren, dann werden in wirtschaftlicher Weise Filamente gewonnen, da die mit der Rückgewinnung des Acetons verbundenen Kosten merklich gesenkt werden können, ohne daß die wünschenswerten Eigenschaften der Filamente, die sich insbesondere zur Herstellung von Zigarettenfiltertow eignen, beeinträchtigt werden.Filaments are described based on a cellulose acetate soluble in acetone, the degree of polymerization (DP) of the cellulose acetate being between about 110 and 210 and the degree of substitution (DS) preferably between about 2.2 and 2.7. Optically isotropic spinning solutions can be obtained, the concentration of cellulose acetate of which is approximately 35 to 47% by mass. If such an optically isotropic spinning solution is spun, in particular according to the dry spinning process, then filaments are obtained economically, since the costs associated with the recovery of the acetone can be markedly reduced without reducing the desirable properties of the filaments, which are particularly suitable for the production of cigarette filters are impaired.
Description
Die Erfindung betrifft Filamente auf der Basis eines in Aceton löslichen Celluloseacetats, eine optisch isotrope Spinnlösung zur Herstellung von Filamenten, die ein in Aceton gelöstes Celluloseacetat und gegebenenfalls weitere Additive enthält, sowie die Verwendung dieser Spinnlösung zur Herstellung der bezeichneten Filamente.The invention relates to filaments based on a cellulose acetate soluble in acetone, an optically isotropic spinning solution for the production of filaments, which contains a cellulose acetate dissolved in acetone and optionally further additives, and the use of this spinning solution for producing the designated filaments.
Die DE-OS 27 05 382 beschreibt eine umfangreiche Gruppe von Cellulosederivaten, u.a. auch Celluloseacetate. Diese sollen in eine anisotrope Spinnlösung überführt werden, um anhand üblicher Spinnverfahren Filamente herzustellen. Nach Tabelle I soll der Substitutionsgrad (DS) des Celluloseacetats zwischen 1,89 bis 2,45 liegen. Als geeignete Lösungsmittel werden hierfür überwiegend halogenierte und phenolische Verbindungen angegeben. Im Zusammenhang mit den in der DE-OS 27 05 382 angegebenen weiteren Cellulosederivaten wird in einer großen Zahl von Lösungsmitteln auch Aceton aufgelistet. Die Cellulosederivate sollen in der Spinnlösung in einer Menge von mindestens 15 Vol.% vorliegen, um die Forderung nach optischer Anisotropie zu erfüllen. In der DE-OS 27 05 382 ist jedoch die Kombination "Celluloseacetat gelöst in Aceton" nicht erwähnt. Und im übrigen würde eine 15 vol.%ige acetonische Lösung des in der DE-OS 27 05 382 beschriebenen Celluloseacetats auch nicht optisch anisotrop, sondern optisch isotrop sein.DE-OS 27 05 382 describes an extensive group of cellulose derivatives, including also cellulose acetates. These are to be transferred to an anisotropic spinning solution in order to produce filaments using conventional spinning processes. According to Table I, the degree of substitution (DS) of the cellulose acetate should be between 1.89 and 2.45. Halogenated and phenolic compounds are predominantly specified as suitable solvents for this. In connection with the other cellulose derivatives specified in DE-OS 27 05 382, acetone is also listed in a large number of solvents. The cellulose derivatives should be present in the spinning solution in an amount of at least 15% by volume in order to meet the requirement for optical anisotropy. In DE-OS 27 05 382, however, the combination "cellulose acetate dissolved in acetone" is not mentioned. And otherwise a 15 vol.% Acetone solution of the cellulose acetate described in DE-OS 27 05 382 would not be optically anisotropic, but optically isotropic.
