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. B. in the U.S. Patent 4,246,221 or in the PCT WO 93/19230 revealed.
• 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.
• Suitable crosslinking agents are for example in the EP 0 538 977 , of the WO 97/49856 and the WO 99/19555 described.
• Other crosslinking agents are for example from WO 94/09191 and the WO 95/28516 known.
• 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.
• 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.
• 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.
• Crosslinked lyocell fibers may vary depending on the process, e.g. Type of applied avivages, in the preparation 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. In turn, changing the 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 suitable range.
• substances having a pK a value just outside the appropriate range for example in the range of in each case up to 1 pH unit, preferably up to 0.5 pH units above or below having the "limit", provided that the Buffering effect towards those pH values at which a deterioration of the storage stability of Fibrillations s occurs.
• X represents halogen
• R H or an ionic radical
• n 0 or 1
• a salt of this compound is known from the WO 99/19555 known.
• Particularly preferred is the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine.
• 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, particularly 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 an optimum range in this case) 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, another limit value at a pH of 10.5, above which the fibrillation protection in turn drops 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.
• crosslinkers of this group also have a pH-altering potential (criterion c), apparently due to the release or the reaction of the halogen groups contained therein.
• 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.
• buffering substance 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.
• This embodiment of the cellulose fiber according to the invention preferably contains the buffers specifically specified above in the amounts indicated there.
• Another aspect of the present invention relates to a bale of cellulosic fibers containing the lyocell fibers of the present invention.
• bales are crimped into bales after their manufacture and are shipped in this form to customers (e.g., yarn producers).
• 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 is meant that minor admixtures of other fibers (e.g., 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 those 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, the majority of reactive groups of crosslinkers reacts as expected, which is why 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.
• 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 content 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
• buffer systems eg acetate, citrate, phosphate, bicarbonate, carbonate, borax
• concentration of the buffering substances of at least 0.1 mol / l and a pKa of the buffer system, which should not deviate more than 0.8 pH units from the adjusted pH.
• the fibrillation protection of the starting fiber treated with the cross-linking agent to be tested is determined by wet rub resistance (test according to US Pat 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 from 4.0 to 10.0 and kept in this liquid in a closed vessel at 50.degree.
• the NSF values obtained are plotted against time for each buffer system.
• criterion a) is fulfilled, ie it is a hydrolysis-sensitive crosslinking system.
• 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 compared to the baseline is the “optimal value” (criterion b1)).
• 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 should also 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.
• a buffer system which should also 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.
• the fibers are gently dried in the laboratory dryer (60 ° C 5 hours).
• 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.
• 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 M NaOH to a pH which is exactly 1.50 units above the previously determined "limit". 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 / l HCl is read off within these 3.00 pH units. This corresponds to 5 ml of a buffer capacity of 10 mmol / kg fiber.
• 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 buffering capacity is (significantly) more than 12 mmol / kg of fiber.

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