US20050022310A1 - Process for treating solvent-spun, cellulosic fibres - Google Patents
Process for treating solvent-spun, cellulosic fibres Download PDFInfo
- Publication number
- US20050022310A1 US20050022310A1 US10/832,693 US83269304A US2005022310A1 US 20050022310 A1 US20050022310 A1 US 20050022310A1 US 83269304 A US83269304 A US 83269304A US 2005022310 A1 US2005022310 A1 US 2005022310A1
- Authority
- US
- United States
- Prior art keywords
- auxiliary agent
- formula
- textile auxiliary
- salt
- process according
- 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.)
- Abandoned
Links
- 0 C.[2*]C(=O)N[1*]([4*])NC([3*])=O Chemical compound C.[2*]C(=O)N[1*]([4*])NC([3*])=O 0.000 description 31
- LVKKFNORSNCNPP-UHFFFAOYSA-N C=CC(=O)NC(NC(=O)C=C)C(=O)O Chemical compound C=CC(=O)NC(NC(=O)C=C)C(=O)O LVKKFNORSNCNPP-UHFFFAOYSA-N 0.000 description 5
- MFCLPFBOEWATMZ-UHFFFAOYSA-N C=CC(=O)NC1=CC=C(SOOO)C(NC(=O)C=C)=C1 Chemical compound C=CC(=O)NC1=CC=C(SOOO)C(NC(=O)C=C)=C1 MFCLPFBOEWATMZ-UHFFFAOYSA-N 0.000 description 3
Classifications
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
-
- 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
- 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
- D06M13/41—Amides derived from unsaturated carboxylic acids, e.g. acrylamide
Definitions
- the invention relates to a process for treating cellulose fibres and assemblies made of those cellulose fibres, wherein the fibres or the fibre assemblies, respectively, are contacted with a textile auxiliary agent in order to impart improved properties to the fibres.
- Fibrillation means the breaking up of the fibre in longitudinal direction at mechanical stress in the wet state, whereby the fibre assumes a hairy, furry appearance.
- a dyed fabric produced from those fibres loses a great deal of its colour intensity. Add to this that bright streaks develop in edges created by scouring and crumpling.
- the reason for fibrillation is thought to be that the fibre consists of fibrils arranged in the direction of the fibre, with crosslinking existing between them only to a small extent.
- streak formation may also occur if the fibres are dyed in the form of tows.
- the formation of knots may result from friction in the dry state, which property is known as “pilling”.
- WO 92/07124 describes a process for the production of a fibre having a reduced tendency to fibrillation, according to which the freshly spun, i.e. not yet dry, fibre is treated with a cationic polymer.
- a polymer comprising imidazole and azetidine groups is mentioned.
- a treatment with an emulsifiable polymer such as polyethylene or polyvinyl acetate, or also a crosslinking with glyoxal may take place.
- EP-A 0 538 977 and WO 94/09191 as well as WO 95/28516 describe a process of the initially mentioned kind, wherein solvent-spun fibres are contacted with a textile auxiliary agent in order to decrease the tendency to fibrillation.
- WO 94/24343 describes a process for the production of cellulose fibres having a decreased tendency to fibrillation, wherein a solution of cellulose is spun to fibres in a tertiary amine oxide and the freshly spun fibres are contacted with a textile auxiliary agent carrying at least two reactive groups and are washed with an aqueous buffer, with glyoxal not being used as the textile auxiliary agent.
- the freshly spun fibres are contacted with the textile auxiliary agent best in an alkaline environment.
- fibre assemblies made of solvent-spun fibres may be crosslinked with methylol compounds.
- methylol compounds it has turned out to be impossible to prevent scouring edges from forming during dyeing when using those compounds.
- crosslinking would have to occur prior to dyeing or at least during dyeing.
- methylol compounds and also the other classic permanent finishing agents are hardly suitable for this.