Ferner ist ein Celluloseacetat eines Substitutionsgrad (DS) von 1,89 in Aceton nicht löslich. Dies ergibt sich aus Houben-Weyl "Methoden der organischen Chemie", Bd.E 20, Teil 3, "Makromolekulare Stoffe", Georg Thieme Verlag Stuttgart, New York, 1987, S. 2099. Nach der DE-OS 27 05 382 sollen Cellulosederivate mit einem mittleren Polymerisationsgrad (DP) von mindestens 100 Anhydroglucose-Einheiten ein hinreichend hohes Molekulargewicht aufweisen, um zur Herstellung von Filamenten geeignet zu sein. Präzise Aussagen zu dem Polymerisationsgrad des Celluloseacetats des Substitutionsgrades zwischen 1,89 bis 2,45 finden sich in der DE-OS 27 05 382 nicht. Hierauf geht Ullmann's Enzyklopedia of Industrial Chemistry, 5., vollständig überarbeitete Auflage., Vol. A5, S. 447/448 im Zusammenhang mit dem Verspinnen von in Aceton gelöstem "secondary acetate" ein. Hierunter soll das "Cellulose-2,5-Acetat" verstanden werden. Die Zahl "2,5" bedeutet die durchschnittliche Anzahl der Acetylgruppen pro Anhydroglucose-Einheit. Für die Herstellung von Fasern und Zigarettenfiltertow wird für das Cellulose-2,5-Acetat ein Polymerisationsgrad (DP) von 300 gefordert (vgl. Seite 447, Tabelle 15). Dieses soll aus einer acetonischen Lösung versponnen werden können, deren Viskosität bei einer Konzentration an Cellulose-2,5-Acetat von 20 bis 30% sowie bei einer Temperatur von 45 bis 55°C zwischen 300 und 500 Pa.s (gemeint ist wohl: ....zwischen 30 und 50 Pa.s...) liegt. Hiermit erhaltene Filamente haben die folgenden physikalischen Eigenschaften: Zugfestigkeit (cN/dtex) 1,0 bis 1,5, Dehnung (%) 25 bis 30, Dichte (g/cm³) 1,33, Schmelzpunkt (°C) 225 bis 250 und, wie bereits angegeben, einen Polymerisationsgrad von 300.Furthermore, a cellulose acetate with a degree of substitution (DS) of 1.89 is not soluble in acetone. This results from Houben-Weyl "Methods of Organic Chemistry", Vol. E 20, Part 3, "Macromolecular Substances", Georg Thieme Verlag Stuttgart, New York, 1987, p. 2099. According to DE-OS 27 05 382 Cellulose derivatives with an average degree of polymerization (DP) of at least 100 anhydroglucose units have a sufficiently high molecular weight to be suitable for the production of filaments. Precise statements on the degree of polymerization of the cellulose acetate and the degree of substitution between 1.89 to 2.45 are not found in DE-OS 27 05 382. This is discussed by Ullmann's Encyclopedia of Industrial Chemistry, 5th, completely revised edition., Vol. A5, pp. 447/448 in connection with the spinning of "secondary acetate" dissolved in acetone. This should be understood to mean the "cellulose-2.5-acetate". The number "2.5" means the average number of acetyl groups per anhydroglucose unit. For the manufacture of fibers and cigarette filter tow, a degree of polymerization (DP) of 300 is required for the cellulose-2,5-acetate (see page 447, table 15). This should be able to be spun from an acetone solution, the viscosity of which at a concentration of cellulose 2,5-acetate of 20 to 30% and at a temperature of 45 to 55 ° C between 300 and 500 Pa.s (probably meant: .... between 30 and 50 Pa.s ...). Filaments thus obtained have the following physical properties: tensile strength (cN / dtex) 1.0 to 1.5, elongation (%) 25 to 30, density (g / cm³) 1.33, melting point (° C) 225 to 250 and , as already stated, a degree of polymerization of 300.
Eine zusammenschauende Betrachtung des Standes der Technik zeigt, daß im Zusammenhang mit Aceton als Lösungsmittel einer Spinnlösung von Cellulose-2,5-Acetat ein hoher Polymerisatonsgrad von 300 mit der Folge verlangt wird, daß die Spinnlösung nur eine niedrige Konzentration von etwa 20 bis 30% an Cellulose-2,5-Acetat aufweist. Bei einem Ausgangsmaterial dieses Polymerisationsgrades kann seine Konzentration in Aceton zur Herstellung einer Spinnlösung nicht weiter angehoben werden, weil damit zwangsläufig ein so starker Anstieg der Viskosität der Spinnlösung verbunden ist, daß diese mit üblichen Spinnvorrichtungen nicht mehr versponnen werden kann (beispielsweise bei 40 bis 50%). Eine merklich angehobene Konzentration würde den Vorteil bieten, daß der Gehalt an Aceton in der Spinnlösung drastisch reduziert werden könnte mit der Folge einer erheblichen Energieeinsparung beim Umlauf und der Rückgewinnung des Acetons.A comprehensive examination of the prior art shows that in connection with acetone as the solvent of a spinning solution of cellulose-2,5-acetate, a high degree of polymerization of 300 is required, with the result that the spinning solution only has a low concentration of about 20 to 30%. of cellulose-2,5-acetate. With a starting material of this degree of polymerization, its concentration in acetone cannot be increased further to produce a spinning solution, because this inevitably leads to a rise in the viscosity of the spinning solution which is so great that it can no longer be spun with conventional spinning devices (for example at 40 to 50% ). A noticeably increased concentration would offer the advantage that the content of acetone in the spinning solution could be drastically reduced, resulting in considerable energy savings in the circulation and recovery of the acetone.
