EP2294259A1 - Cellulose fiber and method for the production thereof - Google Patents
Cellulose fiber and method for the production thereofInfo
- Publication number
- EP2294259A1 EP2294259A1 EP09768599A EP09768599A EP2294259A1 EP 2294259 A1 EP2294259 A1 EP 2294259A1 EP 09768599 A EP09768599 A EP 09768599A EP 09768599 A EP09768599 A EP 09768599A EP 2294259 A1 EP2294259 A1 EP 2294259A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- range
- stability
- cellulose fiber
- cellulose
- 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
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
- D06M13/322—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
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
-
- 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
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2965—Cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
Definitions
- the invention relates to a cellulose fiber of the genus Lyocell and a process for their preparation.
- NMMO N-methylmorpholine-N-oxide
- EP-A 553,070 A process for producing cellulosic molded bodies from a solution of cellulose in a mixture of NMMO and water are, for. In U.S. Patent 4,246,221 or in PCT WO 93/19230. The cellulose solution is extruded from a spinneret, stretched in an air gap and precipitated from the solution in an aqueous precipitation bath.
- amine oxide process or "lyocell process”
- NMMO tertiary amine oxides
- Fibers produced by the amine-oxide process are characterized by high fiber strength in the conditioned and in the wet state, a high wet modulus and a high loop strength.
- lyocell fibers have a certain tendency to fibrillate.
- Many measures have already been proposed against this feature, with the Treatment of the lyocell fiber with a crosslinking agent is a commercially significant procedure.
- crosslinking agents are described, for example, in EP 0 538 977, WO 97/49856 and WO 99/19555.
- Other crosslinking agents are e.g. from WO 94/09191 and WO 95/28516.
- a particularly preferred crosslinking agent is a substance of the formula (I)
- Lyocell fibers treated with such crosslinkers are better protected against fibrillation than untreated Lyocell fibers.
- One measure of fibrillation protection is the wet rub resistance (NSF) of the fibers.
- the fibrillation protection decreases during storage over time. It is believed that in some cases this is due to a slow but steady hydrolysis of the crosslinking bonds. The extent of this Vernetzerhydrolyse and thus the reduction of fibrillation protection can be very different, depending on how long and under which climatic conditions the cellulose fiber is stored.
- the present invention has for its object to provide a cellulose fiber of the genus Lyocell, in which by treatment with a Crosslinking agent resulting fibrillation protection over a longer period of time than in conventional Lyocell fibers is maintained.
- a cellulose fiber of the genus Lyocell which is treated with a crosslinking agent, wherein the crosslinking agent on the fiber induces fibrillation protection and has the following properties:
- the fibrillation protection induced by the crosslinking agent changes during storage of the fiber within a pH range of 4.0 to 10.0, in particular under the action of moisture and / or heat
- the suitable range is limited within the pH range from 4.0 to 10.0 by at least one limit at which the stability to the long-term stability at the optimum value is reduced by 20% and below or above thereof a further reduction of the stability entry
- the crosslinking agent has a pH-changing potential.
- the fiber according to the invention is characterized in that the fiber contains a substance buffering in the suitable range and has a buffer capacity of at least 12 mmol / kg of fiber, preferably 15 to 70 mmol / kg of fiber in the suitable range.
- Fiber Treatment Protection The fiber treated with the crosslinker has a higher resistance to fibrillation than an untreated fiber. This is determined by the wet rub resistance test described in WO 99/19555.
- the fibrillation protection induced by the crosslinking agent changes during storage of the fiber within a pH range of 4.0 to 10.0.
- the treated with the crosslinking agent fiber finds - eg by the action of heat and moisture, especially steam - one Change in fibrillation protection instead. This can be ascertained by means of a below-described wet scrub resistance test of fibers stored at different pHs held constant under buffering for a certain period of time. In each case, that period is determined up to which has reduced wet rub resistance from baseline by 30%.
- suitable range exists around the optimum value" - There must be a region around the optimum value in which stability stability is reduced at the optimum value.
- suitable range refers to the range in which the stability stability is reduced by a maximum of 20% at the optimum value.
- the suitable range is limited within the pH range of 4.0 to 10.0 by at least one limit value" - that means that the suitable range is at least toward one direction (ie in the direction of acidic or in the direction of alkaline pH values) is limited by a pH at which the time to reach a 30% reduction in wet rub resistance has been reduced to 80% of the (maximum) time at the "optimum value”. This value will be referred to as the "limit” below.