- a further disadvantage of the methylol compounds is the formation of formaldehyde, leading to an impairment of the workplace.
- the present invention aims at providing a process for treating cellulose fibres of the genus Lyocell and assemblies made of those fibres, which process may be realized in a simple manner and makes it possible that the treated fibres exhibit a decreased tendency to fibrillation or that the treated fibre assemblies, respectively, exhibit improved scouring and pilling values.
- the process according to the invention for treating solvent-spun fibres, wherein the fibres are contacted with a textile auxiliary agent is characterized in that a compound of the general formula or a salt thereof, respectively, is used as the textile auxiliary agent, wherein
- a 1,3,5-trisacryloyl tetrahydro-1,3,5-triazine as well as N,N′-methylene bisacrylamide are used as textile auxiliary agents.
- Those textile auxiliary agents are present in nonionic form.
- the compounds used according to the invention are present in ionic and dissolved form in an aqueous alkaline environment.
- the compounds used according to the invention are volatile only to a small extent or not at all.
- the residue R 4 is selected from the group consisting of-SO 3 H, —COOH, —OH and —SH.
- R 2 and R 3 both preferably mean (CH 2 ) m —CH ⁇ CH 2 in the textile auxiliary agent used.
- a textile auxiliary agent used with particular preference is a compound of the formula or a salt thereof, respectively.
- a compound of the formula or a salt thereof, respectively is used preferably as a textile auxiliary agent.
- a compound of the formula i.e. the 2,4-bis(acrylamido)benzene sulfonic acid, or a salt thereof, respectively, is used with particular preference as a textile auxiliary agent.
- a compound of the formula or a salt thereof, respectively is used as a textile auxiliary agent.
- the textile auxiliary agent is used in the form of the sodium, lithium, potassium, calcium or magnesium salt.
- other salts in particular metallic salts, may be used.
- the fibres preferably are contacted with an alkaline solution of the textile auxiliary agent.
- the compound used according to the invention is prepared in the impregnating solution virtually in situ by producing the two acrylamido groups from the respective ⁇ -halogen alkyl compound by means of an elimination reaction.
- 2,4-bis(acrylamido)benzene sulfonic acid or, e.g., of its sodium salt, respectively
- it can be produced in the impregnating solution directly from the sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid.
- the process according to the invention is carried out for the treatment of fibres which are provided in the never-dried state.
- the cut fibres washed free from NMMO and having a defined moisture of from 50% to 500% adjusted, for instance, by squeezing may be contacted in a loose structure (“fleece”) on a moving screen belt with the bath containing the textile auxiliary agent and may be soaked, for instance, by spraying (“impregnation”).
- the fleece has a weight per unit area of 0.2-15 kg/m 2 , preferably of between 1 and 8 kg/m 2 , based on the dry fibre, whereby the retention time of the fibre in that field of impregnation may amount to between 1 and 25 min, preferably, however, to from 2 to 10 min.
- the impregnation of the fibre can be effected only from one side but also from both sides of the fleece, whereby the ratio between fibre and treatment bath (kg/kg) may amount to from 1:1 to 1:50.
- the textile auxiliary agent can be applied in a mixture with or separate from the catalyst which optionally is necessary.
- the fleece is squeezed to a defined moisture of from 50% to 500%, the squeezed treatment bath is returned to the impregnation cycle and the temperature of the fleece is adjusted by suitable means, preferably by hot water vapour, and is maintained, whereby the retention time may amount to about 2-15 min.
- the fibre heats up along with the bath to the desired temperature and the cellulose reacts with the textile auxiliary agent.
- the treatment is carried out such that the fibre is thereby not dried.
- an acidified washing bath may be used for that in the first washing stages.
- the number of washing stages complies with the employed concentrations and/or the washing efficiency of the individual stages.
- the textile auxiliary agents used according to the invention are excellently suitable also for the treatment of already dried fibres and for the treatment of fibre assemblies, such as yarns, woven or knitted fabrics, containing solvent-spun fibres.