Der Erfindung liegt somit die Aufgabe zugrunde, Filamente auf der Basis eines in Aceton löslichen Celluloseacetats sowie eine für deren Herstellung besonders geeignete Spinnlösung vorzuschlagen, die die oben geschilderten Nachteile des Standes der Technik, insbesondere die mangelhafte Wirtschaftlichkeit, beheben, ohne daß die Eigenschaften der Filamente, insbesondere die Zugfestigkeit sowie die Dehnung, im Vergleich zu bekannten Erzeugnissen beeinträchtigt werden.The invention is therefore based on the object of proposing filaments based on a cellulose acetate soluble in acetone and a spinning solution which is particularly suitable for their production and which remedy the disadvantages of the prior art described above, in particular the poor economy, without the properties of the filaments being eliminated , in particular the tensile strength and the elongation, are impaired in comparison to known products.
Die obige Aufgabe wird durch Filamente auf der Basis eines in Aceton löslichen Celluloseacetats gelöst, das dadurch gekennzeichnet ist, daß der Polymerisationsgrad (DP) des Celluloseacetats zwischen etwa 110 und 210 liegt. Besonders bevorzugt wird der Bereich des Polymerisationsgrades zwischen etwa 150 und 180 und insbesondere zwischen etwa 160 und 180.The above object is achieved by filaments based on a cellulose acetate soluble in acetone, which is characterized in that the degree of polymerization (DP) of the cellulose acetate is between about 110 and 210. The range of the degree of polymerization between about 150 and 180 and in particular between about 160 and 180 is particularly preferred.
Damit das erwähnte Celluloseacetat in Aceton löslich ist, wird sein Substitutionsgrad (DS) vorzugsweise zwischen etwa 2,2 und 2,7 eingestellt. Besonders bevorzugt ist es, wenn der Substitutionsgrad (DS) zwischen etwa 2,4 und 2,6 und ganz besonders bevorzugt zwischen etwa 2,4 und 2,5 liegt.In order that the cellulose acetate mentioned is soluble in acetone, its degree of substitution (DS) is preferably set between about 2.2 and 2.7. It is particularly preferred if the degree of substitution (DS) is between approximately 2.4 and 2.6 and very particularly preferably between approximately 2.4 and 2.5.
Wenn nachfolgend von einem "Cellulose-2,5-Acetat" gesprochen wird, dann soll dieser Begriff abstrakt verstanden werden. Das bedeutet, daß der Substitutionsgrad von 2,5 mehr oder weniger weit unter- bzw. überschritten werden kann, wobei lediglich die Forderung einzuhalten ist, daß ein derartiges Cellulose-2,5-Acetat bei Raumtemperatur (etwa 20°C) in Aceton löslich ist. Auf jeden Fall soll die Zahl "2,5" in der chemischen Bezeichnung "Cellulose-2,5-Acetat" die zuvor mit dem bevorzugten Substitutionsgrad bezeichneten Celluloseacetate einbeziehen.If the term "cellulose-2.5-acetate" is used below, then this term should be understood in an abstract manner. This means that the degree of substitution of 2.5 can be more or less greatly exceeded or undershot, with the only requirement being that a cellulose-2,5-acetate of this type is soluble in acetone at room temperature (about 20 ° C.) is. In any case, the number "2.5" in the chemical name "cellulose-2,5-acetate" should include the cellulose acetates previously designated with the preferred degree of substitution.
Der Titer der erfindungsgemäßen Filamente ist nicht kritisch. Vorzugsweise liegt er zwischen etwa 1 und 14 dtex, insbesondere zwischen etwa 1,5 bis 9 dtex. Es handelt sich um die Feinheitsbezeichnung für Filamente, d.h. eine Gewichtsangabe pro Länge, deren Einheit das dtex ist.The titer of the filaments according to the invention is not critical. It is preferably between about 1 and 14 dtex, in particular between about 1.5 and 9 dtex. It is the fineness designation for filaments, i.e. a weight per length, the unit of which is the dtex.
