EP1530657A1 - Formulation of a highly viscous mineral oil for the production of filters for tobacco - Google Patents

Formulation of a highly viscous mineral oil for the production of filters for tobacco

Info

Publication number
EP1530657A1
EP1530657A1 EP03732455A EP03732455A EP1530657A1 EP 1530657 A1 EP1530657 A1 EP 1530657A1 EP 03732455 A EP03732455 A EP 03732455A EP 03732455 A EP03732455 A EP 03732455A EP 1530657 A1 EP1530657 A1 EP 1530657A1
Authority
EP
European Patent Office
Prior art keywords
sorbitan
formulation
threads
formulation according
weight
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
EP03732455A
Other languages
German (de)
French (fr)
Other versions
EP1530657B1 (en
Inventor
Hubert Dobbelstein
Emini Shefqet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMINI, SHEFQET
Original Assignee
Shefqet Emini
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shefqet Emini filed Critical Shefqet Emini
Priority to EP03732455A priority Critical patent/EP1530657B1/en
Publication of EP1530657A1 publication Critical patent/EP1530657A1/en
Application granted granted Critical
Publication of EP1530657B1 publication Critical patent/EP1530657B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2243—Mono-, di-, or triglycerides
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D06M2101/08—Esters or ethers of cellulose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to a formulation for use as a lubricant in the manufacture of threads.
  • the threads are first produced by a spinning process, which is preferably the solvent spinning process, and then further processed as a lubricant while applying the formulation according to the invention to the surface of the threads.
  • the threads produced are preferably cellulose acetate threads and these threads are used for the manufacture of filters for tobacco products, especially cigarette filters.
  • the patent specification GB 896,599 describes tobacco filters which can be used in cigarettes, pipes, cigarette holders or cigar holders.
  • the filter elements described consist of bundles of continuous synthetic filaments, water-insoluble calcium or magnesium salts being present in finely divided form on the surface of the filaments. These finely divided particles are fixed on the fibers by oils.
  • these oils can also be high-boiling liquid esters of native origin, liquid esters of natural fats or liquid high-molecular fatty alcohols. 0
  • the patent specification GB 765,962 describes a tobacco filter element which consists of cellulose acetate fibers.
  • the cellulose acetate filter material is subjected to various processing steps, such as, for example, stretching and crimping the fibers.
  • processing steps such as, for example, stretching and crimping the fibers.
  • an electrostatic charging of the fibers must be prevented on the one hand and on the other hand the surface of the fiber must be provided with a lubricant so that the fiber can be subjected to these processing steps.
  • a lubricant contains an o mineral oil with a purity with which it would also be suitable for the manufacture of pharmaceutical products.
  • DE 12 12 459 describes a stiff tobacco smoke filter which consists of a bundle of optionally crimped continuous threads and a paper wrapper.
  • the threads consist of a mixture of a polyalphaolefin and a plasticizer-soluble polymer of an organic plasticizer.
  • liquid high-boiling organic esters or water-insoluble propylene glycols or polybutylene glycols can also be used as the liquid organic plasticizer.
  • U.S. Patent 4,330,422 describes a cleaning composition containing white mineral oil.
  • the emulsion is used to treat and clean metal surfaces.
  • the emulsion of the invention contains 20-50% by weight of a mineral oil with a viscosity of 50-380 Saybolt seconds, measured at 100 ° F and 0.5 to 10% by weight of an emulsifier.
  • a mineral oil with a viscosity of 50-380 Saybolt seconds, measured at 100 ° F and 0.5 to 10% by weight of an emulsifier.
  • nonionic emulsifiers has proven to be advantageous.
  • emulsifiers i.a. Sorbitan esters and polyglycerides of fatty acids specified.
  • emulsifier should be present in the emulsion as is just necessary to form a stable emulsion. 0.5 to 10% by weight of the emulsifier is present in the emulsion, with 1 to 50% by weight of emulsifier being preferred. If there is more emulsifier in the emulsion, milky stains or streaks may remain on the cleaned surface after cleaning.
  • the manufacture of filters for tobacco products usually takes place according to a process in which a thread, which normally contains cellulose acetate, is first produced using a spinning process, which is preferably the solvent spinning process.
  • the solution solidifies into a filament with considerable loss of volume.
  • the filaments When using triangular holes, the filaments have a Y cross section.
  • the thread When a thread, which is composed of several filaments, leaves the spinning shaft, the filaments are tightly packed in the thread, but without sticking to one another.
  • the thread At the exit of the spinning shaft, the thread typically contains a residual proportion of approximately 1 to 6% by weight of acetone.
  • the thread is provided with a preparation (finish) which mainly serves as a lubricant for the subsequent processing steps. This preparation is carried out by an oiler or with the help of an application roller.
  • the content of acetone in the threads is first further reduced, several threads are combined to form the so-called tau, and the tau is subjected to a crimping process using a crimping machine, which preferably works according to the stuffer box principle.
  • this rope is passed through a conical machine part and thus compressed to its final thickness, that is to say the thickness of the filter to be produced.
  • a composition containing glycerol triacetate is applied to the filter rope. After leaving the compression part, this further preparation ensures that the filter is fixed in the desired shape and thickness by curing.
  • the formulation applied after the threads have dried serves as a lubricant. It ensures, among other things, that the friction that occurs during the subsequent processing steps does not exceed a value that leads to the tearing or undesirable heating of the threads or the rope. Both would result in undesirable waste.
  • the lubricant also enables higher machine speeds.
  • the formulation must withstand the high shear forces that occur during this process without loss of effectiveness.
  • This lubricant usually consists of an emulsion that is made from a mixture of low-viscosity mineral oil and emulsifier. Additional components can be contained in the emulsion.
  • the object of the present invention is to provide a stable and storable emulsion which contains highly viscous mineral oils with a viscosity of at least 8.5 mm 2 / s at 100 ° C. For this, it is necessary to find emulsifiers for the production of a processable formulation. The formulation is then used in exchange for the formulations used, which contain low-viscosity mineral oils.
  • the object of the present invention is achieved by a formulation for use as a preparation in the production of threads containing a) 30-90% by weight of a mineral oil with a viscosity of at least 8.5 mm 2 / s at 100 ° C. and b) 11 -60% by weight of an emulsifier selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol esters, derivatives of polyglycerol esters, polyricin oleate, derivatives of polyricinoleate and mixtures thereof.