- the fibres may be provided in dyed or undyed form.
- the present invention relates to the use of a compound of the formula wherein R 1 , R 2 , R 3 and R 4 have the above-indicated meaning, or of a salt thereof, respectively, as a textile auxiliary agent for the treatment of solvent-spun fibres.
- the compounds of formula (I) are particularly suitable for decreasing the tendency to fibrillation of solvent-spun fibres.
- the present invention furthermore relates to solvent-spun fibres which are obtainable in accordance with the process according to the invention as well as to fibre assemblies containing such solvent-spun fibres.
- the textile auxiliary agents used according to the invention in which the residue R 1 is phenyl, are new compounds. Therefore, the invention furthermore relates to a compound of the formula wherein R 2 , R 3 and R 4 each have the above-indicated meaning, as well as to the salts thereof, provided that
- N,N′-(2-hydroxy-1,4-phenylene)-bis-2-propenamide is registered in the “Chemical Abstracts” (American Chemical Society) under registration no. 105298-66-6.
- the compounds according to the invention may be produced in that a compound of the formula is reacted with a compound of the formula wherein R 2 , R 3 and R 4 each have the above-indicated meanings, and the product obtained optionally is converted to the form of a salt.
- the compounds of formula (X) are new as well. They may be produced in that a compound of the formula is reacted with a compound of the formula wherein R 4 , R 5 and R 6 have the above-indicated meanings, and the product obtained optionally is converted to the form of a salt.
- the final product was analyzed by means of HPCL and an NMR spectroscopy.
- Solvent-spun fibres produced according to the process described in WO 93/19230 and having a titre of 1.3 dtex were treated as follows in the never-dried state: At a bath ratio of 1:10, the fibres were impregnated with a solution, containing 50 g/l of sodium salt of the 2,4-bis(acrylamido)benzene sulfonic acid and 100 g/l of sodium sulfate, for 4 minutes at 30° C. Thereupon, 4 g/l of NaOH was added, and impregnation was continued for another 2 minutes. The solution had a pH value of 12.7. Subsequently, the fibres were squeezed to a moisture content of 100%-110% by means of a squeezer and were heat-treated with saturated steam (100%) at 100° C. for 4 minutes, were washed out and dried.
- the degree of fibrillation of the fibres was determined by way of the wet abrasion resistance (testing method in accordance with WO 99/19555) of the individual fibres. According to this testing method, the sample treated according to the invention turns out to exhibit an average value of 560 revolutions. Compared with that, an untreated fibre exhibits a wet abrasion value of only 40-60 revolutions. The nitrogen content of the treated fibres amounts to 0.34%.
- the determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 1180 revolutions.
- the nitrogen content of the fibres amounts to 0.38%.
- a solution containing 50 g/l of sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid, is mixed with 10 g/l of sodium hydroxide at 30° C. and is stirred for 20 minutes at this temperature.
- solvent-spun fibres (titre 1.3 dtex) were impregnated at a bath ratio of 1:10 for more than 2 minutes at 30° C.
- 100 g/l of sodium sulfate was dissolved in the impregnating solution, and after 2 minutes 4 g/l of NaOH was added. After another 4 minutes of impregnation at 30° C., the fibres were squeezed to a pick-up of 100%-110%, were heat-treated with saturated steam for 4 minutes, were washed out and dried.
- the determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 780 revolutions.
- the nitrogen content of the fibres amounts to 0.34%.
- a solution containing 50 g/l of sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid, was mixed with 10 g/l of sodium hydroxide at 30° C. and was stirred for 20 minutes at this temperature. In that solution, 100 g/l of sodium sulfate and 4 g/l of NaOH were dissolved. At a bath ratio of 1:10, a piece of that fleece made of never-dried, solvent-spun fibres (titre 1.3 dtex) was impregnated in that solution for 4 minutes at 30° C.