Vorzugsweise werden die Parameter der erfindungsgemäßen Filamente so eingestellt, daß deren Zugfestigkeit zwischen etwa 0,9 und 1,2 cN/dtex, insbesondere zwischen etwa 1,0 und 1,2 cN/dtex, sowie die Dehnung zwischen etwa 10 und 30%, insbesondere zwischen etwa 15 und 25%, liegt. Damit genügen sie den Anforderungen, die an die bekannten Filamente dieser Art gestellt werden, um sie für die nachfolgend bezeichneten Anwendungsgebiete geeignet zu machen.The parameters of the filaments according to the invention are preferably set such that their tensile strength is between approximately 0.9 and 1.2 cN / dtex, in particular between approximately 1.0 and 1.2 cN / dtex, and the elongation is between approximately 10 and 30%. in particular between about 15 and 25%. They therefore meet the requirements placed on the known filaments of this type in order to make them suitable for the fields of application described below.
Es hat sich gezeigt, daß die den Kern der Erfindung bildenden und in Aceton löslichen Cellulose-2,5-Acetate geeignet sind, in eine optische isotrope Spinnlösung zur Herstellung von Filamenten überführt zu werden, die dieses Cellulose-2,5-Acetat in Aceton gelöst sowie gegebenenfalls weitere Additive enthält. Erfindungsgemäß ist diese optisch isotrope Spinnlösung dadurch gekennzeichnet, daß die Konzentration des Cellulose-2,5-Acetats in der Spinnlösung etwa 35 bis 47 Masse-% beträgt und der Polymerisationsgrad (DP) des Cellulose-2,5-Acetats zwischen etwa 110 und 210 liegt. Hierbei wird es bevorzugt, daß das Cellulose-2,5-Acetat die vorstehend bereits im Zusammenhang mit der Beschreibung der Filamente genannten Polymerisations- und Substitutionsgrade aufweist.It has been found that the cellulose-2,5-acetates which form the core of the invention and are soluble in acetone are suitable for being converted into an optical isotropic spinning solution for the production of filaments which contain this cellulose-2,5-acetate dissolved in acetone and optionally contains other additives. According to the invention, this optically isotropic spinning solution is characterized in that the concentration of the cellulose-2,5-acetate in the spinning solution is about 35 to 47% by mass and the degree of polymerization (DP) of the cellulose-2,5-acetate between about 110 and 210 lies. It is preferred here that the cellulose-2,5-acetate has the degrees of polymerization and substitution already mentioned above in connection with the description of the filaments.
Im Hinblick auf die optimale Konzentration des Cellulose-2,5-Acetats in der erfindungsgemäßen optisch isotropen Spinnlösung ist es von besonderem Vorteil, wenn dessen Konzentration (c) in der Spinnlösung höchstens 8 Masse-% und insbesondere höchstens 6 Masse-% unterhalb der kritischen Konzentration (c*), gemessen bei Raumtemperatur (etwa 20°C), liegt. Wird diese kritische Konzentration an Cellulose-2,5-Acetat zu höheren Konzentrationen der Spinnlösung ohne Einwirkung äußerer Kräfte, wie Scherkräfte, überschritten (c > c*), dann wird die Spinnlösung vom isotropen in den anisotropen Zustand überführt.In view of the optimal concentration of the cellulose-2,5-acetate in the optically isotropic spinning solution according to the invention, it is particularly advantageous if its concentration (c) in the spinning solution is at most 8% by mass and in particular at most 6% by mass below the critical Concentration (c *), measured at room temperature (about 20 ° C), is. If this critical concentration of cellulose-2,5-acetate is exceeded to higher concentrations of the spinning solution without the action of external forces, such as shear forces (c> c *), the spinning solution is converted from the isotropic to the anisotropic state.
Um die erfindungsgemäße optisch isotrope Spinnlösung weiter zu verbessern, können ihr verschiedene Additive einverleibt werden, wie Pigmente und Wasser. Vorzugsweise enthält die erfindungsgemäße optisch isotrope Spinnlösung bis zu etwa 6 Masse-% und insbesondere etwa 2 bis 4 Masse-% Wasser. Mit der Einverleibung von Wasser ist der Vorteil verbunden, daß die Viskosität der Spinnlösung mit der Folge einer verbesserten Verspinnbarkeit herabgesetzt wird.In order to further improve the optically isotropic spinning solution according to the invention, various additives such as pigments and water can be incorporated into it. The optically isotropic spinning solution according to the invention preferably contains up to about 6% by mass and in particular about 2 to 4% by mass of water. The incorporation of water has the advantage that the viscosity of the spinning solution is reduced with the result of improved spinnability.