  • an emulsifier selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol est
  • the stability of a formulation which can be in the form of an emulsion, can be determined by the turbidity of the formulation.
  • the basic principle here is that higher turbidity indicates lower stability.
  • the processing stability of the formulation can be checked by checking the turbidity of the formulation during processing. No or a slight increase in the turbidity is particularly advantageous, while a greater increase in the turbidity indicates insufficient formulation stability.
  • the storage stability of a formulation can be checked by checking the turbidity after, for example, five days of storage at 23 ° C.
  • the viscosity at 100 ° C. is at least 8.5 mm 2 / s.
  • the mineral oil used preferably has a viscosity of 8.5 to 1000, particularly preferably 8.5 to 20 and very particularly preferably 8.5 to 11 mm 2 / s.
  • the proportion of hydrocarbons in the highly viscous mineral oil having less than 25 carbon atoms is not more than 5% by weight.
  • the average molecular weight of the highly viscous mineral oil should not be less than 480 g / mol.
  • the emulsifiers used according to the invention are selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol esters, derivatives of polyglycerol esters and mixtures thereof.
  • the esters can preferably be esters with fatty acids. All fatty acids can be used as fatty acids, e.g. Stearic acid, oleic acid, lauric acid and ricinoleic acid ([R- (Z)] - 12-hydroxy-9-octadecenoic acid).
  • the fatty acids used can alternatively be obtained from corn, cotton oil, palm oil, peanut oil, sesame oil, soybean oil, safflower oil, castor oil or other oils of native origin.
  • the fatty acids can be hydrogenated or non-hydrogenated, and condensed or non-condensed.
  • the sorbitan triester is selected from the group consisting of sorbitan triesters with fatty acids containing 10-25 carbon atoms, ethoxylated sorbitan triesters with fatty acids containing 10-25 carbons and containing 5-30 moles of ethylene oxide units per mole of sorbitan triesters and mixtures thereof.
  • the sorbitan triester can particularly preferably be selected from the group sorbitan tristearate, ethoxylated sorbitan tristearate with 5-30 mol ethylene oxide units per mol sorbitan tristearate, sorbitan trioleate, ethoxylated sorbitan trioleate with 5-30 mol ethylene oxide units per mol sorbitan trioleate, sorbitan trilaurate to 30 mol per mole of sorbitan trilaurate and mixtures thereof.
  • the polyglycerol ester fraction can consist of at least 75% di-, tri- and tetraglyceryl esters. It is preferred that the polyglycerol ester is formed from the group of polyglycerol esters with fatty acids containing 10-25 carbon atoms, derivatives of polyglycerol acids with fatty acids containing 10-25 carbon atoms, polyglycerol polyricinoleate, derivatives of polyglycerol polyricinoleate and Mixtures of the same.
  • the formulation contains as an emulsifier a) o sorbitan tristearate or ethoxylated sorbitan tristearate with 5-30 mol ethylene oxide units per mol sorbitan tristearate, b) polyglycerol polyricinoleate and c) sorbitan monolaurate and d) ethoxylated sorbitan monolaurate with 5-30 mol ethylene oxide units per mol Sorbitan monolaurate and e) sorbitan monooleate.
  • the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation, 1 to 15% by weight of ethoxylated sorbitan tristearate with 5 to 30 mol of ethylene oxide units per mol of sorbitan tristearate is in the mixture of the emulsifiers and / or based on the weight of the formulation 1 to 15 wt .-% polyglycerol polyricinoleate 0 and / or polyricinoleate in the mixture of emulsifiers.
  • the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation, 1 to 15% by weight of ethoxylated sorbitan monolaurate with 5 to 30 mol of ethylene oxide units 5 per mol of sorbitan monolaurate in the mixture of the emulsifiers and / or based on the weight of the formulation, 1 to 15% by weight of sorbitan monooleate with 5 to 30 mol of ethylene oxide units per mol of sorbitan monooleate is contained in the mixture of the emulsifiers.
  • the formulation according to the invention preferably contains 30-80% by weight of the mineral oil, more preferably 40-80% by weight, particularly preferably 45-75% by weight and very particularly preferably 55-72% by weight of the mineral oil.
  • the formulation preferably contains 15-60% by weight of the emulsifier, more preferably 20-60% by weight, particularly preferably 25-55% by weight of the emulsifier.
  • the formulation according to the invention can be a water-in-oil or an oil-in-water emulsion or the formulation forms a water-in-oil or an oil-in-water emulsion in water.
  • the formulation according to the invention is applied in emulsion form to the surface of the threads which are processed into filters for tobacco products. During this processing, the mineral oil remains on the surface of the threads or rope. It is preferred that the threads used contain cellulose acetate, which contains an average of 1.5 to 3 acetate groups per cellulose unit.
  • threads is also understood to mean fibers which can be produced by the process described here.
  • Filters for tobacco products can be produced from these threads. It is preferred that the filters are cigarette filters. In all work steps, the applied emulsion remains on the threads and thus on the rope. To a certain extent, the emulsion is therefore still present in the filters for tobacco products and the tobacco products themselves.
  • the emulsion according to the invention is illustrated by the following examples, but without being limited to these examples.
  • Viscosity according to ASTM D 445 71 mm 2 / s at 40 ° C, 9.0 mm 2 / s at 100 ° C 2 + 20 EO means 20 mol ethylene oxide units per mol ester
  • Formulations 1 and 2 from Table 1 both contain the combination according to the invention of a mineral oil with a viscosity of at least 8.5 mm 2 / s at 100 ° C. and the emulsifier according to the invention.
  • the emulsions can be prepared using standard methods.
  • Both formulations are used for the production of cellulose acetate threads by the solvent spinning process. There was no negative influence of the formulations used according to the invention in the production of the threads.
  • Formulation 1 and Formulation 2 have a storage stability at 23.degree. C. and five days, which is comparable to the formulations usually used, and during the processing of the threads into filters there was no increase in the turbidity of the emulsion due to the shear forces occurring. Both formulations behaved comparable to the formulations usually used.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Edible Oils And Fats (AREA)
  • Colloid Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention relates to an emulsion which is used as a lubricant in the production of threads, containing: a) 30 -90 wt. % mineral oil having a viscosity of at least 8,5 mm2/s at 100 DEG C, and b) 11 - 60 wt. % of an emulsifier selected from sorbitan mono esters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerin esters, derivatives of polyglycerin esters, polyricinoleate, derivatives of polyricinoleate and mixtures thereof. The threads are used in the production of filters for tobacco.