- the piece of fleece was squeezed to a pick-up of 100%-110%, was heat-treated with saturated steam for 4 minutes, was washed out and dried.
- the determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 570 revolutions.
- the nitrogen content of the fibres amounts to 0.39%.
- a dyed knitted fabric made of solvent-spun fibres was impregnated with an aqueous solution, containing 50 g/l of sodium salt of the 2,4-bis(acrylamido)benzene sulfonic acid and 50 g/l of sodium sulfate, to which shortly before impregnation 4 g/l of NaOH had been added, for 2 minutes at room temperature (RT) (pH value of the solution 12.7).
- RT room temperature
- the excess solution was squeezed out at 1 bar.
- the knitted fabric was heat-treated with water vapour at 100° C. Subsequently, the knitted fabric was washed repeatedly with 2% acetic acid and water and was finally dried.
- Example 7 An undyed knitted fabric made of solvent-spun fibres was treated as described in Example 7 and was subjected to a wet abrasion test. The mean value of the wet abrasion test amounted to 620 revolutions.
- the wet abrasion resistance of the individual fibre yielded an average value of 700 revolutions.
- the nitrogen content of the fibre amounted to 0.33%.
- a solution containing 60 g/l of bisacrylamido acetic acid, was mixed with 21 g/l of sodium hydroxide at room temperature, was stirred, and never-dried, solvent-spun fibres having a titre of 1.3 dtex were immediately added to that solution at a bath ratio of 1:10 and were then impregnated for 2 min. at room temperature. Thereupon, 100 g/l of sodium sulfate was added to that solution, and impregnation was continued for another 3 min. at 50° C. Thereupon, squeezing was carried out to a pick-up of 100-110%, and 4 minutes of heat-treatment with saturated steam, washing-out and drying were effected.
- the wet abrasion resistance of the individual fibre yielded an average value of 400 revolutions.
- the nitrogen content amounted to 0.32%.
- a solution containing 60 g/l of bisacrylamido acetic acid, was mixed with 21 g/l of sodium hydroxide at room temperature, was stirred, and never-dried, solvent-spun fibres having a titre of 1.3 dtex were immediately added to that solution at a bath ratio of 1:10 and were then impregnated for 5 min. at room temperature. Thereupon, squeezing was carried out to a pick-up of 100-110%, and 4 minutes of heat-treatment with saturated steam, washing-out and drying were effected.
- the wet abrasion resistance of the individual fibre yielded an average value of 320 revolutions.
- the nitrogen content of the fibre amounted to 0.31%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a process for treating solvent-spun, cellulosic fibres, wherein the fibres are contacted with a textile auxiliary agent in an alkaline environment. The process according to the invention is characterized in that a compound of the general formula
or a salt thereof, respectively, is used as the textile auxiliary agent, wherein
- R1 is a bridging link selected from the group consisting of a linear or branched chain comprising 1 to 4 C-atoms and phenyl,
- R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m=0 to 2, and wherein R4 denotes a ionic group and/or a group ionizable in an alkaline environment.
Description
- The invention relates to a process for treating cellulose fibres and assemblies made of those cellulose fibres, wherein the fibres or the fibre assemblies, respectively, are contacted with a textile auxiliary agent in order to impart improved properties to the fibres.
- As an alternative to the viscose process, in recent years there have been described a number of processes wherein cellulose, without forming a derivative, is dissolved in an organic solvent, a combination of an organic solvent and an inorganic salt, or in an aqueous saline solution. Cellulose fibres made from such solutions are called “solvent-spun fibres” and have received by BISFA (The International Bureau for the Standardisation of man made Fibres) the generic name Lyocell. As Lyocell, BISFA defines a cellulose fibre obtained by a spinning process from an organic solvent. By “organic solvent”, BISFA understands a mixture of an organic chemical and water. “Solvent-spinning” is supposed to mean dissolution and spinning without derivatization.