Wird die erfindungsgemäße optisch isotrope Spinnlösung zur Herstellung von Filamenten eingesetzt, die für ein (Zigaretten)filtertow zur Herstellung von Zigarettenfiltern verwendet werden, dann enthält die Spinnlösung vorzugsweise ein feinteiliges Pigment, insbesondere ein Weißpigment, wie vorzugsweise Titandioxid. Dabei liegt die Teilchengröße zweckmäßigerweise in dem Bereich von etwa 0,3 µm bis 0,5 µm. Die Menge an feinteiligem Pigment in der Spinnlösung beträgt vorzugsweise etwa 0,4 bis 0,8 Masse-%, bezogen auf den Anteil der Spinnlösung an Cellulose-2,5-Acetat. Ganz besonders bevorzugt wird der massenprozentuale Bereich von etwa 0,4 bis 0,6.If the optically isotropic spinning solution according to the invention is used for the production of filaments which are used for a (cigarette) filter tow for the production of cigarette filters, then the spinning solution preferably contains a finely divided pigment, in particular a white pigment, such as preferably titanium dioxide. The particle size is expediently in the range from about 0.3 μm to 0.5 μm. The amount of finely divided pigment in the spinning solution is preferably about 0.4 to 0.8% by mass, based on the proportion of cellulose-2,5-acetate in the spinning solution. The mass percentage range from about 0.4 to 0.6 is very particularly preferred.
Die mit der Erfindung erzielbaren Vorteile lassen sich wie folgt beschreiben: In der Spinnerei läßt sich eine optisch isotrope acetonische Spinnlösung mit einem wesentlich höheren Gehalt an Cellulose-2,5-Acetat herstellen und verspinnen, insbesondere nach dem üblichen Trockenspinnen. Bei der Herstellung von z.B. (Zigaretten)filtertow muß pro Gewichtseinheit produziertem Filtertow aufgrund der hohen Spinnlösungskonzentration sehr viel weniger Aceton als unter den bisherigen Bedingungen zurückgewonnen werden. Auf diese Weise lassen sich, bei z.B. gleicher Filtertow-Produktion, die mit der Rückgewinnung des Acetons verbundenen Kosten merklich veringern. Somit kann in der Spinnerei anhand der ertindungsgemäßen Spinnlösung bei gleicher Viskosität eine Spinnlösung sehr viel höherer Konzentration als bisher hergestellt und verarbeitet werden.The advantages which can be achieved with the invention can be described as follows: In the spinning mill, an optically isotropic acetone spinning solution with a substantially higher content of cellulose-2,5-acetate can be produced and spun, in particular after the usual dry spinning. In the manufacture of e.g. (Cigarettes) filtertow, because of the high concentration of spinning solution, much less acetone has to be recovered per unit weight of filtertow than under the previous conditions. In this way, e.g. same filter tow production, which significantly reduces the costs associated with the recovery of acetone. Thus, in the spinning mill, a spinning solution can be produced and processed at a much higher concentration than before using the inventive spinning solution with the same viscosity.
Die oben angesprochenen Vorteile werden demzufolge mit einer optisch isotropen acetonischen Spinnlösung hoher Konzentration an Cellulose-2,5-Acetat erzielt. Die Anisotropie bzw. Isotropie kann durch Augenschein festgestellt werden. Eine anisotrope Phase sieht trüb und/oder "perlmuttartig" aus, während die isotrope Phase stets klar ist. Auch kann der jeweilige isotrope bzw. anisotrope Zustand einer Spinnlösung mikroskopisch mit gekreuzten Nicols festgestellt werden. Wenn beispielsweise eine Probe einer anisotropen Spinnlösung zwischen Objektträger und Deckglas eines Mikroskops nach dem Niederdrücken des Deckglases zwischen gekreuzten Nicols beobachtet wird, ist mindestens ein Teil der Lösung lichtdurchlässig. Hierbei spielt auch die Temperatur eine Rolle; wenn die Temperatur einer anisotropen Celluloseacetatlösung von anfänglich Raumtemperatur gesteigert wird, dann kann die anisotrope Phase allmählich in die isotrope Phase übergehen. Wird die Temperatur weiter erhöht, wandelt sich die gesamte Spinnlösung in ein isotropes System um. Die Temperaturbereiche, bei denen diese Übergänge stattfinden, variieren je nach Art des Cellulosederivats, dessen Konzentration in der Spinnlösung und dessen Substitutionsgrad.The advantages mentioned above are therefore achieved with an optically isotropic acetone spinning solution with a high concentration of cellulose-2,5-acetate. The anisotropy or isotropy can be determined by visual inspection. An anisotropic phase looks cloudy and / or "mother-of-pearl", while the isotropic phase is always clear. The respective isotropic or anisotropic state of a spinning solution can also be determined microscopically with crossed Nicols. If, for example, a sample of an anisotropic spinning solution is observed between the slide and the cover glass of a microscope after the cover glass has been pressed down between crossed Nicols, at least part of the solution is translucent. The temperature also plays a role here; if the temperature of an anisotropic cellulose acetate solution is raised from room temperature initially, then the anisotropic phase may gradually transition to the isotropic phase. If the temperature is increased further, the entire spinning solution is converted into an isotropic system. The temperature ranges at which these transitions take place vary depending on the type of cellulose derivative, its concentration in the spinning solution and its degree of substitution.
