EP0943027B1 - Method for treating cellulosic shaped bodies - Google Patents
Method for treating cellulosic shaped bodies Download PDFInfo
- Publication number
- EP0943027B1 EP0943027B1 EP98947226A EP98947226A EP0943027B1 EP 0943027 B1 EP0943027 B1 EP 0943027B1 EP 98947226 A EP98947226 A EP 98947226A EP 98947226 A EP98947226 A EP 98947226A EP 0943027 B1 EP0943027 B1 EP 0943027B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- fibers
- salt
- textile auxiliary
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 21
- 239000004753 textile Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 22
- 206010061592 cardiac fibrillation Diseases 0.000 claims description 20
- 230000002600 fibrillogenic effect Effects 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims 3
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004744 fabric Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229920000433 Lyocell Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OPOJRMTZHYUKLY-UHFFFAOYSA-N 1h-1,3,5-triazin-2-one Chemical compound O=C1N=CN=CN1 OPOJRMTZHYUKLY-UHFFFAOYSA-N 0.000 description 1
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical class ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 1
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- D06M13/322—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 nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
-
- 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
-
- 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
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
-
- 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
- D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
- D06M2400/01—Creating covalent bondings between the treating agent and the fibre
Definitions
- the fibers, which are freshly spun or already can be dried, treated in an alkaline medium with an aqueous system which a chemical reagent with 2 to 6 functional groups that react with cellulose can contains.
- derivatives of Cyanuric chlorides especially substituted dichlorotriazines.
- addition products of cyanuric chloride with poly (ethylene glycol) monomethyl ether used.
- Cyanuric chloride and nonionic residues are the compounds of the invention in the aqueous solution in an alkaline medium in ionic form.
- a metal salt the sodium, potassium or lithium salt are preferably used.
- the treated are cellulosic Shaped body never dried fibers.
- “never dried” fibers solvent-spun fibers in the state before the first drying. It has shown that the use of compounds of formula (I) in particular never dried fibers gives a significant reduction in the tendency to fibrillation.
- the pH of the aqueous solution of the textile auxiliary is preferably when it is brought into contact with the shaped bodies 12 to 14.
- the moldings are preferred during or after being brought into contact with the exposed aqueous solution of the textile auxiliary to a heat treatment.
- Two-bath process control can heat treatment during and / or after Contact with the weakly alkaline solution of the textile auxiliary, but also after Bringing the pressed molded articles into contact with the more alkaline aqueous solution occur. Satisfactory results are also achieved when heat treated only after contacting the shaped body with the more alkaline aqueous Solution takes place.
- the stepwise reaction of the two reactive groups of the Textile auxiliaries can be specifically controlled by the respective use of the heat treatment.
- the friction of the fibers against each other during washing or finishing operations in the Wet condition is simulated by the following test: 8 fibers are mixed with 4 ml of water 20 ml vials were given and placed in a laboratory shaker for 3 hours Type RO-10 from Gerhardt, Bonn (FRG) shaken at level 12. The Fibrillation behavior of the fibers is then counted under the microscope Number of fibrils per 0.276 mm fiber length is assessed and is converted into a fibrillation value from 0 (no fibrils) to 6 (strong fibrillation).
- the fibers After shaking for 3 hours, the fibers had an average of 9 fibrils per 0.276 mm and a fibrillation value of 2.75. In contrast, fibers not treated with the textile auxiliary had an average of 12 fibrils per 0.276 mm and a fibrillation value of 4 after shaking for 3 hours. After 9 hours of shaking in the test device, an analogous behavior was shown.
- Solvent-spun fibers treated according to Example 3 or Example 4 were used measured the reflectance of UV radiation. In all cases, compared to untreated solvent-spun fibers a significant reduction in Remission value. The order of magnitude of the no longer remitted, therefore absorbed The proportion of UV radiation is approximately 40%.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Behandlung von cellulosischen Formkörpern gemäß dem Oberbegriff des Anspruches 1.The invention relates to a method for the treatment of cellulosic moldings the preamble of claim 1.
In den letzten Jahrzehnten wurden bedingt durch die Umweltproblematik des bekannten Viskoseverfahrens zur Herstellung cellulosischer Fasern intensive Anstrengungen unternommen, alternative, umweltfreundlichere Verfahren zur Verfügung zu stellen. Als eine besonders interessante Möglichkeit hat sich dabei in den letzten Jahren herauskristallisiert, Cellulose ohne Ausbildung eines Derivates in einem organischen Lösungsmittel aufzulösen und aus dieser Lösung Formkörper zu extrudieren. Fasern, welche aus solchen Lösungen ersponnen werden, erhielten von der BISFA (The International Bureau for the Standardization of man made fibers) den Gattungsnamen Lyocell zugeteilt, wobei unter einem organischen Lösungsmittel ein Gemisch aus einer organischen Chemikalie und Wasser verstanden wird. Weiters sind solche Fasern auch unter dem Begriff "lösungsmittelgesponnene Fasern" bekannt.In recent decades, the environmental problems of the known Viscose process for the production of cellulosic fibers intensive efforts undertook to provide alternative, more environmentally friendly processes. As one a particularly interesting possibility has emerged in recent years, Dissolve cellulose in an organic solvent without the formation of a derivative and to extrude moldings from this solution. Fibers made from such solutions obtained from BISFA (The International Bureau for the Standardization of man made fibers) the generic name Lyocell, with an organic Solvent is a mixture of an organic chemical and water is understood. Furthermore, such fibers are also referred to as "solvent-spun fibers" known.