Description

Formulierung eines hochviskosen Mineralöls zur Herstellung von Filtern für Tabakwaren Formulation of a highly viscous mineral oil for the manufacture of filters for tobacco products
Die vorliegende Erfindung bezieht sich auf eine Formulierung zur Verwendung als 5 Schmiermittel bei der Herstellung von Fäden. Die Fäden werden zunächst nach einem Spinnverfahren, das bevorzugt das Lösungsmittelspinnverfahren ist, hergestellt und anschließend unter Aufbringung der erfindungsgemäßen Formulierung auf die Oberfläche der Fäden als Schmiermittel weiterverarbeitet. Die hergestellten Fäden sind bevorzugt Celluloseacetatfäden und diese Fäden werden zur Her- 0 Stellung von Filtern für Tabakwaren, speziell Zigarettenfiltern, verwendet.The present invention relates to a formulation for use as a lubricant in the manufacture of threads. The threads are first produced by a spinning process, which is preferably the solvent spinning process, and then further processed as a lubricant while applying the formulation according to the invention to the surface of the threads. The threads produced are preferably cellulose acetate threads and these threads are used for the manufacture of filters for tobacco products, especially cigarette filters.
Die Patentschrift GB 896,599 beschreibt Tabakfilter, die in Zigaretten, Pfeifen, Zigarettenspitzen oder Zigarrenspitzen eingesetzt werden können. Die beschriebenen Filterelemente bestehen aus Bündeln kontinuierlicher synthetischer Filamen- 5 te, wobei wasserunlösliche Calcium- oder Magnesiumsalze fein verteilt auf der Oberfläche der Filamente vorhanden sind. Diese fein verteilten Partikel werden durch Öle auf den Fasern fixiert. Diese öle können neben Mineralölen auch hochsiedende flüssige Ester nativer Herkunft, flüssige Ester von natürlichen Fetten oder flüssige hochmolekulare Fettalkohole sein. 0The patent specification GB 896,599 describes tobacco filters which can be used in cigarettes, pipes, cigarette holders or cigar holders. The filter elements described consist of bundles of continuous synthetic filaments, water-insoluble calcium or magnesium salts being present in finely divided form on the surface of the filaments. These finely divided particles are fixed on the fibers by oils. In addition to mineral oils, these oils can also be high-boiling liquid esters of native origin, liquid esters of natural fats or liquid high-molecular fatty alcohols. 0
Die Patentschrift GB 765,962 beschreibt ein Tabakfilterelement, das aus Cellulo- seacetatfasern besteht. Bei der Herstellung von Zigarettenfiltern wird das Cellulo- seacetatfiltermaterial vielfältigen Verarbeitungsschritten unterworfen, wie z.B. dem Recken und dem Kräuseln der Fasern. Bei diesen Verarbeitungsschritten muss 5 einerseits eine elektrostatische Aufladung der Fasern verhindert werden und andererseits muss die Oberfläche der Faser mit einem Schmiermittel versehen werden, so dass die Faser diesen Verarbeitungsschritten unterworfen werden kann. Hierbei zeigte sich, dass die Präparierung mit einem Schmiermittel, das zu keiner Elektrizitätsentladung führt, am geeignetsten ist. Dieses Schmiermittel enthält ein o Mineralöl mit einer Reinheit, mit der es sich auch zur Herstellung pharmazeutischer Produkte eignen würde. - Z -The patent specification GB 765,962 describes a tobacco filter element which consists of cellulose acetate fibers. In the manufacture of cigarette filters, the cellulose acetate filter material is subjected to various processing steps, such as, for example, stretching and crimping the fibers. During these processing steps, 5 an electrostatic charging of the fibers must be prevented on the one hand and on the other hand the surface of the fiber must be provided with a lubricant so that the fiber can be subjected to these processing steps. It was found that the most suitable preparation is a lubricant that does not lead to electricity discharge. This lubricant contains an o mineral oil with a purity with which it would also be suitable for the manufacture of pharmaceutical products. - Z -
ln der DE 12 12 459 wird ein steifes Tabakrauchfilter, das aus einem Bündel gegebenenfalls gekräuselter fortlaufender Fäden und einer Papierumhüllung besteht, beschrieben. Die Fäden bestehen aus einer Mischung eines Polyalphaolefins und eines weichmacherlöslichen Polymeren eines organischen Weichmachers. Als s flüssiger organischer Weichmacher können neben leichten, mittleren und schweren Mineralölen auch flüssige hochsiedende organische Ester oder wasserunlösliche Propylenglycole oder Polybutylenglycole verwendet werden.DE 12 12 459 describes a stiff tobacco smoke filter which consists of a bundle of optionally crimped continuous threads and a paper wrapper. The threads consist of a mixture of a polyalphaolefin and a plasticizer-soluble polymer of an organic plasticizer. In addition to light, medium and heavy mineral oils, liquid high-boiling organic esters or water-insoluble propylene glycols or polybutylene glycols can also be used as the liquid organic plasticizer.
In dem US-Patent 4,330,422 wird eine Reinigungszusammensetzung, die weißes o Mineralöl enthält, beschrieben. Die Emulsion wird zur Behandlung und Reinigung von Metalloberflächen verwendet. Die erfindungsgemäße Emulsion enthält 20-50 Gew.% eines Mineralöls mit einer Viskosität von 50-380 Saybolt-Sekunden, gemessen bei 100° F und 0,5 bis 10 Gew.% eines Emulgators. Um eine solche E- mulsion herzustellen hat sich die Verwendung von nichtionischen Emulgatoren als 5 vorteilhaft herausgestellt. Neben einer Vielzahl von Emulgatoren werden u.a. Sorbitanester und Polyglyceride von Fettsäuren angegeben. Zur Erzielung eines sehr guten Reinigungseffektes sollte nur so viel Emulgator in der Emulsion vorhanden sein, wie gerade eben notwendig ist, um eine stabile Emulsion zu bilden. Hierbei sind 0,5 bis 10 Gew-% des Emulgators in der Emulsion vorhanden, wobei 1 bis 5 0 Gew-% an Emulgator bevorzugt sind. Ist mehr Emulgator in der Emulsion vorhanden, so können nach Reinigung milchige Flecken oder Streifen auf der gereinigten Oberfläche zurückbleiben.U.S. Patent 4,330,422 describes a cleaning composition containing white mineral oil. The emulsion is used to treat and clean metal surfaces. The emulsion of the invention contains 20-50% by weight of a mineral oil with a viscosity of 50-380 Saybolt seconds, measured at 100 ° F and 0.5 to 10% by weight of an emulsifier. In order to produce such an emulsion, the use of nonionic emulsifiers has proven to be advantageous. In addition to a variety of emulsifiers, i.a. Sorbitan esters and polyglycerides of fatty acids specified. To achieve a very good cleaning effect, only as much emulsifier should be present in the emulsion as is just necessary to form a stable emulsion. 0.5 to 10% by weight of the emulsifier is present in the emulsion, with 1 to 50% by weight of emulsifier being preferred. If there is more emulsifier in the emulsion, milky stains or streaks may remain on the cleaned surface after cleaning.
Die Herstellung von Filtern für Tabakwaren findet in der Regel nach einem Pro- 5 zess statt, bei dem zunächst ein Faden, der normalerweise Celluloseacetat enthält, mit Hilfe eines Spinnverfahrens, das bevorzugt das Lösungsmittelspinnverfahren ist, hergestellt wird.The manufacture of filters for tobacco products usually takes place according to a process in which a thread, which normally contains cellulose acetate, is first produced using a spinning process, which is preferably the solvent spinning process.
Beim acetonischen Verfahren wird eine acetonische Lösung von Celluloseacetat und Mattierungsmittel TiO2 durch brauseähnliche Düsen (Spinndüsen) gepresst. o Die Bohrungen haben üblicherweise Querschnitte in Form eines gleichseitigen Dreieckes. Unterhalb der Spinndüsen befindet sich ein beheizter Spinnschacht. Die durch den Spinnschacht gesaugte Luft erwärmt sich und nimmt das aus dem gebildeten Filament ausdiffundierende Lösungsmittel Aceton auf, welches fast - ά -In the acetone process, an acetone solution of cellulose acetate and matting agent TiO 2 is pressed through spray-like nozzles (spinnerets). o The holes usually have cross sections in the form of an equilateral triangle. A heated spinning shaft is located below the spinnerets. The air sucked through the spinning shaft heats up and absorbs the solvent acetone, which diffuses out of the formed filament, which is almost - ά -