- the cross-linking agent has a pH-changing potential" - this criterion means that the cross-linking agent itself in the course of storage, for example by exposure to moisture or heat or by reacting with the fiber - be it by cleavage from the fiber or by further reacting unbound or free reactive groups - affects the pH of the fiber. This is determined by observing the evolution of the fiber pH of a fiber treated with the particular crosslinker (see below). The pH of the fiber is determined by the method given below.
- the buffer capacity of a fiber is also determined by a test described below.
- the term "contains" for the purposes of the present invention also includes an attachment of the buffering substance to the surface of the fiber.
- a crosslinking agent meets the above criteria, i. a) changes upon storage of the fiber treated with the crosslinking agent within a pH range of 4.0 to 10.0, in particular under the action of moisture and / or heat, the fibrillation protection, bl) exists within the pH range of 4, 0 to 10.0 is an optimal value at which the
- B2 exists around the optimum value, a suitable range in which stability to stability at the optimum value is reduced by a maximum of 20%, b3) is the appropriate range within the range pH range from 4.0 to 10.0 is limited by at least one limit at which the stability to long-term stability at the optimum value is reduced by 20% and c) the crosslinking agent has a pH-changing potential,
- Crosslinked lyocell fibers may vary depending on the process, e.g. Type of applied coatings, in the production of an initial pH in each case for the particular crosslinking agent used optimal range.
- the fibers have a more or less large proportion of partially reacted crosslinker molecules, which are e.g. may contain acid-forming radicals (e.g., chlorine radicals).
- acid-forming radicals e.g., chlorine radicals
- These reactive radicals may be used in further processing steps, e.g. in the dryer, during the rewetting, steaming, but also during storage abreagieren. This will change the pH of the fiber.
- the change in pH away from the optimum pH range accelerates crosslinker hydrolysis.
- the present invention is now based on this knowledge, which is not previously known, by using a substance which has a buffering effect in this pH range in order to maintain the pH of the fiber in the optimum range for the particular crosslinker.
- the fiber according to the invention preferably has a pH in the suitable range.
- At least one of the buffering substances used preferably also has a pK a value in the appropriate range.
- substances which have a pK a value just outside the suitable range for example in the range of up to 1 pH unit in each case, preferably up to 0.5 pH units above or below the "limit value", provided that the Buffering towards those pH values at which a deterioration of the storage stability of Fibrillations s occurs, is given.
- a crosslinking agent which satisfies the above criteria a) to c) and is particularly preferably used is a substance of the formula (I) X
- crosslinking agents of this group satisfy the above criterion a), i. upon storage of the crosslinker-treated fiber within a pH range of 4.0 to 10.0, especially under the action of moisture and / or heat, the fibrillation protection changes.
- these crosslinking agents in particular the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine, have an "optimum value” (or in this case an optimum range) at a pH in the range from 9 to 9.5 to (criterion b1)), in which the stability of the fibrillation protection during storage is best.
- these crosslinking agents in particular the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine, have a "limit value" (as defined above) at a pH of 8.5 (criterion b2)). , Below this limit, the fibrillation protection during storage of the fiber drops much faster than above this value.
- the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine has, in addition, a further limit value at a pH of 10.5, above which the fibrillation protection in turn falls much faster during storage.
- a further limit value at a pH of 10.5 above which the fibrillation protection in turn falls much faster during storage.
- storage of cellulosic fibers at pH values above 10.5 is not realistic, so that the use of buffering substances in this area is not necessary.
- crosslinking agents in this group also have a pH-altering potential (criterion c), apparently due to the release or the abreaction of the halogen groups present.
- a fiber treated with this crosslinking agent should preferably have a pH in the range of 8.5 to 10.5.
- the buffering substances used in this preferred embodiment advantageously have a pKa in the range from 8.0 to 11.0.
- substances from the group consisting of borax are suitable as the buffering substance;
- Carbonates or bicarbonates of alkali metal ions eg Li, Na, K ions, ammonium or cations derived from substituted amines (eg mono-, di-, trimethyl-ammonium or mono-, di-, triethyl-ammonium), phosphates, hydrogen phosphates or dihydrogen phosphates cations derived from alkali metal ions, ammonium or substituted amines, ammonia, substituted amines (eg mono-, di-, trimethyl-amine or mono-, di-, triethyl-amine), guanidine or guanidinium salts, and mixtures thereof and mixtures with carboxylic acids and their salts.