Es hat sich herausgestellt, daß sich als organisches Lösungsmittel insbesondere ein Gemisch aus einem tertiären Aminoxid und Wasser hervorragend zur Herstellung von Lyocell-Fasern bzw. anderen Formkörpern eignet. Als Aminoxid wird dabei vorwiegend N-Methylmorpholin-N-oxid (NMMO) verwendet. Andere geeignete Aminoxide sind in der EP-A 0 553 070 geoffenbart. Verfahren zur Herstellung cellulosischer Formkörper aus einer Lösung der Cellulose in einem Gemisch aus NMMO und Wasser sind z.B. in der US-PS 4,246,221 oder in der PCT-WO 93/19230 geoffenbart. Dabei wird die Cellulose aus der Lösung in einem wäßrigen Fällbad ausgefällt. Solcherart hergestellte Fasern zeichnen sich durch eine hohe Faserfestigkeit im konditionierten sowie im nassen Zustand, einen hohen Naßmodul und eine hohe Schlingenfestigkeit aus.It has been found that a mixture, in particular, as the organic solvent from a tertiary amine oxide and water excellent for the production of Lyocell fibers or other moldings. The amine oxide used is predominantly N-methylmorpholine-N-oxide (NMMO) used. Other suitable amine oxides are in EP-A 0 553 070. Process for the production of cellulosic moldings from a Solutions of the cellulose in a mixture of NMMO and water are e.g. in the US PS 4,246,221 or disclosed in PCT-WO 93/19230. The cellulose is made from the Solution precipitated in an aqueous precipitation bath. Fibers produced in this way stand out due to a high fiber strength in the conditioned as well as in the wet state, a high Wet modulus and high loop strength.
Eine spezielle Eigenschaft dieser Fasern ist ihre hohe Neigung zur Fibrillation, insbesondere unter Beanspruchung im nassen Zustand, wie z.B. während eines Waschvorganges. Während diese Eigenschaft für bestimmte Anwendungen der Fasern durchaus erwünscht ist und interessante Effekte ergibt, wird hingegen die Brauchbarkeit für andere Zwecke, wie z.B. Textilien, die Waschbeständigkeit aufweisen sollen, vermindert.A special property of these fibers is their high tendency to fibrillation, in particular under stress when wet, e.g. during a washing process. While this property is quite desirable for certain applications of the fibers and interesting effects, however, the usability for other purposes, such as Textiles that are said to be wash-resistant are reduced.
Es hat daher nicht an Anstrengungen gefehlt, mit bestimmten Maßnahmen das Fibrillationsverhalten zu reduzieren. Efforts have therefore not been lacking with certain measures Reduce fibrillation behavior.
Zahlreiche Veröffentlichungen beschäftigen sich insbesondere mit der Möglichkeit, die Fibrillationstendenz der Fasern durch die Behandlung mit Substanzen, welche eine vernetzende Wirkung für Cellulose besitzen, herabzusetzen.Numerous publications deal in particular with the possibility of Fibrillation tendency of the fibers due to the treatment with substances which have a cross-linking effect on cellulose.
Gemäß der EP-A-0 538 977 werden die Fasern, welche frisch versponnen oder bereits getrocknet sein können, in alkalischem Milieu mit einem wäßrigen System behandelt, welches ein chemisches Reagenz mit 2 bis 6 funktionellen Gruppen, welche mit Cellulose reagieren können, enthält. In der EP-A-0 538 977 werden als geeignete Substanzen auch Derivate des Cyanurchlorides, insbesondere substituierte Dichlortriazine genannt. Unter anderem werden auch Additionsprodukte von Cyanurchlorid mit Poly(ethylenglykol)monomethylether eingesetzt.According to EP-A-0 538 977, the fibers, which are freshly spun or already can be dried, treated in an alkaline medium with an aqueous system which a chemical reagent with 2 to 6 functional groups that react with cellulose can contains. In EP-A-0 538 977, derivatives of Cyanuric chlorides, especially substituted dichlorotriazines. Among other things also addition products of cyanuric chloride with poly (ethylene glycol) monomethyl ether used.
Aus der EP-A 0 616 071 ist es bekannt, Cellulose enthaltende Fasermaterialien wie z.B. Textilien unter anderem mit Metallsalzen von Teilhydrolysaten des Cyanurchlorides zu behandeln, um den Textilien Knitterfest- und Pflegeleichteigenschaften zu verleihen. Die Verwendung solcher Substanzen zur Behandlung lösungsmittelgesponnener Fasern wird jedoch nicht erwähnt.From EP-A 0 616 071 it is known to use cellulose-containing fiber materials such as e.g. Textiles including metal salts of partial hydrolyzates of cyanuric chloride treat to give the textiles anti-crease and easy-care properties. The Use of such substances for the treatment of solvent-spun fibers however not mentioned.