vollständig zurückgewonnen wird. Hierbei verfestigt sich die Lösung unter erheblichem Volumenschwund zu einem Filament. Bei der Verwendung von dreieckigen Bohrungen haben die Filamente einen Y-Querschnitt. Wenn ein Faden, der aus mehreren Filamenten zusammengesetzt wird den Spinnschacht verlässt, so sind s die Filamente im Faden dicht gepackt, ohne jedoch aneinander zu kleben. Am Ausgang des Spinnschachts enthält der Faden typischerweise einen Restanteil von ca. 1 bis 6 Gew-% Aceton. Hier wird der Faden mit einer Präparation (Avi- vage), die hauptsächlich als Schmiermittel für die nachfolgenden Verarbeitungsschritte dient, versehen. Diese Präparation erfolgt durch einen Öler oder mit Hilfe o einer Auftragswalze. In den nachfolgen Schritten wird zunächst der Gehalt an A- ceton in den Fäden weiter reduziert, mehrere Fäden zu dem sogenannten Tau zusammengeführt und das Tau einem Kräuselungsprozess mittels einer Kräuselmaschine, die vorzugsweise nach dem Stauchkammerprinzip arbeitet, unterworfen. Zur Herstellung von Filtern für Tabakwaren wird dieses Tau durch ein koni- 5 sches Maschinenteil geführt und so auf seine endgültige Dicke, also der Dicke des herzustellenden Filters komprimiert. Vor Einlauf in dieses konische Maschinenteil wird eine Glycerintriacetat enthaltende Zusammensetzung auf das Filtertau aufgebracht. Diese weitere Präparierung sorgt nach dem Verlassen des Komprimierteils durch Aushärten zu einer Fixierung des Filters in der gewünschten Form und Di- o cke.is fully recovered. Here, the solution solidifies into a filament with considerable loss of volume. When using triangular holes, the filaments have a Y cross section. When a thread, which is composed of several filaments, leaves the spinning shaft, the filaments are tightly packed in the thread, but without sticking to one another. At the exit of the spinning shaft, the thread typically contains a residual proportion of approximately 1 to 6% by weight of acetone. Here the thread is provided with a preparation (finish) which mainly serves as a lubricant for the subsequent processing steps. This preparation is carried out by an oiler or with the help of an application roller. In the subsequent steps, the content of acetone in the threads is first further reduced, several threads are combined to form the so-called tau, and the tau is subjected to a crimping process using a crimping machine, which preferably works according to the stuffer box principle. To produce filters for tobacco products, this rope is passed through a conical machine part and thus compressed to its final thickness, that is to say the thickness of the filter to be produced. Before entering this conical machine part, a composition containing glycerol triacetate is applied to the filter rope. After leaving the compression part, this further preparation ensures that the filter is fixed in the desired shape and thickness by curing.
Bei der Zusammenführung der Fäden zum Tau und der Komprimierung des Taus auf die endgültige Dicke dient die nach dem Trocknen der Fäden aufgebrachte Formulierung als Schmiermittel. Sie stellt u.a. sicher, dass die Reibung, die wäh- 5 rend der nachfolgenden Verarbeitungsschritte auftritt, einen Wert nicht überschreitet, der zum Abriß oder zu einer unerwünschten Erwärmung der Fäden bzw. des Taus führt. Beides würde unerwünschten Ausschuß bedingen. Zusätzlich werden durch das Schmiermittel höhere Maschinengeschwindigkeiten ermöglicht. Die Formulierung muss die bei diesem Prozess auftretenden hohen Scherkräfte o ohne Wirkungsverlust überstehen. Dieses Schmiermittel besteht üblicherweise aus einer Emulsion, die aus einer Mischung aus niedrigviskosem Mineralöl und Emulgator hergestellt wird. Weitere Komponenten können in der Emulsion enthalten sein.When the threads are brought together to form the rope and the dew is compressed to the final thickness, the formulation applied after the threads have dried serves as a lubricant. It ensures, among other things, that the friction that occurs during the subsequent processing steps does not exceed a value that leads to the tearing or undesirable heating of the threads or the rope. Both would result in undesirable waste. The lubricant also enables higher machine speeds. The formulation must withstand the high shear forces that occur during this process without loss of effectiveness. This lubricant usually consists of an emulsion that is made from a mixture of low-viscosity mineral oil and emulsifier. Additional components can be contained in the emulsion.
5 Die Mineralöle verbleiben nach der Herstellung der Filter und der entsprechenden Tabakwaren, die diese Filter enthalten, auf den Fäden.5 The mineral oils remain on the threads after the filters and the corresponding tobacco products containing these filters have been manufactured.
Beim Rauchen z.B. einer Zigarette, die ein solches Filter enthält, kann ein Teil des Mineralöls, das sich auf dem Filter befindet, vom Raucher aufgenommen werden. Mitte der 90'er Jahre haben Baldwin et al. (M.K. Baldwin et al.; „Feeding studies in o rats with mineral hydrocarbon food grade white mineral oils", Toxicol. Pathol. 20, 426 (1992)) sowie Smith et al. (J.H. Smith et al.; "Ninety-day feeding study in Fischer 344-rats of highly refined petroleum-derived food-grade white oils and waxes", Toxicol. Pathol. 24, 214 (1996)) 90-Tage-Verfütterungsstudien mit Fischer 344-Ratten durchgeführt und folgende pathologischen Merkmale gefunden: Zu- 5 nähme des Gewichts und der Mineralölmenge in der Leber, Zunahme der Leberenzyme im Serum sowie Gewichtszunahme der Lymphknoten. Diese Effekte sind mit niedrigviskosen Mineralölen signifikant ausgeprägter als mit mittel- und hochviskosen Mineralölen. Hochviskose Mineralöle sind nach dem „Scientific Commit- tee for Food" der europäischen Kommission dadurch gekennzeichnet, dass ihre o Viskosität größer 8,5 mm2/s bei 100°C bzw. größer 70 mm2/s bei 40°C ist. In der EU (Directive 1999/91/EC of 23.11.1999 amending Directive 90/128/EEC „relating to plastic materials and articles intended to come into contact with foodstuff, OJ 310/41 (4.12.1999)) wird die Verwendung von niedrigviskosen Mineralölen für Produkte mit indirektem Lebensmittelkontakt nach 2002 nicht mehr erlaubt sein. 5 Versuche, hochviskose Mineralöle in eine Formulierung einzuarbeiten, die den technischen Anforderungen des Hersteilens von Filtermaterialien entsprechen, sind bislang gescheitert. Die Emulgatoren, die zur Emulgierung von niedrigviskosen Mineralölen eingesetzt werden, führen zu keiner stabilen und verarbeitbaren Formulierung, wenn hochviskose Mineralöle eingesetzt werden. Erschwerend 0 kommt hinzu, dass an die Emulgatoren hohe Anforderungen in bezug auf die Lebensmittelunbedenklichkeit und eine eventuelle Veränderung des Geschmacks der Filterzigaretten gestellt werden. - 0 -When smoking a cigarette that contains such a filter, for example, some of the mineral oil on the filter can be absorbed by the smoker. In the mid 90 's Baldwin et al. (MK Baldwin et al .; "Feeding studies in o rats with mineral hydrocarbon food grade white mineral oils", Toxicol. Pathol. 20, 426 (1992)) and Smith et al. (JH Smith et al .; "Ninety-day feeding study in Fischer 344-rats of highly refined petroleum-derived food-grade white oils and waxes ", Toxicol. Pathol. 24, 214 (1996)) 90-day feeding studies were carried out with Fischer 344 rats and the following pathological features were found: Increases in the weight and amount of mineral oil in the liver, increased liver enzymes in the serum and increased weight in the lymph nodes. These effects are significantly more pronounced with low-viscosity mineral oils than with medium- and high-viscosity mineral oils Food "of the European Commission, characterized in that its viscosity is greater than 8.5 mm 2 / s at 100 ° C or greater than 70 mm 2 / s at 40 ° C. In the EU (Directive 1999/91 / EC of 23.11.1999 amending Directive 90/128 / EEC "relating to plastic materials and articles intended to come into contact with foodstuff, OJ 310/41 (4.12.1999)) the use of low-viscosity mineral oils for products with indirect food contact after 2002 are no longer permitted. 5 attempts to incorporate highly viscous mineral oils into a formulation that meet the technical requirements for the manufacture of filter materials have so far failed. The emulsifiers which are used to emulsify low-viscosity mineral oils do not lead to a stable and processable formulation if high-viscosity mineral oils are used. To make matters worse, the emulsifiers have high requirements with regard to food safety and a possible change in the taste of the filter cigarettes. - 0 -
Die Aufgabe der vorliegenden Erfindung ist es, eine stabile und lagerfähige Emulsion bereit zu stellen, die hochviskose Mineralöle mit einer Viskosität von mindestens 8,5 mm2/s bei 100°C enthält. Hierzu ist es notwendig, Emulgatoren zur Herstellung einer verarbeitbaren Formulierung zu finden. Die Formulierung wird dann im Austausch gegen die verwendeten Formulierungen, die niedrigviskose Mineralöle enthalten, eingesetzt.The object of the present invention is to provide a stable and storable emulsion which contains highly viscous mineral oils with a viscosity of at least 8.5 mm 2 / s at 100 ° C. For this, it is necessary to find emulsifiers for the production of a processable formulation. The formulation is then used in exchange for the formulations used, which contain low-viscosity mineral oils.