- alkali metal ions eg Li, Na, K ions, ammonium or cations derived from substituted amines (eg mono-, di-, trimethyl-ammonium or mono-, di-,
- Borax Na 2 B 4 O 7 ⁇ 10 H 2 O
- Borax and phosphate buffer are particularly suitable for inorganic buffer systems.
- a mixture of carbonate and phosphate buffer can also be used.
- Particular preference is given to using borax as the buffering substance.
- borax can also be used together with other buffer systems (bicarbonate / carbonate and / or phosphate buffer).
- borax in amounts of 0.05% to 1.4% borax based on cellulose is added to the fiber, preferably 0.3-0.6%, wherein the application can be carried out simultaneously with the application of a finishing agent.
- borax is added as a solid over a Feststoffdosierü, since you do not need to dilute the lubricant.
- Borax can also be added as an aqueous solution when applying the finish.
- the concentration of borax in the fiber is preferably at least 1525 mg borax per kg fiber. This corresponds to a content of at least 173 mg / kg boron on fiber. In particular, concentrations of 2860 mg to 14000 mg borax per kg fiber are favorable. This corresponds to a content of 324 to 1600 mg / kg boron on fiber.
- buffer system Also suitable as a buffering substance is the buffer system
- Sodium bicarbonate / sodium carbonate in particular in concentrations of at least 848 mg per kg of fiber (calculated as sodium carbonate). Particularly preferred is a concentration range of 1580 mg to 7420 mg per kg of fiber (calculated as sodium carbonate).
- the cellulose fiber according to the invention furthermore preferably has a fiber moisture content of 8-10%.
- buffering as provided according to the invention, is all the more important.
- the invention also relates to a cellulose fiber of the genus Lyocell, which is reacted with a crosslinking agent of the formula (I)
- This embodiment of the cellulose fiber according to the invention preferably contains the buffers specifically specified above in the amounts indicated there.
- bale of cellulosic fibers containing the lyocell fibers of the present invention relates to a bale of cellulosic fibers containing the lyocell fibers of the present invention.
- Lyocell fibers as well as other man-made fibers are pressed into bales after their production and are shipped in this form to the customers (eg manufacturers of yarns).
- the storage of the fibers thus takes place both at the manufacturer (before shipping) and at the customer (before further processing) in the form of bales.
- the bale according to the invention contains Lyocell fibers stabilized by the presence of a buffering substance.
- the bale may consist essentially completely of the fibers according to the invention.
- substantially it is meant that minor admixtures of other fibers (eg, tag fibers to better identify the product) may be included.
- the present invention also relates to such textile articles as yarns, fabrics, knits, braids and knitted fabrics which contain the lyocell fibers according to the invention.
- the invention relates to such textile articles which have not yet been subjected to a wet process (eg reactive dyeing), since in conventional wet processes of cellulosic fibers in the textile chain, as expected, the majority of reactive groups reacts from crosslinking agents, and therefore no (or hardly any) pH-changing potential is present, which would make the buffering invention necessary.
- a method which comprises the step of applying a substance which buffers in a suitable range to a cellulose fiber of the genus Lyocell.
- the application of the buffering substance preferably takes place in the course of the production process of the cellulose fiber, prior to its compression into a bale.
- the application should be done either during or after the last wet process intended to treat the fiber. If, after the application of the buffering substances, a wet step still takes place, they would be washed out of the fiber again.
- the buffering substance can be applied to the fiber at the same time as the drying bath with the oiling bath.
- the buffering substance may be applied in an application process immediately prior to treatment of the fiber with the oiling bath. It is also possible to apply the buffering substance to the fiber immediately before, during or at the end of the drying process, prior to pressing the fibers into a bale.
- the buffering substance can be applied in liquid form or sprayed as an aerosol onto the fiber, applied via a contact lip or mixed in the powdery state in a solid state in the fiber.
- crosslinkers of formula (I) When using crosslinkers of formula (I), the addition of alkaline buffer systems such as borax, e.g. in all the cases examined, a pronounced stabilizing effect on the crosslinking of the lyocell fibers was observed in the bath. It can be assumed that the addition of borax in the lubricant, depending on the edition and content of partially reacted crosslinker, the period in which the crosslinked lyocell fiber can be used without restrictions of Fibrillationsschutzes, compared to a non-buffered fiber approximately doubled. This can be ensured over a much longer period, the quality consistency in networked lyocell fibers.