In bezug auf die Senkung der Fibrillationstendenz von cellulosischen Formkörpern, welche aus einer Lösung der Cellulose in tertiären Aminoxiden geformt werden, existiert trotz der zahlreichen Anstrengungen auf diesem Gebiet bislang keine Veröffentlichung, welche den Einsatz von mehrfunktionellen Textilhilfsmitteln beschreibt, deren Wirksamkeit den zumeist hohen Preis dieser Substanzen rechtfertigt.Regarding the lowering of the fibrillation tendency of cellulosic molded articles which are formed from a solution of cellulose in tertiary amine oxides, exists despite the numerous efforts in this area so far no publication that the Use of multifunctional textile auxiliaries describes their effectiveness justifies the high price of these substances.
Es ist daher Aufgabe der Erfindung, ein Verfahren zur Behandlung von cellulosischen Formkörpern, welche aus Lösungen der Cellulose in wäßrigen tertiären Aminoxiden geformt werden, mittels mehrfunktionellen Textilhilfsmitteln zur Verfügung zu stellen, welche durch den Einsatz kostengünstiger Behandlungssubstanzen eine effiziente Verbesserung der Eigenschaften der Formkörper, im Falle von Fasern insbesondere der Fibrillationstendenz bewirkt. It is therefore an object of the invention to provide a method for treating cellulosic Shaped bodies, which are formed from solutions of cellulose in aqueous tertiary amine oxides are to be made available by means of multifunctional textile auxiliaries, which by the use of inexpensive treatment substances an efficient improvement of Properties of the moldings, in the case of fibers in particular the tendency to fibrillation causes.
Diese Aufgabe wird gelöst durch ein Verfahren gemäß dem Oberbegriff des Anspruches 1,
welches dadurch gekennzeichnet ist, daß als Textilhilfsmittel eine Verbindung der Formel
Als Halogenrest X ist insbesondere Chlor bevorzugt.Chlorine is particularly preferred as the halogen radical X.
Es hat sich überraschenderweise gezeigt, daß die erfindungsgemäß eingesetzten
Textilhilfsmittel, welche relativ kostengünstig erhältlich sind, eine ebenso große bzw. sogar
größere Verbesserung der Eigenschaften der behandelten Formkörper bewirken wie die z.B.
aus der EP-A 0 538 977 bekannten aufwendig herzustellenden Substanzen.
Es ist damit möglich, in wirtschaftlicher Weise z.B. das Problem der Fibrillationstendenz
lösungsmittelgesponnener Fasern zu lösen.It has surprisingly been found that the textile auxiliaries used according to the invention, which are relatively inexpensive to obtain, bring about an improvement in the properties of the shaped articles which is just as great or even greater than that of the substances which are known, for example from EP-A 0 538 977, and which are difficult to produce.
It is thus possible, for example, to solve the problem of the fibrillation tendency of solvent-spun fibers in an economical manner.
Im Unterschied zu den in der EP-A 0 538 977 beschriebenen Additionsprodukten aus Cyanurchlorid und nicht-ionischen Resten liegen die erfindungsgemäßen Verbindungen in der wäßrigen Lösung in alkalischem Milieu in ionischer Form vor.In contrast to the addition products described in EP-A 0 538 977 Cyanuric chloride and nonionic residues are the compounds of the invention in the aqueous solution in an alkaline medium in ionic form.
Bevorzugt wird ein Salz, insbesondere Metallsalz einer Verbindung gemäß Formel (I), in der n=0 ist, also ein Salz des 2,4-Dichlor-6-hydroxy 1.3.5-triazins, eingesetzt. Als Metallsalz werden bevorzugt das Natrium-, Kalium- oder Lithiumsalz eingesetzt.A salt, in particular a metal salt of a compound of the formula (I) in which n = 0, ie a salt of 2,4-dichloro-6-hydroxy 1.3.5-triazine, is used. As a metal salt the sodium, potassium or lithium salt are preferably used.
Es ist jedoch auch möglich, das 2,4-Dichlor-6-hydroxy 1.3.5-triazin als solches einzusetzen, wobei sich die ionische Form im alkalischen Milieu der Behandlung der Formkörper einstellt.However, it is also possible to use 2,4-dichloro-6-hydroxy 1,3.5-triazine as such, whereby the ionic form is established in the alkaline environment of the treatment of the shaped bodies.
Bevorzugt sind die Reste R anionische Reste, z.B. -SO3 - oder -C1-C6-Alkyl-SO3 - oder CO2 - oder -C1-C6-Alkyl-CO2 - eingesetzt. Die Reste R können aber auch kationisch sein. Bevorzugt sind Reste R mit z.B. -C1-C6-Alkyl-N+(C1-C4-Alkyl)3. The radicals R are preferably anionic radicals, for example -SO 3 - or -C 1 -C 6 -alkyl-SO 3 - or CO 2 - or -C 1 -C 6 -alkyl-CO 2 - . The radicals R can also be cationic. R are preferred with, for example, -C 1 -C 6 alkyl-N + (C 1 -C 4 alkyl) 3 .
In einer bevorzugten Ausgestaltung der Erfindung sind die behandelten cellulosischen Formkörper niemals getrocknete Fasern. Als "niemals getrocknete" Fasern werden lösungsmittelgesponnene Fasern im Zustand vor der ersten Trocknung bezeichnet. Es hat sich gezeigt, daß der Einsatz von Verbindungen der Formel (I) insbesondere auf niemals getrockneten Fasern eine wesentliche Reduzierung der Fibrillationstendenz ergibt.In a preferred embodiment of the invention, the treated are cellulosic Shaped body never dried fibers. As "never dried" fibers solvent-spun fibers in the state before the first drying. It has shown that the use of compounds of formula (I) in particular never dried fibers gives a significant reduction in the tendency to fibrillation.