Die Aufgabe der vorliegenden Erfindung wird durch eine Formulierung zur Verwendung als Präparation bei der Herstellung von Fäden enthaltend a) 30-90 Gew.-% eines Mineralöls mit einer Viskosität von mindestens 8,5 mm2/s bei 100°C und b) 11-60 Gew.-% eines Emulgators ausgewählt aus Sorbitanmonoester, Derivate von Sorbitanmonoestern, Sorbitandiestern, Derivate von Sorbitandiestern, Sorbitantriestern, Derivate von Sorbitantriestern, Polyglycerinestem, Derivate von Polyglycerinestern, Polyricinoleat, Derivate von Polyricinoleat und Mischungen derselben erreicht.The object of the present invention is achieved by a formulation for use as a preparation in the production of threads containing a) 30-90% by weight of a mineral oil with a viscosity of at least 8.5 mm 2 / s at 100 ° C. and b) 11 -60% by weight of an emulsifier selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol esters, derivatives of polyglycerol esters, polyricin oleate, derivatives of polyricinoleate and mixtures thereof.
Unerwarteterweise zeigte sich, dass solche Formulierungen eine vergleichbare und teilweise sogar bessere Lager- und Verarbeitungsstabilität haben. Die Stabilität einer Formulierung, die als Emulsion vorliegen kann, lässt sich durch die Trü- bung der Formulierung bestimmen. Dabei gilt grundsätzlich, dass eine höhere Trübung eine geringere Stabilität anzeigt. Die Verarbeitungsstabilität der Formulierung lässt sich dadurch prüfen, indem die Trübung der Formulierung während der Verarbeitung überprüft wird. Dabei ist keine oder eine geringe Zunahme der Trübung besonders vorteilhaft, während eine stärkere Zunahme der Trübung auf eine nicht ausreichende Formulierungssstabilität schließen lässt. Die Lagerstabilität einer Formulierung lässt sich durch Überprüfung der Trübung nach z.B. fünf Tagen Lagerung bei 23°C überprüfen. Ist eine Zunahme der Trübung nach einer solchen Lagerzeit nicht feststellbar oder sehr gering, so ist die Lagerstabilität der Formulierung als sehr gut zu beurteilen, während eine Zunahme der Trübung bzw. ein eventuelles Entmischen der Phasen als schlechte Lagerstabilität zu charakterisieren ist. - t> -It was unexpectedly found that such formulations have comparable and in some cases even better storage and processing stability. The stability of a formulation, which can be in the form of an emulsion, can be determined by the turbidity of the formulation. The basic principle here is that higher turbidity indicates lower stability. The processing stability of the formulation can be checked by checking the turbidity of the formulation during processing. No or a slight increase in the turbidity is particularly advantageous, while a greater increase in the turbidity indicates insufficient formulation stability. The storage stability of a formulation can be checked by checking the turbidity after, for example, five days of storage at 23 ° C. If an increase in the turbidity after such a storage time cannot be determined or is very slight, the storage stability of the formulation can be assessed as very good, while an increase in the turbidity or a possible separation of the phases can be characterized as poor storage stability. - t> -
Bei dem erfindungsgemäßen hochviskosen Mineralöl ist die Viskosität bei 100°C gemessen nach ASTM D 445 mindestens 8,5 mm2/s. Das eingesetzte Mineralöl hat bevorzugt eine Viskosität von 8,5 bis 1000, besonders bevorzugt von 8,5 bis 20 und ganz besonders bevorzugt von 8,5 bis 11 mm2/s.In the case of the high-viscosity mineral oil according to the invention, the viscosity at 100 ° C., measured according to ASTM D 445, is at least 8.5 mm 2 / s. The mineral oil used preferably has a viscosity of 8.5 to 1000, particularly preferably 8.5 to 20 and very particularly preferably 8.5 to 11 mm 2 / s.
Es ist bevorzugt, dass der Anteil an Kohlenwasserstoffen in dem hochviskosen Mineralöl mit weniger als 25 Kohlenstoffatomen nicht mehr als 5 Gew.-% beträgt. Das mittlere Molekulargewicht des hochviskosen Mineralöls sollte nicht weniger als 480 g/mol betragen.It is preferred that the proportion of hydrocarbons in the highly viscous mineral oil having less than 25 carbon atoms is not more than 5% by weight. The average molecular weight of the highly viscous mineral oil should not be less than 480 g / mol.
Die erfindungsgemäß eingesetzten Emulgatoren sind ausgewählt aus Sorbitan- monoester, Derivate von Sorbitanmonoestern, Sorbitandiester, Derivate von Sorbitandiestern, Sorbitantriester, Derivate von Sorbitantriestern, Polyglycerinester, Derivate von Polyglycerinestern und Mischungen derselben. Die Ester können bevorzugt Ester mit Fettsäuren sein. Als Fettsäure können alle Fettsäuren verwendet werden, wie z.B. Stearinsäure, Ölsäure, Laurinsäure und Ricinolsäure ([R- (Z)]-12-Hydroxy-9-Octadecensäure). Die eingesetzten Fettsäuren können alternativ aus Mais, Baumwollöl, Palmöl, Erdnussöl, Sesamöl, Sojabohnenöl, Safloröl, Ricinusöl oder anderen ölen nativer Herkunft gewonnen werden. Hierbei können die Fettsäuren hydriert oder nicht hydriert, sowie kondensiert oder nicht kondensiert vorliegen.The emulsifiers used according to the invention are selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol esters, derivatives of polyglycerol esters and mixtures thereof. The esters can preferably be esters with fatty acids. All fatty acids can be used as fatty acids, e.g. Stearic acid, oleic acid, lauric acid and ricinoleic acid ([R- (Z)] - 12-hydroxy-9-octadecenoic acid). The fatty acids used can alternatively be obtained from corn, cotton oil, palm oil, peanut oil, sesame oil, soybean oil, safflower oil, castor oil or other oils of native origin. The fatty acids can be hydrogenated or non-hydrogenated, and condensed or non-condensed.
Es ist bevorzugt, dass der Sorbitantriester ausgewählt wird aus der Gruppe Sorbitantriester mit Fettsäuren, die 10-25 Kohlenstoffatome enthalten, ethoxylierte Sorbitantriester mit Fettsäuren, die 10-25 Kohlenstoffe enthalten und 5-30 mol E- thylenoxideinheiten pro mol Sorbitantriester enthalten und Mischungen derselben. Besonders bevorzugt kann der Sorbitantriester ausgewählt werden aus der Gruppe Sorbitantristearat, ethoxyliertes Sorbitantristearat mit 5-30 mol Ethylenoxidein- heiten pro Mol Sorbitantristearat, Sorbitantrioleat, ethoxyliertes Sorbitantrioleat mit 5-30 mol Ethylenoxideinheiten pro mol Sorbitantrioleat, Sorbitantrilaurat, ethoxyliertes Sorbitantrilaurat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantrilaurat und Mischungen derselben. - ( -It is preferred that the sorbitan triester is selected from the group consisting of sorbitan triesters with fatty acids containing 10-25 carbon atoms, ethoxylated sorbitan triesters with fatty acids containing 10-25 carbons and containing 5-30 moles of ethylene oxide units per mole of sorbitan triesters and mixtures thereof. The sorbitan triester can particularly preferably be selected from the group sorbitan tristearate, ethoxylated sorbitan tristearate with 5-30 mol ethylene oxide units per mol sorbitan tristearate, sorbitan trioleate, ethoxylated sorbitan trioleate with 5-30 mol ethylene oxide units per mol sorbitan trioleate, sorbitan trilaurate to 30 mol per mole of sorbitan trilaurate and mixtures thereof. - (-
Wenn als Emulgator ein Polygylcerinester eingesetzt wird, dann kann der Polygly- cerinesteranteil zusammengesetzt aus mindestens 75% Di-, Tri- und Tetraglyce- rinestern bestehen. Hierbei ist es bevorzugt, dass der Polyglycerinester ausgebildet wird aus der Gruppe Polyglycerinester mit Fettsäuren, die 10-25 Kohlenstoff- s atome enthalten, Derivate von Polyglycerinsäuren mit Fettsäuren, die 10-25 Kohlenstoffatome enthalten, Polyglycerin-Polyrizinoleat, Derivate von Polyglycerin- Polyrizinoleat und Mischungen derselben.If a polyglycerol ester is used as the emulsifier, the polyglycerol ester fraction can consist of at least 75% di-, tri- and tetraglyceryl esters. It is preferred that the polyglycerol ester is formed from the group of polyglycerol esters with fatty acids containing 10-25 carbon atoms, derivatives of polyglycerol acids with fatty acids containing 10-25 carbon atoms, polyglycerol polyricinoleate, derivatives of polyglycerol polyricinoleate and Mixtures of the same.
In einer bevorzugten Ausführungsform enthält die Formulierung als Emulgator a) o Sorbitantristearat oder ethoxyliertes Sorbitantristearat mit 5-30 mol Ethylenoxideinheiten pro mol Sorbitantristearat, b) Polyglycerin-Polyrizinoleat und c) Sorbi- tanmonolaurat und d) ethoxyliertes Sorbitanmonolaurat mit 5-30 mol Ethylenoxideinheiten pro mol Sorbitanmonolaurat und e) Sorbitanmonooleat.In a preferred embodiment, the formulation contains as an emulsifier a) o sorbitan tristearate or ethoxylated sorbitan tristearate with 5-30 mol ethylene oxide units per mol sorbitan tristearate, b) polyglycerol polyricinoleate and c) sorbitan monolaurate and d) ethoxylated sorbitan monolaurate with 5-30 mol ethylene oxide units per mol Sorbitan monolaurate and e) sorbitan monooleate.