- So far, however, only a single process for the production of a solvent-spun cellulose fibre has achieved industrial-scale realization. In this process a tertiary amine-oxide, particularly N-methylmorpholine-N-oxide (NMMO), is used as a solvent. Such a process is described for instance in U.S. Pat. No. 4,246,221 and provides fibres which are distinguished by a high tensile strength, a high wet-modulus and a high loop strength.
- However, the usability of textile fabrics, for instance woven fabrics, produced from the above-mentioned fibres, is restricted to a large extent by those fibres' pronounced tendency to fibrillate in the wet state. Fibrillation means the breaking up of the fibre in longitudinal direction at mechanical stress in the wet state, whereby the fibre assumes a hairy, furry appearance. In the course of a couple of washings, a dyed fabric produced from those fibres loses a great deal of its colour intensity. Add to this that bright streaks develop in edges created by scouring and crumpling. The reason for fibrillation is thought to be that the fibre consists of fibrils arranged in the direction of the fibre, with crosslinking existing between them only to a small extent.
- Furthermore, streak formation may also occur if the fibres are dyed in the form of tows. In textile areas, the formation of knots may result from friction in the dry state, which property is known as “pilling”.
- WO 92/07124 describes a process for the production of a fibre having a reduced tendency to fibrillation, according to which the freshly spun, i.e. not yet dry, fibre is treated with a cationic polymer. As such a polymer, a polymer comprising imidazole and azetidine groups is mentioned. In addition, furthermore a treatment with an emulsifiable polymer, such as polyethylene or polyvinyl acetate, or also a crosslinking with glyoxal may take place.
- In a lecture given by S. Mortimer at the CELLUCON conference in 1993 in Lund, Sweden, it was mentioned that the tendency to fibrillation rises as drawing is increased.
- EP-A 0 538 977 and WO 94/09191 as well as WO 95/28516 describe a process of the initially mentioned kind, wherein solvent-spun fibres are contacted with a textile auxiliary agent in order to decrease the tendency to fibrillation.
- WO 94/24343 describes a process for the production of cellulose fibres having a decreased tendency to fibrillation, wherein a solution of cellulose is spun to fibres in a tertiary amine oxide and the freshly spun fibres are contacted with a textile auxiliary agent carrying at least two reactive groups and are washed with an aqueous buffer, with glyoxal not being used as the textile auxiliary agent. According to this previously known process, the freshly spun fibres are contacted with the textile auxiliary agent best in an alkaline environment.
- Furthermore, it is known that, for the manufacture of washproof woven and knitted fabrics, fibre assemblies made of solvent-spun fibres may be crosslinked with methylol compounds. However, it has turned out to be impossible to prevent scouring edges from forming during dyeing when using those compounds. For that purpose, crosslinking would have to occur prior to dyeing or at least during dyeing. However, methylol compounds and also the other classic permanent finishing agents are hardly suitable for this. A further disadvantage of the methylol compounds is the formation of formaldehyde, leading to an impairment of the workplace.
- Further processes for treating cellulose fibres of the genus Lyocell are known, for instance, from WO 97/49856, the Austrian Utility Model no. 2527 and WO 99/19555.
- However, the processes suggested in the prior art for treating cellulose fibres of the genus Lyocell exhibit a number of disadvantages:
- For instance, a great number of the textile auxiliary agents suggested up to now are very tedious in their manufacture and hence are expensive. With other textile auxiliary agents, it may be observed that they are subject to hydrolysis in the alkaline environment necessary for the reaction with the cellulose. Therefore, losses of hydrolysis occur. Furthermore, many of the proposed textile auxiliary agents are not soluble enough in the necessary alkaline environment and must be used in the form of a dispersion. This can lead to irregular treatment effects. Finally, it must be mentioned that the use of some known textile auxiliary agents is difficult because of their toxicity.