Aber auch die Anwendung von Verbindungen der Formel (1) auf bereits getrocknete lösungsmittelgesponnen Fasern oder textile Flächengebilde daraus, z.B. Gewebe, Gewirke oder Gestricke ergibt hervorragende Ergebnisse.But also the application of compounds of formula (1) to those already dried solvent-spun fibers or textile fabrics, e.g. Fabrics, knitted fabrics or knitted fabrics gives excellent results.
Bevorzugt beträgt der pH-Wert der wäßrigen Lösung des Textilhilfsmittels beim In-Kontakt-Bringen mit den Formkörpern 12 bis 14.The pH of the aqueous solution of the textile auxiliary is preferably when it is brought into contact with the shaped bodies 12 to 14.
In einer anderen bevorzugten Verfahrensführung wird der pH-Wert der wäßrigen Lösung des Textilhilfsmittels beim In-Kontakt-Bringen mit den Formkörpern nur im schwach alkalischem Bereich von 7 bis 9, z.B. bei 7,5 bis 8,5, vorzugsweise von 8 bis 9, gehalten. Da die beiden reaktiven Halogen-Substituenten der Verbindungen gemäß Formel (I) unterschiedliche Reaktivitäten aufweisen, findet dabei zunächst eine Reaktion der ersten reaktiven Gruppe des Textilhilfsmittels mit der Cellulose statt. Die Formkörper werden anschließend abgepreßt und mit einer alkalischen wäßrigen Lösung mit einem pH-Wert von 11 bis 14, beispielsweise bei pH=13 in Kontakt gebracht. Dabei findet nun die Reaktion der zweiten reaktiven Gruppe des Textilhilfsmittels mit der Cellulose statt. Diese Verfahrensführung wird im folgenden als "zweibadige" Verfährensführung bezeichnet.In another preferred procedure, the pH of the aqueous solution of the Textile auxiliaries when brought into contact with the shaped bodies only in a weakly alkaline state Range from 7 to 9, e.g. maintained at 7.5 to 8.5, preferably from 8 to 9. Since the two reactive halogen substituents of the compounds of formula (I) different Having reactivities, a reaction of the first reactive group of Textile auxiliary with the cellulose instead. The moldings are then pressed and with an alkaline aqueous solution with a pH of 11 to 14, for example at pH = 13 contacted. The reaction of the second reactive group of Textile auxiliary with the cellulose instead. This procedure is referred to below as Designated "two-bath" procedure.
Der Vorteil dieser bevorzugten Verfahrensführung liegt darin, daß eine Hydrolyse der Substanz gemäß Formel (I) bei nur schwach alkalischen pH-Werten hintan gehalten werden kann und somit weniger Hydrolyseverluste in Kauf genommen werden müssen. Dies trägt zur Wirtschaftlichkeit des Verfahrens bei.The advantage of this preferred procedure is that hydrolysis of the Substance according to formula (I) are kept behind at only weakly alkaline pH values can and thus less hydrolysis losses have to be accepted. This contributes to Economics of the process.
Bevorzugt werden die Formkörper während oder nach dem In-Kontakt-Bringen mit der wäßrigen Lösung des Textilhilsmittels einer Hitzebehandlung ausgesetzt. Im Falle der zweibadigen Verfahrensführung kann die Hitzebehandlung während und/oder nach dem Kontaktieren mit der schwach alkalischen Lösung des Textilhilfsmittels, aber auch nach dem In-Kontakt-Bringen der abgepreßten Formkörper mit der stärker alkalischen wäßrigen Lösung stattfinden. Zufriedenstellende Ergebnisse werden auch erzielt, wenn eine Hitzebehandlung nur nach dem In-Kontakt-Bringen der Formkörper mit der stärker alkalischen wäßrigen Lösung stattfindet. Es kann somit die stufenweise Reaktion der beiden reaktiven Gruppen des Textilhilfsmittel durch den jeweiligen Einsatz der Hitzebehandlung gezielt gesteuert werden. The moldings are preferred during or after being brought into contact with the exposed aqueous solution of the textile auxiliary to a heat treatment. In case of Two-bath process control can heat treatment during and / or after Contact with the weakly alkaline solution of the textile auxiliary, but also after Bringing the pressed molded articles into contact with the more alkaline aqueous solution occur. Satisfactory results are also achieved when heat treated only after contacting the shaped body with the more alkaline aqueous Solution takes place. The stepwise reaction of the two reactive groups of the Textile auxiliaries can be specifically controlled by the respective use of the heat treatment.
Die Erfindung betrifft auch die Verwendung einer Verbindung der Formel
Es wurde weiters auch überraschenderweise gefunden, daß Verbindungen der Formel (I) die Erhöhung der UV-Absorption von Formkörpern aus Lösungen der Cellulose in wäßrigen Lösungen von tertiären Aminoxiden bewirken.It was also surprisingly found that compounds of formula (I) Increase in the UV absorption of moldings from solutions of cellulose in aqueous Effect solutions of tertiary amine oxides.