5 In einer weiteren Ausführungsform ist, falls der Emulgator als Mischung von mindestens zwei Emulgatoren vorliegt, bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% ethoxyliertes Sorbitantristearat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantristearat in der Mischung der Emulgatoren und/oder bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% Polyglyzerin-Polyricinoleat 0 und/oder Polyricinoleat in der Mischung der Emulgatoren enthalten.In a further embodiment, if the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation, 1 to 15% by weight of ethoxylated sorbitan tristearate with 5 to 30 mol of ethylene oxide units per mol of sorbitan tristearate is in the mixture of the emulsifiers and / or based on the weight of the formulation 1 to 15 wt .-% polyglycerol polyricinoleate 0 and / or polyricinoleate in the mixture of emulsifiers.
Weiterhin ist bevorzugt, dass falls der Emulgator als Mischung von mindestens zwei Emulgatoren vorliegt, bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% ethoxyliertes Sorbitanmonolaurat mit 5 bis 30 mol Ethylenoxideinheiten 5 pro mol Sorbitanmonolaurat in der Mischung der Emulgatoren und/oder bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% Sorbitanmonooleat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitanmonooleat in der Mischung der E- mulgatoren enthalten ist.It is further preferred that if the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation, 1 to 15% by weight of ethoxylated sorbitan monolaurate with 5 to 30 mol of ethylene oxide units 5 per mol of sorbitan monolaurate in the mixture of the emulsifiers and / or based on the weight of the formulation, 1 to 15% by weight of sorbitan monooleate with 5 to 30 mol of ethylene oxide units per mol of sorbitan monooleate is contained in the mixture of the emulsifiers.
0 Die erfindungsgemäße Formulierung enthält bevorzugt 30-80 Gew.% des Mineralöls, weiter bevorzugt 40-80 Gew.-%, besonders bevorzugt 45-75 Gew.-% und ganz besonders bevorzugt 55-72 Gew.% des Mineralöls. - ö -The formulation according to the invention preferably contains 30-80% by weight of the mineral oil, more preferably 40-80% by weight, particularly preferably 45-75% by weight and very particularly preferably 55-72% by weight of the mineral oil. - ö -
ln der Formulierung sind bevorzugt 15-60 Gew.-% des Emulgators, weiter bevorzugt 20-60 Gew.-%, besonders bevorzugt 25-55 Gew.-% des Emulgators, vorhanden.The formulation preferably contains 15-60% by weight of the emulsifier, more preferably 20-60% by weight, particularly preferably 25-55% by weight of the emulsifier.
Die erfindungsgemäße Formulierung kann eine Wasser-in-ÖI oder eine Öl-inWasser-Emulsion sein oder die Formulierung bildet in Wasser eine Wasser-in-ÖI oder eine öl-in-Wasser-Emulsion. Die erfindungsgemäße Formulierung wird nach dem Spinnvorgang in Emulsionsform auf die Oberfläche der Fäden, die zu Filtern für Tabakwaren verarbeitet werden, aufgebracht. Bei dieser Verarbeitung verbleibt das Mineralöl auf der Oberfläche der Fäden bzw. des Taus. Es ist bevorzugt, dass die verwendeten Fäden Celluloseacetat enthalten, das im Mittel 1 ,5 bis 3 Acetat- gruppen pro Celluloseeinheit enthält.The formulation according to the invention can be a water-in-oil or an oil-in-water emulsion or the formulation forms a water-in-oil or an oil-in-water emulsion in water. After the spinning process, the formulation according to the invention is applied in emulsion form to the surface of the threads which are processed into filters for tobacco products. During this processing, the mineral oil remains on the surface of the threads or rope. It is preferred that the threads used contain cellulose acetate, which contains an average of 1.5 to 3 acetate groups per cellulose unit.
Unter der Bezeichnung Fäden sind im Sinne dieser Erfindung auch Fasern zu ver- stehen, die nach dem hier beschriebenen Verfahren hergestellt werden können.For the purposes of this invention, the term threads is also understood to mean fibers which can be produced by the process described here.
Aus diesen Fäden lassen sich Filter für Tabakwaren herstellen. Hierbei ist es bevorzugt, dass die Filter Zigarettenfilter sind. Bei allen Arbeitsschritten verbleibt die aufgebrachte Emulsion auf den Fäden und somit auf dem Tau. Somit ist die Emul- sion zu einem gewissen Anteil auch noch in den Filtern für Tabakwaren und den Tabakwaren selbst vorhanden.Filters for tobacco products can be produced from these threads. It is preferred that the filters are cigarette filters. In all work steps, the applied emulsion remains on the threads and thus on the rope. To a certain extent, the emulsion is therefore still present in the filters for tobacco products and the tobacco products themselves.
Die erfindungsgemäße Emulsion wird an folgenden Beispielen erläutert, ohne jedoch auf diese Beispiele beschränkt zu sein. The emulsion according to the invention is illustrated by the following examples, but without being limited to these examples.
yy
BeispieleExamples
Tabelle 1Table 1
1 Primol® 352 ist ein hochviskoses Mineralöl der ESSO AG 1 Primol ® 352 is a highly viscous mineral oil from ESSO AG
Viskosität nach ASTM D 445: 71 mm2/s bei 40°C, 9,0 mm2/s bei 100°C 2 + 20 EO bedeutet 20 mol Ethylenoxideinheiten pro mol EsterViscosity according to ASTM D 445: 71 mm 2 / s at 40 ° C, 9.0 mm 2 / s at 100 ° C 2 + 20 EO means 20 mol ethylene oxide units per mol ester
Die Formulierungen 1 und 2 aus Tabelle 1 enthalten beide die erfindungsgemäße Kombination aus einem Mineralöl mit einer Viskosität von wenigstens 8,5 mm2/s bei 100°C und dem erfindungsgemäßen Emulgator. Die Emulsionen lassen sich nach Standardmethoden herstellen.Formulations 1 and 2 from Table 1 both contain the combination according to the invention of a mineral oil with a viscosity of at least 8.5 mm 2 / s at 100 ° C. and the emulsifier according to the invention. The emulsions can be prepared using standard methods.
Zur Herstellung der Formulierung 1 wird Primol 352 bei Raumtemperatur vorgelegt und unter ständigem Rühren werden die Rohstoffe in der Reihenfolge Sorbitanmonolaurat, Sorbitanmonolaurat + 20 EO, Sorbitanmonooleat, Polyglyzerin- Polyricinoleat und Wasser zugegeben. Formulierung 1 wird für weitere 30 Minuten gerührt.To prepare formulation 1, Primol 352 is initially introduced at room temperature and the raw materials are added in the order of sorbitan monolaurate, sorbitan monolaurate + 20 EO, sorbitan monooleate, polyglycerol polyricinoleate and water with constant stirring. Formulation 1 is stirred for an additional 30 minutes.
Zur Herstellung der Formulierung 2 wird auf 50°C erwärmtes Primol 352 in einem Rührer vorgelegt. Unter ständigem Rühren und bei 50°C werden die weiteren Rohstoffe in der Reihenfolge Sorbitanmonolaurat, Sorbitanmonolaurat + 20 EO, Sorbitantristearat + 20 EO, Polyglycerin-Polyrizinoleat und Wasser zugegeben. Nach 30 Minuten rühren bei 50 °C lässt man die Formulierung auf Raumtemperatur abkühlen und rührt sie bei dieser Temperatur für weitere 30 Minuten. - T U -To prepare formulation 2, Primol 352, heated to 50 ° C., is placed in a stirrer. With constant stirring and at 50 ° C, the other raw materials are added in the order sorbitan monolaurate, sorbitan monolaurate + 20 EO, sorbitan tristearate + 20 EO, polyglycerol polyricinoleate and water. After stirring for 30 minutes at 50 ° C., the formulation is allowed to cool to room temperature and is stirred at this temperature for a further 30 minutes. - TU -
Beide Formulierungen werden zur Herstellung von Celluloseacetatfäden nach dem Lösungsmittelspinnverfahren eingesetzt. Hierbei zeigte sich bei der Herstellung der Fäden kein negativer Einfluss der erfindungsgemäß eingesetzten Formulierungen. Formulierung 1 und Formulierung 2 zeigen eine Lagerstabilität bei 23°C und fünf Tagen, die mit den üblicherweise eingesetzten Formulierungen vergleichbar ist und während der Verarbeitung der Fäden zu Filtern trat keine Zunahme der Trübung der Emulsion bedingt durch auftretende Scherkräfte ein. Beide Formulierungen verhielten sich vergleichbar mit den üblicherweise eingesetzten Formulierungen. Both formulations are used for the production of cellulose acetate threads by the solvent spinning process. There was no negative influence of the formulations used according to the invention in the production of the threads. Formulation 1 and Formulation 2 have a storage stability at 23.degree. C. and five days, which is comparable to the formulations usually used, and during the processing of the threads into filters there was no increase in the turbidity of the emulsion due to the shear forces occurring. Both formulations behaved comparable to the formulations usually used.