- alkaline buffer systems such as borax
- the fibers are treated with deionised (DI) water. Subsequently, the pH of the water is measured.
- DI deionised
- the fibrillation protection of the starting fiber treated with the cross-linking agent to be investigated is determined on the basis of the wet abrasion resistance (test according to WO 99/19555) in at least 3 parallel determinations.
- the value for the wet abrasion resistance (“NSF") is given in x U / dtex (revolutions / dtex), where x should have a value> 450 for good fibrillation protection.
- fibers in a liquor ratio of 1: 10 are introduced into each of the said buffer systems in the pH range 4.0 to 10.0 and kept in this liquid in a closed vessel at 50 ° C.
- the NSF values obtained are plotted against time for each buffer system.
- criterion a) is fulfilled, ie it is a hydrolysis-sensitive crosslinking system. If the presence of the criterion a) is established, the slopes of the curves at the various pH values are compared and, in particular, the time to reach a 30% reduction in the NSF. The pH at which the time to reach a 30% reduction in NSF is the longest from baseline is the "optimal value" (criterion bl)).
- the range around the "optimal value” at which the time to reach a 30% decrease in the NSF has decreased by less than 20% from the maximum duration is the “appropriate range” (criterion b2)), within which the fiber should be buffered according to the invention.
- the pH at which the time to reach a 30% reduction has decreased to 80% of the maximum time is referred to as the "limit” (criterion b3)).
- Variant 2 By impregnating the fibers with buffers, then drying and storing under humid climatic conditions
- the method is similar to variant 1, except that in this case the starting material treated with a crosslinking agent, after determination of the original NSF in each case in a buffer system, which is also to contain about 0.1 mol / l of the respective buffer, in the pH range of 4 , 0 to 10.0 is impregnated with gradations of the pH in steps of 0.5 pH units. By subsequent pressing or spinning, care is taken to ensure an equally high liquor pickup of all fibers treated in this way. Subsequently, the fibers are gently dried in the laboratory dryer (60 ° C 5 hours).
- the hydrolytic stability of the crosslinking agent can now be determined as follows:
- the storage test must be carried out for 12 weeks. Ix per week is a provision of the NSF perform. (It can be assumed that, under these climatic conditions, the change in the fibrillation protection takes place about 10 times as fast as when storing a bale with an average moisture content at 25 ° C.)
- the fibers are positioned at some distance above the liquid. It is important to ensure that the fibers have no walls oa touch to avoid condensation.
- the rapid test is complete as system 1) after 25 days, with a determination of the NSF being performed every other day.
- the "threshold" is the pH at which the time to reach a 30% reduction has dropped to 80% of the maximum time.
- a crosslinking agent according to the invention is then maintained in its proper pH range by the use of buffering substances when it is present in the fiber or in a fiber containing article such as e.g. Bales, yarns and textile raw materials still reactive groups that during storage and / or typical moist or thermal treatment processes of yarn / text.
- Surfaces are capable of altering the fiber pH in a manner that will leave the appropriate pH range without buffering.
- starting fiber the fiber may also be in the form of a yarn or a textile raw material. See the measurement method described above
- washed fiber Removal of water-soluble substances (salts, buffers, lubricants) by washing the starting fiber 10 times with demineralized water in a liquor ratio of at least 1:10 at room temperature and gentle drying (60 ° C. for 5 h).
- the fiber obtained by washing is hereinafter called "washed fiber”.
- Fibers are extracted with deionized water for one hour at room temperature in a liquor ratio of exactly 1:10. Fibers and extract are separated and an aliquot of exactly 50 ml of this extract is first titrated with 0.01 mol / 1 HCl to a pH which is exactly 1.50 units below the previously determined "limit”. Thereafter, the solution is back-titrated with 0.01 mol / l NaOH to a pH which is exactly 1.50 pH units above the "limit”. From the titration curve, the consumption of 0.01 mol / 1 NaOH is read off within these 3.00 pH units. This corresponds to 5 ml of a buffer capacity of 10 mmol / kg fiber.