Es ist bekannt, Textilien zur Erhöhung der Sonnenschutzwirksamkeit mit bestimmten, als UV-Absorber bezeichneten Substanzen zu modifizieren (z.B. Textilveredlung 31 (1996) 11/12, 227-234). Solche UV-Absorber reduzieren die Remission bzw. die Transmission von UV-Strahlung durch das Textil. Die UV-Absorber müssen in Abhängigkeit vom Fasermaterial sorgfältig ausgewählt werden. Es hat sich nun gezeigt, daß die Verbindungen der Formel (I) bei der Anwendung auf lösungsmittelgesponnenen Fasern oder textilen Flächengebilden daraus als hervorragende UV-Absorber wirken.It is known to modify textiles to increase the sun protection effectiveness with certain substances known as UV absorbers (for example textile finishing 31 (1996) 11/12 , 227-234). Such UV absorbers reduce the reflectance or the transmission of UV radiation through the textile. The UV absorbers must be carefully selected depending on the fiber material. It has now been shown that the compounds of the formula (I), when used on solvent-spun fibers or textile fabrics, act as excellent UV absorbers.
Die Erfindung betrifft daher auch die Verwendung einer Verbindung der Formel
Es können somit durch den Einsatz einer einzigen Substanz bei der Behandlung lösungsmittelgesponnener Fasern zwei gewünschte Effekte, nämlich die Reduzierung der Fibrillationstendenz und eine Erhöhung der UV-Absorption erreicht werden. Eine doppelte Wirkung dieser Art war bislang aus dem Stand der Technik nicht bekannt.It can thus be treated by using a single substance solvent-spun fibers two desired effects, namely the reduction of Fibrillation tendency and an increase in UV absorption can be achieved. A double one This type of effect was previously not known from the prior art.
Die Reibung der Fasern aneinander bei Waschvorgängen bzw. bei Ausrüstevorgängen im nassen Zustand wird durch folgenden Test simuliert: 8 Fasern werden mit 4 ml Wasser in ein 20 ml Probenfläschchen gegeben und während 3 Stunden in einem Laborschüttelgerät der Type RO-10 der Fa. Gerhardt, Bonn (BRD) auf Stufe 12 geschüttelt. Das Fibrillationsverhalten der Fasern wird danach unter dem Mikroskop mittels Auszählen der Anzahl der Fibrillen pro 0,276 mm Faserlänge beurteilt und wird in einem Fibrillationswert von 0 (keine Fibrillen) bis 6 (starke Fibrillation) angegeben.The friction of the fibers against each other during washing or finishing operations in the Wet condition is simulated by the following test: 8 fibers are mixed with 4 ml of water 20 ml vials were given and placed in a laboratory shaker for 3 hours Type RO-10 from Gerhardt, Bonn (FRG) shaken at level 12. The Fibrillation behavior of the fibers is then counted under the microscope Number of fibrils per 0.276 mm fiber length is assessed and is converted into a fibrillation value from 0 (no fibrils) to 6 (strong fibrillation).
Zwanzig 40 mm lange Fasern werden über eine 1 cm dicke Metallwalze gelegt und mit einem
vom Titer der Fasern abhängigen Vorspanngewicht beschwert. Die Walze ist mit einem
Viskosefilamentgarnstrumpf überzogen und wird kontinuierlich befeuchtet. Während der
Messung wird die Walze mit einer Geschwindigkeit von 500 Umdrehungen/Minute gedreht
und gleichzeitig quer zur Faserachse hin und zurück bewegt, wobei eine Pendelbewegung von
ca. 1 cm ausgeführt wird.
Gemessen wird die Anzahl der Umdrehungen, bis die Fasern durchgescheuert sind. Als
Meßwert wird der Mittelwert der Scheuerzyklen der 20 Fasern genommen. Je höher die Zahl
der Umdrehungen ist, bis die Fasern durchgescheuert sind, umso besser ist das
Fibrillationsverhalten der Fasern. Twenty 40 mm long fibers are placed over a 1 cm thick metal roller and weighted with a pretension weight depending on the titer of the fibers. The roller is covered with a viscose filament yarn stocking and is continuously moistened. During the measurement, the roller is rotated at a speed of 500 revolutions / minute and at the same time moved back and forth transversely to the fiber axis, a pendulum movement of approx. 1 cm being carried out.
The number of revolutions is measured until the fibers are worn through. The mean value of the abrasion cycles of the 20 fibers is taken as the measured value. The higher the number of revolutions until the fibers are worn through, the better the fibrillation behavior of the fibers.
Ein gefärbtes Gestrick aus lösungsmittelgesponnenen Fasern wurde in einem Floltenverhältnis von 1:30 mit einer wäßrigen Lösung, enthaltend 20 g/l Natriumsalz des 2,4-Dichlor-6-hydroxy 1.3.5-triazins, 20 g/l NaOH und 1 g/l Leonil SR (Netzmittel, Hersteller: Fa. Hoechst) in Kontakt gebracht. Die Lösung besaß einen pH-Wert von 13. Das Gestrick wurde mit der Lösung 5 Minuten imprägniert, die überschüssige Lösung mit einem Foulard bei 1 bar abgepreßt und 5 Minuten bei 100°C mit Wasserdampf wärmebehandelt. Anschließend wurde das Gestrick mit 2%-iger Essigsäure und Wasser wiederholt gewaschen und abschließend getrocknet.A colored knitted fabric made of solvent-spun fibers was in a flute ratio from 1:30 with an aqueous solution containing 20 g / l of sodium salt of 2,4-dichloro-6-hydroxy 1.3.5-triazines, 20 g / l NaOH and 1 g / l Leonil SR (wetting agent, manufacturer: Hoechst) brought into contact. The solution had a pH of 13. The knitted fabric was covered with the Solution impregnated for 5 minutes, the excess solution with a pad at 1 bar pressed and heat-treated with steam at 100 ° C for 5 minutes. Then was repeatedly washed the knitted fabric with 2% acetic acid and water and finally dried.