Claims

Patentansprüche claims
1. Formulierung zur Verwendung als Schmiermittel bei der Herstellung von Fäden enthaltend: a) 30 bis 90 Gew.-% eines Mineralöls mit einer Viskosität von mindestens 8,5 s mm2/s bei 100°C, und b) 11 bis 60 Gew.-% eines Emulgators ausgewählt aus Sorbitanmonoestern, Derivate von Sorbitanmonoestern, Sorbitandiestern, Derivate von Sorbitandiestern, Sorbitantriestern, Derivate von Sorbitantriestern, Polyglycerinestem, Derivate von Polyglycerinestem, Polyricinoleat, Derivate von Polyricinoleat und o Mischungen derselben.1. Formulation for use as a lubricant in the production of threads containing: a) 30 to 90 wt .-% of a mineral oil with a viscosity of at least 8.5 s mm 2 / s at 100 ° C, and b) 11 to 60 wt .-% of an emulsifier selected from sorbitan monoesters, derivatives of sorbitan monoesters, sorbitan diesters, derivatives of sorbitan diesters, sorbitan triesters, derivatives of sorbitan triesters, polyglycerol esters, derivatives of polyglycerol esters, polyricinoleate, derivatives of polyricinoleate and mixtures thereof.
2. Formulierung nach Anspruch 1 , dadurch gekennzeichnet, dass der Sorbitantriester ausgewählt wird aus der Gruppe Sorbitantriester mit Fettsäuren, die 10 bis 25 Kohlenstoff-Atome enthalten, ethoxylierter Sorbitantriester mit Fett- 5 säuren die 10 bis 25 Kohlenstoff-Atome enthalten und 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantriester und Mischungen derselben.2. Formulation according to claim 1, characterized in that the sorbitan triester is selected from the group sorbitan triesters with fatty acids containing 10 to 25 carbon atoms, ethoxylated sorbitan triesters with fatty acids containing 5 to 30 carbon atoms and 5 to 30 moles of ethylene oxide units per mole of sorbitan triesters and mixtures thereof.
3. Formulierung nach Anspruch 2, dadurch gekennzeichnet, dass der Sorbitantriester ausgewählt wird aus der Gruppe Sorbitantristearat, ethoxyliertes 0 Sorbitantristearat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantristearat, Sorbitantrioleat, ethoxyliertes Sorbitantrioleat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantrioleat, Sorbitantrilaurat, ethoxyliertes Sorbitantrilaurat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantrilaurat und Mischungen derselben. 53. Formulation according to claim 2, characterized in that the sorbitan triester is selected from the group sorbitan tristearate, ethoxylated 0 sorbitan tristearate with 5 to 30 mol ethylene oxide units per mol sorbitan tristearate, sorbitan trioleate, ethoxylated sorbitan trioleate with 5 to 30 mol ethylene oxide units per mol sorbitan triolate, sorbitan trilaurate Sorbitan trilaurate with 5 to 30 moles of ethylene oxide units per mole of sorbitan trilaurate and mixtures thereof. 5
4. Formulierung nach Anspruch 1 , dadurch gekennzeichnet, dass der Polyglycerinester ausgewählt wird aus der Gruppe Polyglycerinester mit Fettsäuren die 10 bis 25 Kohlenstoff-Atome enthalten, Derivate von Polyglycerinestem mit Fettsäuren die 10 bis 25 Kohlenstoff-Atom enthalten, Polyglycerin- 0 Polyricinoleat, Derivate von Polyglycerin-Polyricinoleat und Mischungen derselben. 4. Formulation according to claim 1, characterized in that the polyglycerol ester is selected from the group polyglycerol esters with fatty acids containing 10 to 25 carbon atoms, derivatives of polyglycerol esters with fatty acids containing 10 to 25 carbon atoms, polyglycerol-0 polyricinoleate, derivatives polyglycerol polyricin oleate and mixtures thereof.
5. Formulierung nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Emulsion 30 bis 80 Gew.-% des Mineralöls enthält.5. Formulation according to one or more of claims 1 to 4, characterized in that the emulsion contains 30 to 80 wt .-% of the mineral oil.
5 6. Formulierung nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Emulsion 15 bis 60 Gew.-% des Emulgators enthält.5 6. Formulation according to one or more of claims 1 to 5, characterized in that the emulsion contains 15 to 60 wt .-% of the emulsifier.
7. Formulierung nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass in der Formulierung als Emulgator folgende Komponenten o enthalten sind: a) Sorbitantristearat oder ethoxyliertes Sorbitantristearat mit 5 bis 30 mol E- thylenoxideinheiten pro mol Sorbitantristearat b) Polyglyzerin-Polyricinoleat und c) Sorbitanmonolaurat und 5 d) ethoxyliertes Sorbitanmonolaurat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitanmonolaurat und e) Sorbitanmonooleat.7. Formulation according to one or more of claims 1 to 6, characterized in that the following components o are contained in the formulation as emulsifier: a) sorbitan tristearate or ethoxylated sorbitan tristearate with 5 to 30 mol ethylene oxide units per mol sorbitan tristearate b) polyglycerol polyricinoleate and c) sorbitan monolaurate and 5 d) ethoxylated sorbitan monolaurate with 5 to 30 mol ethylene oxide units per mol sorbitan monolaurate and e) sorbitan monooleate.
8. Formulierung nach einem oder mehreren der Ansprüche 1 bis 7, dadurch ge- o kennzeichnet, dass falls der Emulgator als Mischung von mindestens zwei E- mulgatoren vorliegt, bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.- % ethoxyliertes Sorbitantristearat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitantristearat in der Mischung der Emulgatoren und/oder bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% Polyglyzerin-Polyricinoleat 5 und/oder Polyricinoleat in der Mischung der Emulgatoren enthalten ist.8. Formulation according to one or more of claims 1 to 7, characterized in that if the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation, 1 to 15% by weight of ethoxylated sorbitan tristearate with 5 up to 30 mol ethylene oxide units per mol sorbitan tristearate in the mixture of the emulsifiers and / or based on the weight of the formulation 1 to 15% by weight polyglycerol polyricinoleate 5 and / or polyricinoleate is contained in the mixture of the emulsifiers.
9. Formulierung nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass falls der Emulgator als Mischung von mindestens zwei E- mulgatoren vorliegt, bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.- 0 % ethoxyliertes Sorbitanmonolaurat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitanmonolaurat in der Mischung der Emulgatoren und/oder bezogen auf das Gewicht der Formulierung 1 bis 15 Gew.-% Sorbitanmonooleat mit 5 bis 30 mol Ethylenoxideinheiten pro mol Sorbitanmonooleat in der Mischung der Emulgatoren enthalten ist.9. Formulation according to one or more of claims 1 to 8, characterized in that if the emulsifier is present as a mixture of at least two emulsifiers, based on the weight of the formulation 1 to 15% by weight of 0% ethoxylated sorbitan monolaurate with 5 to 30 moles of ethylene oxide units per mole of sorbitan monolaurate in the mixture of the emulsifiers and / or, based on the weight of the formulation, 1 to 15% by weight of sorbitan monooleate with 5 up to 30 moles of ethylene oxide units per mole of sorbitan monooleate is contained in the mixture of the emulsifiers.
10. Formulierung nach Anspruch 1 , dadurch gekennzeichnet, dass das Mineralöl bevorzugt eine Viskosität von 8,5 bis 1000 mm2/s bei 100°C hat.10. Formulation according to claim 1, characterized in that the mineral oil preferably has a viscosity of 8.5 to 1000 mm 2 / s at 100 ° C.
11. Formulierung nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Formulierung eine Wasser-in-ÖI oder eine Öl-inWasser Emulsion ist.11. Formulation according to one or more of claims 1 to 10, characterized in that the formulation is a water-in-oil or an oil-in-water emulsion.
12. Fäden, erhältlich durch ein Spinnverfahren, wobei die Fäden nach dem Spinnen mit der Formulierung nach einem oder mehreren der Ansprüche 1 bis 11 als Schmiermittel, unter Aufbringung auf die Oberfläche der Fäden, präpariert werden.12. Threads obtainable by a spinning process, the threads being prepared after spinning with the formulation according to one or more of claims 1 to 11 as a lubricant, with application to the surface of the threads.
13. Fäden nach Anspruch 12, dadurch gekennzeichnet, dass die Fäden Celluloseacetat mit im Mittel 1 ,5 bis 3 Acetatgruppen pro Cellulose-Einheit enthalten.13. Threads according to claim 12, characterized in that the threads contain cellulose acetate with an average of 1.5 to 3 acetate groups per cellulose unit.
14. Zigarettenfilter, enthaltend Fäden nach Anspruch 12 oder 13.14. Cigarette filter containing threads according to claim 12 or 13.
15. Verwendung der Formulierung nach einem oder mehreren der Ansprüche 1 bis 11 als Schmiermittel bei der Herstellung von Fäden für Filter für Tabakwaren.15. Use of the formulation according to one or more of claims 1 to 11 as a lubricant in the manufacture of threads for filters for tobacco products.
16. Verwendung der Formulierung nach Anspruch 15, dadurch gekennzeichnet, dass die Fäden zur Herstellung von Zigarettenfiltern verwendet werden. 16. Use of the formulation according to claim 15, characterized in that the threads are used for the production of cigarette filters.
EP03732455A 2002-07-11 2003-05-24 Formulation of a highly viscous mineral oil for the production of filters for tobacco Expired - Lifetime EP1530657B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03732455A EP1530657B1 (en) 2002-07-11 2003-05-24 Formulation of a highly viscous mineral oil for the production of filters for tobacco

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02015405 2002-07-11
EP02015405A EP1380684A1 (en) 2002-07-11 2002-07-11 Formulation of a high viscosity mineral oil for the production of filters for tobacco articles
EP03732455A EP1530657B1 (en) 2002-07-11 2003-05-24 Formulation of a highly viscous mineral oil for the production of filters for tobacco
PCT/EP2003/005440 WO2004007831A1 (en) 2002-07-11 2003-05-24 Formulation of a highly viscous mineral oil for the production of filters for tobacco

Publications (2)

Publication Number Publication Date
EP1530657A1 true EP1530657A1 (en) 2005-05-18
EP1530657B1 EP1530657B1 (en) 2010-04-28

Family

ID=29724429

Family Applications (2)

Application Number Title Priority Date Filing Date
EP02015405A Withdrawn EP1380684A1 (en) 2002-07-11 2002-07-11 Formulation of a high viscosity mineral oil for the production of filters for tobacco articles
EP03732455A Expired - Lifetime EP1530657B1 (en) 2002-07-11 2003-05-24 Formulation of a highly viscous mineral oil for the production of filters for tobacco