- Fibers (yarns, raw materials) are extracted with deionized water for one hour at room temperature in a liquor ratio of exactly 1:10. Fibers and extract are separated and an aliquot of exactly 50 ml of this extract is first titrated with 0.01 mol / l NaOH to a pH which is exactly 1.50 units above the previously determined "threshold". Thereafter, the solution is back-titrated with 0.01 mol / l HCl to a pH which is exactly 1.50 pH units below the limit. From the titration curve, the consumption of 0.01 mol / 1 HCl within these 3.00 pH units is read. This corresponds to 5 ml of a buffer capacity of 10 mmol / kg fiber.
- Lyocell fibers prepared in accordance with the prior art and crosslinked in each case in the same way with a crosslinker of the above formula (I) were treated as follows:
- the wet rub resistance (NSF) of the fibers was measured according to the method described, for example, in WO 99/19555. Subsequently, the fibers were stored under identical conditions in an extreme climate with high humidity and temperature. The so-called “half-life” has been determined, which is the time in which the NSF has fallen to half the original value:
- the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine has been found by the method described above to have a "cut-off" at pH 8.5, below which the storage stability of the fibrillation protection deteriorates.
- the buffer capacity was determined by titrating the extract of the fiber with 0.01 mol / l HCl to pH 7.0 and back-titration with 0.01 mol / l on different samples of lyocell fibers each treated with the same amount of this crosslinking agent.
- 1 NaOH to pH 10.0 determined:
- Sample 1 Fiber treated with 2 g borax / kg fiber
- Sample 2 Fiber treated with 3.5 g borax / kg fiber
- Sample 3 Fiber treated with 12 g borax / kg fiber
- Sample 4 Fiber treated with 6 g borax / kg sample 5: fiber treated with 1.5 g sodium carbonate / kg fiber
- Sample 6 fiber treated with 1 g sodium carbonate / kg fiber
- Samples 7 to 11 Samples of non-buffered fibers respectively
- the buffering capacity is (significantly) more than 12 mmol / kg of fiber.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Woven Fabrics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA1030/2008A AT507051B1 (en) | 2008-06-27 | 2008-06-27 | CELLULOSE FIBER AND METHOD FOR THE PRODUCTION THEREOF |
PCT/AT2009/000242 WO2009155624A1 (en) | 2008-06-27 | 2009-06-18 | Cellulose fiber and method for the production thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2294259A1 true EP2294259A1 (en) | 2011-03-16 |
EP2294259B1 EP2294259B1 (en) | 2017-08-02 |
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EP09768599.4A Not-in-force EP2294259B1 (en) | 2008-06-27 | 2009-06-18 | Cellulose fiber and method for the production thereof |
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US (1) | US9963820B2 (en) |
EP (1) | EP2294259B1 (en) |
JP (1) | JP5722769B2 (en) |
KR (2) | KR101970626B1 (en) |
CN (2) | CN105040427A (en) |
AT (1) | AT507051B1 (en) |
BR (1) | BRPI0914774A2 (en) |
ES (1) | ES2645691T3 (en) |
PT (1) | PT2294259T (en) |
WO (1) | WO2009155624A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR102440861B1 (en) | 2020-05-26 | 2022-09-05 | 오영세 | Method for manufacturing lyocell fiber and lyocell fiber therefrom |
Family Cites Families (25)
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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 |
US4555348A (en) * | 1984-06-28 | 1985-11-26 | Sybron Chemicals Inc. | Liquid buffer system |
JP2776850B2 (en) * | 1988-12-22 | 1998-07-16 | 日本化薬株式会社 | Fixative composition of reactive dye for cellulose fiber and dyeing method using the same |
GB9103297D0 (en) | 1991-02-15 | 1991-04-03 | Courtaulds Plc | Fibre production method |
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 |