Aus dem Gestrick wurden einzelne Fasern präpariert und gemäß obiger Vorschrift einer Naßscheucrprüfung unterzogen. Der Mittelwert aus den Prüfungen betrug 470 Umdrehungen. Dies entspricht einer Verringerung der Fibrillationsneigung um ca. 75% gegenüber einer unbehandelten Faser.Individual fibers were prepared from the knitted fabric and one according to the above regulation Subjected to wet scrubbing. The mean value from the tests was 470 revolutions. This corresponds to a reduction in the tendency to fibrillation by approx. 75% compared to one untreated fiber.
Ein ungefärbtes Gestrick aus lösungsmittelgesponnenen Fasern wurde wie in Beispiel 1 beschrieben behandelt und einer Naßscheuerprüfung unterzogen. Der Mittelwert aus den Prüfungen betrug 620 Umdrehungen.An undyed knitted fabric made of solvent-spun fibers was made as in Example 1 treated and subjected to a wet abrasion test. The mean of the Tests were 620 revolutions.
Gemäß dem Verfahren der PCT-WO 93/19230 hergestellte niemals getrocknete lösungsmittelgesponnene Cellulosefasem mit einem Titer von 3,3 dtex wurden bei einem Flottenverhältnis von 1:25 mit einer Lösung, enthaltend 30 g/l Natriumsalz des 2,4-Dichlor-6-hydroxy 1.3.5-triazins, 20 g/l NaOH und 30 g/l Na2SO4 5 Minuten bei Raumtemperatur imprägniert. Die Lösung hatte einen pH-Wert von 13. Anschließend wurden die Fasern 10 Minuten bei 110°C mit Wasserdampf wärmebehandelt, ausgewaschen und getrocknet. An den Fasern wurde gemäß der obigen Vorschrift der Fibrillationsgrad gemessen. Nach 3 Stunden Schütteln wiesen die Fasern im Durchschnitt 9 Fibrillen pro 0,276 mm und einen Fibrillationswert von 2,75 auf. Demgegenüber wiesen nicht mit dem Textilhilfsmittel behandelte Fasern nach 3 Stunden Schütteln im Durchschnitt 12 Fibrillen pro 0,276 mm und einen Fibrillationswert von 4 auf. Nach 9 Stunden Schütteln im Testgerät zeigte sich ein analoges Verhalten. Never dried solvent-spun cellulose fibers with a titer of 3.3 dtex produced according to the process of PCT-WO 93/19230 were mixed with a solution containing 30 g / l of sodium salt of 2,4-dichloro-6- at a liquor ratio of 1:25. hydroxy 1.3.5-triazine, 20 g / l NaOH and 30 g / l Na 2 SO 4 impregnated for 5 minutes at room temperature. The solution had a pH of 13. The fibers were then heat-treated with steam at 110 ° C. for 10 minutes, washed out and dried. The degree of fibrillation was measured on the fibers in accordance with the above specification. After shaking for 3 hours, the fibers had an average of 9 fibrils per 0.276 mm and a fibrillation value of 2.75. In contrast, fibers not treated with the textile auxiliary had an average of 12 fibrils per 0.276 mm and a fibrillation value of 4 after shaking for 3 hours. After 9 hours of shaking in the test device, an analogous behavior was shown.
Im Scheuertest wiesen die behandelten Fasern einen Mittelwert von 125 Umdrehungen auf, während unbehandelte Fasern einen Mittelwert von 13 Umdrehungen aufweisen.In the abrasion test, the treated fibers had an average value of 125 revolutions, while untreated fibers have an average of 13 turns.
Gemäß dem Verfahren der PCT-WO 93/19230 hergestellte niemals getrocknete lösungsmittelgesponnene Fasern mit einem Titer von 1,3 dtex wurden bei einem Flottenverhältnis von 1:10 mit einer Lösung, enthaltend 30 g/l Natriumsalz des 2,4-Dichlor-6-hydroxy 1.3.5-triazins und 16 g/l NaOH (pH-Wert der Lösung:13) 2 Minuten bei 20°C imprägniert. Anschließend wurden die Fasern für 1 Minute mit Wasserdampf bei 110°C wärmebehandelt, ausgewaschen und getrocknet. An den Fasern wurden Naßscheuerprüfungen vorgenommen. Der Mittelwert der Naßscheuerprüfung betrug 702 Umdrehungen.Never dried according to the method of PCT-WO 93/19230 Solvent-spun fibers with a titer of 1.3 dtex were used in one Liquor ratio of 1:10 with a solution containing 30 g / l of sodium salt of 2,4-dichloro-6-hydroxy 1.3.5-triazine and 16 g / l NaOH (pH of the solution: 13) for 2 minutes at 20 ° C impregnated. The fibers were then steamed at 110 ° C for 1 minute heat treated, washed out and dried. Wet abrasion tests were carried out on the fibers performed. The average value of the wet abrasion test was 702 revolutions.