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP02015405A Withdrawn EP1380684A1 (en) 2002-07-11 2002-07-11 Formulation of a high viscosity mineral oil for the production of filters for tobacco articles

Country Status (6)

Country Link
US (1) US7153447B2 (en)
EP (2) EP1380684A1 (en)
AT (1) ATE466130T1 (en)
AU (1) AU2003238389A1 (en)
DE (1) DE50312667D1 (en)
WO (1) WO2004007831A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1574142A1 (en) * 2004-03-08 2005-09-14 Acetate Products Limited Process for making filter tow
US20050287368A1 (en) * 2004-06-25 2005-12-29 Celanese Acetate Llc Cellulose acetate tow and method of making same
US7585442B2 (en) * 2004-06-25 2009-09-08 Celanese Acetate, Llc Process for making cellulose acetate tow
GB0517551D0 (en) * 2005-08-27 2005-10-05 Acetate Products Ltd Process for making filter tow
US8336557B2 (en) 2007-11-28 2012-12-25 Philip Morris Usa Inc. Smokeless compressed tobacco product for oral consumption
CA2728086A1 (en) 2008-06-20 2009-12-23 3M Innovative Properties Company An aqueous lubricant emulsion for medical or apparatus and a method of washing
GB201400990D0 (en) * 2014-01-21 2014-03-05 British American Tobacco Co Filter materials and filters made therefrom
EP3409829B1 (en) * 2017-05-30 2020-08-12 Rhodia Acetow GmbH Composition comprising hydrocarbons, emulsifiers and water, its use and products comprising such composition

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US765962A (en) * 1904-03-25 1904-07-26 American Paper Goods Co Feeder for sheets of paper, &c.
US896599A (en) * 1908-03-03 1908-08-18 James A Thomason Railroad bumping-post.
US2461043A (en) * 1944-11-10 1949-02-08 American Viscose Corp Process of conditioning cellulose ester filaments
US2436980A (en) * 1945-01-01 1948-03-02 Ind Rayon Corp Tire cord and method of manufacture
US2565403A (en) * 1948-04-27 1951-08-21 Standard Oil Dev Co Textile oils
US2690426A (en) * 1950-03-07 1954-09-28 Atlas Powder Co Lubricating compositions
IT599386A (en) * 1952-12-05
US2839464A (en) * 1954-02-16 1958-06-17 Exxon Research Engineering Co Textile oil
US3050465A (en) * 1959-05-04 1962-08-21 Shell Oil Co Water-in-oil emulsion hydraulic fluids
US3192159A (en) * 1961-10-17 1965-06-29 Shell Oil Co Water-in-oil emulsion lubricant and hydraulic fluid
US3038478A (en) 1960-05-23 1962-06-12 Eastman Kodak Co Method for producing rigid tobacco smoke filters
US3242074A (en) * 1963-03-22 1966-03-22 Eastman Kodak Co Fiber treating compositions and fibers treated therewith
US3297570A (en) * 1964-05-28 1967-01-10 Eastman Kodak Co Yarn treating compositions
US3306850A (en) * 1964-12-17 1967-02-28 Du Pont Composition
US3522175A (en) * 1965-02-13 1970-07-28 Kao Corp Lubricant composition for synthetic fibers
GB1211551A (en) * 1967-01-17 1970-11-11 Courtalds Ltd Crimped tow finish
US3428560A (en) * 1967-02-27 1969-02-18 Du Pont Yarn-lubricating composition
US3652419A (en) * 1968-03-06 1972-03-28 Witco Chemical Corp Antistatic fiber lubricant
US3756253A (en) * 1970-12-18 1973-09-04 Mitsubishi Acetate Co Ltd Cellulose acetate fiber tobacco smoke filter and process of manufacturing the same
US3781202A (en) * 1972-01-28 1973-12-25 Allied Chem Spin finish for polyamide yarn processed at high temperature
US4330422A (en) 1977-02-01 1982-05-18 Minnesota Mining And Manufacturing Company Treating composition containing white oil
US4995884A (en) * 1989-12-08 1991-02-26 Henkel Corporation Polyalphaolefin emulsions for fiber and textile applications
JPH0717919B2 (en) * 1991-12-05 1995-03-01 三洋化成工業株式会社 Oil agent for dust adsorption
US5232742A (en) * 1992-05-15 1993-08-03 Bridgestone/Firestone, Inc. Spin finish composition
JP2882718B2 (en) * 1992-07-30 1999-04-12 旭化成工業株式会社 Manufacturing method of synthetic fiber
JP3639876B2 (en) * 1994-06-29 2005-04-20 新日本石油株式会社 Rust preventive lubricant composition for plastic working

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004007831A1 *

Also Published As

Publication number Publication date
WO2004007831A1 (en) 2004-01-22
ATE466130T1 (en) 2010-05-15
DE50312667D1 (en) 2010-06-10
US7153447B2 (en) 2006-12-26
US20040007687A1 (en) 2004-01-15
EP1380684A1 (en) 2004-01-14
EP1530657B1 (en) 2010-04-28
AU2003238389A1 (en) 2004-02-02

Similar Documents

Publication Publication Date Title
EP0797563B1 (en) Synthetic esters from alcohols and fatty acid mixtures of vegetable oils high in oleic acid and low in stearic acid
DE3241197C2 (en) Metal-rolling oil composition
DE2034383A1 (en) Mixtures of synthetic esters and their uses
DE1079521B (en) Filter rod and filter elements consisting of it for tobacco smoke and manufacturing processes for this
EP1530657B1 (en) Formulation of a highly viscous mineral oil for the production of filters for tobacco
DE10327026A1 (en) Airlaid process with improved throughput
DE1771597B2 (en) LUBRICANT AND RELEASE AGENT FOR GLASS MOLDING
DE3611027A1 (en) COLD ROLLING OIL FOR STEEL
DE69803491T2 (en) WATER-IN-OIL EMULSIFIED FAT COMPOSITION
DE19632088A1 (en) Fast crystallizing fat with low trans fatty acid content
DE69603953T2 (en) METHOD FOR PURIFYING POLYVINYL ALCOHOL
DE69421523T2 (en) OIL ADDITIVES AND COMPOSITIONS
EP0147726A2 (en) Defoamer for water dispersions and synthetic resin solutions
DE2618263C3 (en) Mouldable collagen masses and food casings made therefrom
DE1224034B (en) Process for stabilizing polypropylene
DE1644871B2 (en) LUBRICANT
DE3316523C2 (en) Process and device for deodorising and deacidifying fats and oils
DE60003460T2 (en) IMPREGNIERUNGSVERFAHREN
DE3047503C2 (en) Aqueous sizing composition for glass fibers and their application
EP0337237A1 (en) Combination of stabilisators for Ca/Zn-stabilized PVC-moulding masses, PVC-moulding masses and process for their preparation
DE19822775B4 (en) Process for the production of hardened filter rods in the cigarette industry
EP3409829B1 (en) Composition comprising hydrocarbons, emulsifiers and water, its use and products comprising such composition
DE1770768C3 (en) Plasticizers for cellulose esters
DE2516736A1 (en) POLYOXYAETHYLENE-POLYOXYPROPYLENE GLYCOL MONOESTER AND THE METHOD FOR ITS MANUFACTURING
DE1569399C3 (en) Production of a polymer-wax mixture

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050131

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: DOBBELSTEIN, HUBERT

Inventor name: EMINI, SHEFQET

17Q First examination report despatched

Effective date: 20090417

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: EMINI, SHEFQET

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50312667

Country of ref document: DE

Date of ref document: 20100610

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100428

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100808

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

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

Ref country code: MC

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

Effective date: 20100531

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100729

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100830

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

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

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: LI

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

Effective date: 20100531

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: CH

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

Effective date: 20100531

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

26N No opposition filed

Effective date: 20110131

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

Ref country code: AT

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

Effective date: 20100524

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

Ref country code: FR

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

Effective date: 20100628

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

Ref country code: LU

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

Effective date: 20100524

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101029

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100428

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

Ref country code: GB

Payment date: 20130522

Year of fee payment: 11

Ref country code: DE

Payment date: 20130531

Year of fee payment: 11

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

Ref country code: BE

Payment date: 20130521

Year of fee payment: 11

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

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100728

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50312667

Country of ref document: DE

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

Effective date: 20140524

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50312667

Country of ref document: DE

Effective date: 20141202

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

Ref country code: DE

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

Effective date: 20141202

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

Ref country code: GB

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

Effective date: 20140524

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

Ref country code: BE

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

Effective date: 20140531