Die Verwendungsmöglichkeiten der erfindungsgemäß erhaltenen Filamente sind im Verlgeich zu den bekannten Filamenten dieser Art nicht eingeschränkt. So können sie zur Herstellung von Filtertow (zu einem Band zusammengefaßte Filamentbündel), für Tabakrauchfilter, insbesondere Zigarettenfilter, aber auch beispielsweise zur Herstellung von - textilen - Garnen für Futterstoffe oder von Mischgeweben mit Baumwolle verwendet werden.The possible uses of the filaments obtained according to the invention are not restricted in comparison with the known filaments of this type. They can be used for the production of filter tow (bundles of filaments combined into a band), for tobacco smoke filters, in particular cigarette filters, but also for example for the production of - textile - yarns for linings or of mixed fabrics with cotton.
Technologisch könnte die vorliegende Erfindung wie folgt erklärt werden: Ausgangspunkt ist eine isotrope acetonische Lösung von Cellulose-2,5-Acetat der bezeichneten Art, deren Konzentration bis dicht an den kritischen Konzentrationswert (c*) angehoben werden kann, von dem an eine anisotrope Phase entsteht. Wird eine derartige isotrope Lösung in die Spinndüsenkanäle (Kapillaren) eingeführt, dann bewirken die durch die Strömungskräfte auftretenden Scherkräfte im Spinndüsenkanal, daß sich überwiegend eine Orientierung und damit Anisotropie einstellt. Im Bereich der Kapillare und nach Austritt aus der Kapillare unterscheidet sich die isotrope Phase nicht von einer echten anisotropen Phase. Aus diesem Grund erhält man in beiden Fällen nahezu gleiche Faserfestigkeiten. Verläßt die Spinnlösung den Spinndüsenkanal, dann treten zwei Abläufe in Konkurrenz, einerseits die Relaxation der orientierten Polymerketten und andererseits die Verdampfung des Acetons. Aufgrund der hohen Konzentration, die nur wenig unter der zuvor bereits erwähnten kritischen Konzentration (c*) liegt, ist die Relaxationszeit der orientierten Polymerketten länger als die Zeit, innerhalb derer durch die Verdampfung des Acetons die kritische Konzentration (c*) erreicht wird. Mit anderen Worten ist die Verdampfungsgeschwindigkeit höher als die Relaxationsgeschwindigkeit. Der anisotrope Zustand stellt sich beispielsweise bei einer Konzentration des Cellulose-2,5-acetas von etwa 47 bis 48 Masse-% in der acetonischen Lösung ein, wenn dessen DP-Wert etwa 150 und dessen DS-Wert etwa 2,45 beträgt. Diese Angabe ist nur beispielhaft. Durch eine möglichst schnelle Verdampfung soll demzufolge die acetonische Spinnlösung des Cellulose-2,5-Acetats in einen solchen Konzentrationsbereich überführt werden, in dem das System Anisotropie zeigt. Im Ergebnis überrascht es also, daß erfindungsgemäß eine sotrope Spinnlösung eingesetzt werden kann und mit dieser in höchst wirtschaftlicher Weise Filamente gewonnen werden können, die bisher nur mit anisotropen Spinnlösungen herstellbar waren.Technologically, the present invention could be explained as follows: the starting point is an isotropic acetone solution of cellulose-2,5-acetate of the type described, the concentration of which can be raised to close to the critical concentration value (c *), from which an anisotropic phase arises. If such an isotropic solution is introduced into the spinneret channels (capillaries), then the shear forces in the spinneret channel caused by the flow forces cause predominantly orientation and thus anisotropy. In the area of the capillary and after exiting the capillary, the isotropic phase does not differ from a real anisotropic phase. For this reason, almost identical fiber strengths are obtained in both cases. If the spinning solution leaves the spinneret channel, two processes compete, on the one hand the relaxation of the oriented polymer chains and on the other hand the evaporation of the acetone. Due to the high concentration, which is only slightly below the previously mentioned critical concentration (c *), the relaxation time of the oriented polymer chains is longer than the time within which the critical concentration (c *) is reached by the evaporation of the acetone. In other words, the rate of evaporation is higher than the rate of relaxation. The anisotropic state occurs, for example, at a concentration of cellulose-2,5-acetas of approximately 47 to 48% by mass in the acetone solution, if its DP value is approximately 150 and its DS value is approximately 2.45. This information is only an example. As a result, the acetone spinning solution of the cellulose-2,5-acetate should be transferred into a concentration range in which the system shows anisotropy by means of rapid evaporation. As a result, it is surprising that a sotropic spinning solution can be used in accordance with the invention and that filaments can be obtained in a highly economical manner, which previously could only be produced with anisotropic spinning solutions.