Niemals getrocknete lösungsmittelgesponnene Fasern mit einem Titer von 1.3 dtex wurden mit einer wäßrigen Lösung, enthaltend 30 g/l Natriumsalz des 2,4-Dichlor-6-hydroxy 1.3.5-triazins bei einem Flottenverhältnis für 2 Minuten bei 20°C imprägniert. Die wäßrige Lösung wies einen pH-Wert von ca. 8 auf. Nach der Imprägnierung wurden die Fasern abgepreßt, mit einer wäßrigen Lösung, enthaltend 16 g/l NaOH (pH-Wert ca. 13) kontaktiert, abgepreßt, 2 Minuten bei 110°C mit Wasserdampf wärmebehandelt, ausgewaschen und getrocknet.Solvent-spun fibers with a titer of 1.3 dtex were never dried with an aqueous solution containing 30 g / l of sodium salt of 2,4-dichloro-6-hydroxy 1,3.5-triazine impregnated at a liquor ratio for 2 minutes at 20 ° C. The aqueous solution had a pH of about 8. After the impregnation, the fibers were pressed, with an aqueous solution containing 16 g / l NaOH (pH approx. 13) contacted, pressed, 2 Minutes at 110 ° C with steam, washed and dried.
Die Naßscheuerprüfung der so behandelten Fasern ergab einen Wert von 270 Umdrehungen. Dies entspricht einer Verringerung der Fibrillationsneigung um ca. 50% gegenüber einer unbehandelten Faser.The wet abrasion test of the fibers treated in this way gave a value of 270 revolutions. This corresponds to a reduction in the tendency to fibrillation by approximately 50% compared to one untreated fiber.
An gemäß Beispiel 3 bzw. Beispiel 4 behandelten lösungsmittelgesponnenen Fasern wurde die Remission von UV-Strahlung gemessen. In allen Fällen zeigte sich im Vergleich zu unbehandelten lösungsmittelgesponnenen Fasern eine deutliche Reduktion des Remissionswertes. Die Größenordnung des nicht mehr remittierten, daher absorbierten Anteiles der UV-Strahlung beträgt ca. 40%.Solvent-spun fibers treated according to Example 3 or Example 4 were used measured the reflectance of UV radiation. In all cases, compared to untreated solvent-spun fibers a significant reduction in Remission value. The order of magnitude of the no longer remitted, therefore absorbed The proportion of UV radiation is approximately 40%.
Claims (9)
- A process for the treatment of cellulosic moulded bodies which are formed from a solution of cellulose in an aqueous tertiary amine oxide, in particular fibres, wherein the moulded bodies are contacted with an aqueous solution of a textile auxiliary carrying two reactive groups in an alkaline environment, characterized in that a compound of the formulawherein X represents halogen, R=H or a ionic residue and n=0 or 1, or a salt of said compound, respectively, is used as the textile auxiliary.
- A process according to claim 1, characterized in that the salt, preferably the metallic salt of a compound wherein n=0, is used.
- A process according to claim 1, characterized in that a compound wherein n=1 and R represents an anionic residue or the salt of said compound, respectively, preferably a metallic salt, is used.
- A process according to claim 1, 2 or 3, characterized in that the cellulosic moulded bodies are never dried fibres.
- A process according to any of the preceding claims, characterized in that the pH of the aqueous solution of the textile auxiliary amounts to from 12 to 14 when being contacted with the moulded bodies.
- A process according to any of claims 1 to 4, characterized in that the pH of the aqueous solution of the textile auxiliary amounts to between 7 and 9, preferably between 8 and 9, when being contacted with the moulded bodies, wherein a reaction of the first reactive group of the textile auxiliary with the cellulose takes place, the moulded bodies subsequently are squeezed and are contacted with an alkaline aqueous solution having a pH of from 11 to 14, wherein the reaction of the second reactive group of the textile auxiliary with the cellulose takes place.
- A process according to any of the preceding claims, characterized in that the moulded bodies are exposed to heat treatment during or after contacting the aqueous solution of the textile auxiliary.
- The use of a compound of the formulawherein X represents halogen, R=H or a ionic residue and n=0 or 1, or of a salt of said compound, respectively, for reducing the tendency toward fibrillation of solvent-spun cellulosic fibres.
- The use of a compound of the formulawherein X represents halogen, R=H or a ionic residue and n=0 or 1, or of a salt of said compound, respectively, for increasing the ultraviolet absorption of solvent-spun cellulosic fibres.