GB9222059D0 (en) | 1992-10-21 | 1992-12-02 | Courtaulds Plc | Fibre treatment |
GB9304887D0 (en) * | 1993-03-10 | 1993-04-28 | Courtaulds Plc | Fibre treatment |
TR27503A (en) * | 1993-04-21 | 1995-06-07 | Chemiefaser Lenzing Ag | A method for manufacturing cellulose fibers, which have a reduced tendency to fibrilles. |
US5662858A (en) * | 1993-04-21 | 1997-09-02 | Lenzing Aktiengesellschaft | Process for the production of cellulose fibres having a reduced tendency to fibrillation |
GB9407496D0 (en) * | 1994-04-15 | 1994-06-08 | Courtaulds Fibres Holdings Ltd | Fibre treatment |
GB9408742D0 (en) * | 1994-05-03 | 1994-06-22 | Courtaulds Fibres Holdings Ltd | Fabric treatment |
FR2737408B1 (en) * | 1995-07-31 | 1997-09-05 | Oreal | USE OF A BRADYKININE ANTAGONIST IN A COSMETIC, PHARMACEUTICAL OR DERMATOLOGICAL COMPOSITION AND COMPOSITION OBTAINED |
AT402642B (en) * | 1995-08-18 | 1997-07-25 | Chemiefaser Lenzing Ag | CELLULOSE FIBER CELLULOSE FIBER |
AT409144B (en) | 1996-06-21 | 2002-05-27 | Chemiefaser Lenzing Ag | METHOD FOR TREATING CELLULOSE FIBERS AND FORMS OF THESE FIBERS |
ATE228590T1 (en) * | 1997-09-17 | 2002-12-15 | Chemiefaser Lenzing Ag | METHOD FOR TREATING CELLULOSE FIBERS |
AT2256U1 (en) * | 1997-10-15 | 1998-07-27 | Chemiefaser Lenzing Ag | METHOD FOR TREATING CELLULOSIC MOLDED BODIES |
AT406588B (en) | 1998-09-29 | 2000-06-26 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FIBERS |
JP2000234267A (en) * | 1999-02-12 | 2000-08-29 | Bosuko:Kk | Improvement of textile product |
US6495058B1 (en) * | 2000-02-14 | 2002-12-17 | The Procter & Gamble Company | Aqueous wrinkle control compositions dispensed using optimal spray patterns |
JP2003176275A (en) * | 2001-12-12 | 2003-06-24 | Toshio Hagiwara | Method for producing stabilized shape-stabilizing agent |
AT413287B (en) * | 2003-11-25 | 2006-01-15 | Chemiefaser Lenzing Ag | PROCESS FOR PRODUCING CELLULOSIC FIBERS |
JP5010175B2 (en) * | 2006-04-13 | 2012-08-29 | 萩原 敏夫 | Modification process for cellulosic fiber materials |
JP2008063708A (en) * | 2006-09-09 | 2008-03-21 | Kanehisa:Kk | Producing method for modifying and hydrophobilizing organic fiber structure |
-
2008
- 2008-06-27 AT ATA1030/2008A patent/AT507051B1/en not_active IP Right Cessation
-
2009
- 2009-06-18 EP EP09768599.4A patent/EP2294259B1/en not_active Not-in-force
- 2009-06-18 CN CN201510394252.1A patent/CN105040427A/en active Pending
- 2009-06-18 WO PCT/AT2009/000242 patent/WO2009155624A1/en active Application Filing
- 2009-06-18 JP JP2011515014A patent/JP5722769B2/en not_active Expired - Fee Related
- 2009-06-18 KR KR1020167035944A patent/KR101970626B1/en active IP Right Grant
- 2009-06-18 ES ES09768599.4T patent/ES2645691T3/en active Active
- 2009-06-18 KR KR1020117000017A patent/KR20110025204A/en active Search and Examination
- 2009-06-18 PT PT97685994T patent/PT2294259T/en unknown
- 2009-06-18 CN CN2009801242518A patent/CN102076903A/en active Pending
- 2009-06-18 BR BRPI0914774A patent/BRPI0914774A2/en not_active Application Discontinuation
- 2009-06-18 US US13/001,098 patent/US9963820B2/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2009155624A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2011525571A (en) | 2011-09-22 |
CN105040427A (en) | 2015-11-11 |
US9963820B2 (en) | 2018-05-08 |
US20110171865A1 (en) | 2011-07-14 |
EP2294259B1 (en) | 2017-08-02 |
JP5722769B2 (en) | 2015-05-27 |
AT507051B1 (en) | 2015-05-15 |
KR101970626B1 (en) | 2019-04-19 |
ES2645691T3 (en) | 2017-12-07 |
BRPI0914774A2 (en) | 2015-10-20 |
CN102076903A (en) | 2011-05-25 |
KR20170002677A (en) | 2017-01-06 |
AT507051A3 (en) | 2015-04-15 |
AT507051A2 (en) | 2010-01-15 |
WO2009155624A1 (en) | 2009-12-30 |
PT2294259T (en) | 2017-11-14 |
KR20110025204A (en) | 2011-03-09 |
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