Die Erfindung soll nachfolgend anhand zweier Beispiele noch näher erläutert werden:The invention will be explained in more detail below with the aid of two examples:
Eingesetzt wurde eine Spinnlösung folgender Zusammensetzung:
Die Spinnlösung wurde in einer üblichen Trockenspinnanlage versponnen, die eine Düsenplatte mit 125 Düsenkanälen aufwies. Die Düsenkanäle waren im Querschnitt dreieckig. Das Dreieck hatte eine Kantenlänge von 45 µm. Die Düsentemperatur betrug 47°C und der Düsendruck 88 bar. Die Spinngeschwindigkeit betrug 340 m/min bei einem Verstreckungsfaktor von 1,6. In dem sich unter der Spinndüse befindenden Spinnschacht einer Gesamtlänge von 4 m herrschte eine Temperatur von 70°C. Pro Stunde wurden 10 m³ Aceton-Luftgemisch abgesaugt. Die erhaltenen Filamente hatten die folgenden physikalischen Eigenschaften:
Die mit dem Verfahren nach diesem Beispiel erhaltenen 125 Filamente wurden zu einem Filamentbündeln vereinigt. 80 solcher Filamentbündel wurden zu einem Zigarettenfiltertow (Englisch: cigarette filter tow) zusammengefaßt.The 125 filaments obtained by the process according to this example were combined into a filament bundle. 80 such filament bundles were combined into a cigarette filter tow.
Eingesetzt wurde eine Spinnlösung folgender Zusammensetzung:
Die Spinnlösung wurde auf derselben Trockenspinnanlage wie gemäß Beispiel 1 versponnen, allerdings wies die Düsenplatte 240 Düsenkanäle auf. Die Düsenkanäle ware im Querschnitt dreieckig. Das Dreieck hatte eine Kantenlänge von 45 µm. Die Düsentemperatur wurde auf 52°C eingeregelt, und der Düsendruck betrug 80 bar. Die Spinngeschwindigkeit betrug 310 m/min bei einem Verstreckungsfaktor von 1,3. Die Temperatur in dem sich unter der Spinndüse befindenden Spinnschacht mit einer Gesamtlänge von 4 m betrug 70°C. Pro Stunde wurden 10 m³ Aceton-Luftgemisch abgesaugt. Die erhaltenen Filamente hatten die folgenden physikalischen Eigengschaften:
Claims (19)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4302055A DE4302055C1 (en) | 1993-01-26 | 1993-01-26 | Cellulose acetate filaments prepd. by spinning from an acetone soln. - are useful for the prodn. of cigarette filter tow |
| DE4302055 | 1993-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0608744A1 true EP0608744A1 (en) | 1994-08-03 |
| EP0608744B1 EP0608744B1 (en) | 1999-03-31 |
Family
ID=6478940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94100584A Expired - Lifetime EP0608744B1 (en) | 1993-01-26 | 1994-01-17 | Cellulose acetate filaments, an optically isotropic spinning solution therefor and its use for the production of the filaments |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5449555A (en) |
| EP (1) | EP0608744B1 (en) |
| JP (1) | JP2950490B2 (en) |
| KR (1) | KR960011600B1 (en) |
| CN (1) | CN1100478A (en) |
| AT (1) | ATE178368T1 (en) |
| BR (1) | BR9400301A (en) |
| CA (1) | CA2113142A1 (en) |
| DE (2) | DE4302055C1 (en) |
| ES (1) | ES2131594T3 (en) |
| RU (1) | RU2085629C1 (en) |
Cited By (1)
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|---|---|---|---|---|
| WO1999004071A1 (en) * | 1997-07-16 | 1999-01-28 | Rhodia Acetow Gmbh | Cellulose acetate with trilobal cross section |
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| JP3342763B2 (en) * | 1994-02-04 | 2002-11-11 | ダイセル化学工業株式会社 | Cigarette filter material |
| ATE180844T1 (en) * | 1994-03-01 | 1999-06-15 | Kuraray Co | REGENERATED CELLULOSE FIBER DYEABLE WITH DISPERSED DYE AND TEXTILE PRODUCT CONTAINING THE SAME |
| US5856006A (en) * | 1994-09-19 | 1999-01-05 | Daicel Chemical Industries, Ltd. | Tobacco filter material and a method for producing the same |