Priority Applications (1)
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|---|---|---|---|
| AT98947226T ATE257189T1 (en) | 1997-10-15 | 1998-10-07 | METHOD FOR TREATING CELLULOSIC MOLDED BODY |
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| AT175397 | 1997-10-15 | ||
| AT175397 | 1997-10-15 | ||
| PCT/AT1998/000236 WO1999019555A1 (en) | 1997-10-15 | 1998-10-07 | Method for treating cellulosic shaped bodies |
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| EP0943027A1 EP0943027A1 (en) | 1999-09-22 |
| EP0943027B1 true EP0943027B1 (en) | 2004-01-02 |
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| EP98947226A Expired - Lifetime EP0943027B1 (en) | 1997-10-15 | 1998-10-07 | Method for treating cellulosic shaped bodies |
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| DE10007794A1 (en) | 2000-02-21 | 2001-06-28 | Zimmer Ag | Composition useful for making containers, films, membranes and fibers, comprises a biodegradable polymer and a marine plant or shell material |
| GB2373784A (en) * | 2001-03-30 | 2002-10-02 | Tencel Ltd | Lyocell fibre and treatment to reduce fibrillation |
| AT410319B (en) * | 2001-07-25 | 2003-03-25 | Chemiefaser Lenzing Ag | CELLULOSE SPONGE AND METHOD FOR THE PRODUCTION THEREOF |
| AT413824B (en) * | 2001-11-02 | 2006-06-15 | Chemiefaser Lenzing Ag | METHOD FOR THE TREATMENT OF SOLVENT-SPUN CELLULOSIC FIBERS |
| DE10155066A1 (en) * | 2001-11-09 | 2003-05-28 | Degussa | Process for flame retardant treatment of cellulose fibers |
| AT413988B (en) * | 2001-12-20 | 2006-08-15 | Chemiefaser Lenzing Ag | METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES |
| EP2150649B1 (en) | 2007-05-09 | 2012-09-12 | Institute of Natural Fibres and Medicinal Plants | Cellulose fibre textiles containing nanolignins, a method of applying nanolignins onto textiles and the use of nanolignins in textile production |
| JP5421291B2 (en) * | 2008-01-16 | 2014-02-19 | レンツィング アクチェンゲゼルシャフト | Fiber mixtures, yarns and fabrics produced therefrom |
| AT506334B1 (en) | 2008-01-22 | 2010-12-15 | Chemiefaser Lenzing Ag | METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES |
| AT507051B1 (en) | 2008-06-27 | 2015-05-15 | Chemiefaser Lenzing Ag | CELLULOSE FIBER AND METHOD FOR THE PRODUCTION THEREOF |
| AT507387A1 (en) * | 2008-09-22 | 2010-04-15 | Chemiefaser Lenzing Ag | USE OF LYOCELL FIBERS AND ARTICLES CONTAINING LYOCELL FIBERS |
| AT507386A1 (en) * | 2008-09-22 | 2010-04-15 | Chemiefaser Lenzing Ag | METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES |
| AT507758A1 (en) | 2008-12-23 | 2010-07-15 | Chemiefaser Lenzing Ag | YARN AND THREADS FROM BLENDS OF FIBERS AND ARTICLES THEREFROM |
| AT509289B1 (en) * | 2009-12-28 | 2014-06-15 | Chemiefaser Lenzing Ag | FUNCTIONALIZED CELLULOSIC FORM BODY AND METHOD FOR THE PRODUCTION THEREOF |
| CN103031712A (en) * | 2012-12-21 | 2013-04-10 | 江南大学 | Method for improving color fastness to light of fabric dyed by active dye |
| US9416494B2 (en) * | 2012-12-26 | 2016-08-16 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
| US8980054B2 (en) * | 2012-12-26 | 2015-03-17 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
| TWI667378B (en) | 2014-01-03 | 2019-08-01 | 奧地利商蘭精股份有限公司 | Cellulosic fibre |
| AT518061B1 (en) | 2016-04-28 | 2017-07-15 | Chemiefaser Lenzing Ag | Modified viscose fiber |
| EP3536853A1 (en) | 2018-03-06 | 2019-09-11 | Lenzing Aktiengesellschaft | Lyocell fiber with decreased pill formation |
| TWI804699B (en) * | 2018-12-17 | 2023-06-11 | 奧地利商蘭仁股份有限公司 | Process for the treatment of lyocell fibres |
| EP3771755A1 (en) * | 2019-08-02 | 2021-02-03 | Lenzing Aktiengesellschaft | Method for the preparation of lyocell staple fibres |
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| US4246221A (en) | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
| GB9122318D0 (en) * | 1991-10-21 | 1991-12-04 | Courtaulds Plc | Treatment of elongate members |
| AT396930B (en) | 1992-01-23 | 1993-12-27 | Chemiefaser Lenzing Ag | AMINOXIDE |
| ATA53792A (en) | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
| DE4308075A1 (en) * | 1993-03-13 | 1994-09-15 | Pfersee Chem Fab | Process for treating fiber materials using triazine derivatives |
| AT409144B (en) * | 1996-06-21 | 2002-05-27 | Chemiefaser Lenzing Ag | METHOD FOR TREATING CELLULOSE FIBERS AND FORMS OF THESE FIBERS |
| DE59806420D1 (en) | 1997-09-17 | 2003-01-09 | Chemiefaser Lenzing Ag | Process for the treatment of cellulose fibers |
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| CN1241230A (en) | 2000-01-12 |
| NO992854L (en) | 1999-06-11 |
| BR9806713A (en) | 2000-04-04 |
| CA2274819C (en) | 2008-12-23 |
| ATE257189T1 (en) | 2004-01-15 |
| PT943027E (en) | 2004-05-31 |
| EP0943027A1 (en) | 1999-09-22 |
| US6241933B1 (en) | 2001-06-05 |
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