| US5491024A (en) * | 1995-03-14 | 1996-02-13 | Hoechst Celanese Corporation | Photodegradable cellulose ester tow |
| JP3942669B2 (en) * | 1995-03-31 | 2007-07-11 | ダイセル化学工業株式会社 | Cellulose acetate with excellent physical strength and method for producing the same |
| US5914397A (en) * | 1995-03-31 | 1999-06-22 | Daicel Chemical Industries, Ltd. | Cellulose acetate excellent in physical strength, and process for production thereof |
| DE69630089T2 (en) * | 1995-03-31 | 2004-04-01 | Daicel Chemical Industries, Ltd., Sakai | CELLULOSE ACETATE WITH HIGH DEFORMABILITY AND METHOD FOR THE PRODUCTION THEREOF |
| US8039531B2 (en) | 2003-03-14 | 2011-10-18 | Eastman Chemical Company | Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions |
| US8461234B2 (en) | 2003-03-14 | 2013-06-11 | Eastman Chemical Company | Refinish coating compositions comprising low molecular weight cellulose mixed esters |
| US7893138B2 (en) | 2003-03-14 | 2011-02-22 | Eastman Chemical Company | Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions |
| US8124676B2 (en) | 2003-03-14 | 2012-02-28 | Eastman Chemical Company | Basecoat coating compositions comprising low molecular weight cellulose mixed esters |
| GB2504495A (en) * | 2012-07-30 | 2014-02-05 | British American Tobacco Co | Fleece for smokeless tobacco pouch |
| RU2515313C2 (en) * | 2012-08-27 | 2014-05-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тюменский государственный нефтегазовый университет" (ТюмГНГУ) | Method of modifying cellulose diacetate fibres |
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- 1994-01-10 CA CA002113142A patent/CA2113142A1/en not_active Abandoned
- 1994-01-17 DE DE59408019T patent/DE59408019D1/en not_active Expired - Lifetime
- 1994-01-17 ES ES94100584T patent/ES2131594T3/en not_active Expired - Lifetime
- 1994-01-17 AT AT94100584T patent/ATE178368T1/en not_active IP Right Cessation
- 1994-01-17 EP EP94100584A patent/EP0608744B1/en not_active Expired - Lifetime
- 1994-01-21 BR BR9400301A patent/BR9400301A/en not_active Application Discontinuation
- 1994-01-21 US US08/185,596 patent/US5449555A/en not_active Expired - Lifetime
- 1994-01-25 RU RU9494002339A patent/RU2085629C1/en active
- 1994-01-25 CN CN94102664A patent/CN1100478A/en active Pending
- 1994-01-25 JP JP6006657A patent/JP2950490B2/en not_active Expired - Fee Related
- 1994-01-26 KR KR1019940001393A patent/KR960011600B1/en not_active IP Right Cessation
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| US1688531A (en) * | 1922-08-11 | 1928-10-23 | Dreyfus Henry | Manufacture of artificial silk, artificial horsehair, and the like |
| US1620636A (en) * | 1923-03-07 | 1927-03-15 | Dreyfus Henry | Manufacture of artificial threads and filaments |
| US2829027A (en) * | 1953-12-28 | 1958-04-01 | Eastman Kodak Co | Dry spinning process for making y-shaped filaments |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999004071A1 (en) * | 1997-07-16 | 1999-01-28 | Rhodia Acetow Gmbh | Cellulose acetate with trilobal cross section |
| US6177194B1 (en) | 1997-07-16 | 2001-01-23 | Rhodia Acetow Gmbh | Cellulose acetate filaments with a trilobal cross section |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2131594T3 (en) | 1999-08-01 |
| US5449555A (en) | 1995-09-12 |
| KR960011600B1 (en) | 1996-08-24 |
| ATE178368T1 (en) | 1999-04-15 |
| DE59408019D1 (en) | 1999-05-06 |
| RU2085629C1 (en) | 1997-07-27 |
| EP0608744B1 (en) | 1999-03-31 |
| DE4302055C1 (en) | 1994-03-24 |
| JP2950490B2 (en) | 1999-09-20 |
| CA2113142A1 (en) | 1994-07-27 |
| CN1100478A (en) | 1995-03-22 |
| JPH06280107A (en) | 1994-10-04 |
| KR940018496A (en) | 1994-08-18 |
| BR9400301A (en) | 1994-08-16 |
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