- The present invention aims at providing a process for treating cellulose fibres of the genus Lyocell and assemblies made of those fibres, which process may be realized in a simple manner and makes it possible that the treated fibres exhibit a decreased tendency to fibrillation or that the treated fibre assemblies, respectively, exhibit improved scouring and pilling values.
-
- R1 is a bridging link selected from the group consisting of a linear or branched chain comprising 1 to 4 C-atoms and phenyl,
- R2 and R3 are the same or different and are selected from the group consisting of (CH2)n—CH═CH2 with m=0 to 2, and wherein R4 denotes a ionic group and/or a group ionizable in an alkaline environment.
- Surprisingly, it was found that the textile auxiliary agents used according to the invention, which are available at relatively low costs, give rise to an improvement of the properties of the treated fibres to the same or even to a larger extent as do, for instance, the substances known from EP-A 0 538 977, which are to be manufactured with effort.
- Furthermore, it was found that the substances used according to the invention are extremely resistant to hydrolysis in an alkaline environment. Therefore, in comparison with the textile auxiliary agents disclosed, for instance, in the Austrian Utility Model no. 2527 or in WO 99/19555, no losses of hydrolysis occur in the course of the treatment. For that reason, less textile auxiliary agent is needed in order to achieve equivalent or even better properties of the treated fibres.
- In the processes described in WO 94/09191 and WO 95/28516, respectively, a 1,3,5-trisacryloyl tetrahydro-1,3,5-triazine as well as N,N′-methylene bisacrylamide are used as textile auxiliary agents. Those textile auxiliary agents are present in nonionic form. As opposed to that, the compounds used according to the invention are present in ionic and dissolved form in an aqueous alkaline environment.
- Also, the compounds used according to the invention are volatile only to a small extent or not at all.
- Preferably, the residue R4 is selected from the group consisting of-SO3H, —COOH, —OH and —SH.
- Furthermore, R2 and R3 both preferably mean (CH2)m—CH═CH2 in the textile auxiliary agent used.
-
-
-
-
-
- Preferably, the textile auxiliary agent is used in the form of the sodium, lithium, potassium, calcium or magnesium salt. But also other salts, in particular metallic salts, may be used.
- In the process according to the invention, the fibres preferably are contacted with an alkaline solution of the textile auxiliary agent.
- A particularly interesting and inexpensive variant of the process according to the invention consists in that an alkaline solution of a compound of the formula
wherein R5 and R6 both are (CH2)n—X, n=2 to 4, X=halogen, is produced and that, prior to or during contacting with the fibres, this compound in an alkaline solution is reacted to a textile auxiliary agent according to formula (I), wherein R2 and R3 both mean (CH2)m—CH═CH2, wherein m=n−2. - Thus, prior to or during contacting with the fibres, the compound used according to the invention is prepared in the impregnating solution virtually in situ by producing the two acrylamido groups from the respective ω-halogen alkyl compound by means of an elimination reaction.
- In case of the preferably used 2,4-bis(acrylamido)benzene sulfonic acid (or, e.g., of its sodium salt, respectively), it can be produced in the impregnating solution directly from the sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid.
- Preferably, the process according to the invention is carried out for the treatment of fibres which are provided in the never-dried state.
- For the continuous treatment of never-dried, solvent-spun fibres, the cut fibres washed free from NMMO and having a defined moisture of from 50% to 500% adjusted, for instance, by squeezing may be contacted in a loose structure (“fleece”) on a moving screen belt with the bath containing the textile auxiliary agent and may be soaked, for instance, by spraying (“impregnation”). The fleece has a weight per unit area of 0.2-15 kg/m2, preferably of between 1 and 8 kg/m2, based on the dry fibre, whereby the retention time of the fibre in that field of impregnation may amount to between 1 and 25 min, preferably, however, to from 2 to 10 min. The impregnation of the fibre can be effected only from one side but also from both sides of the fleece, whereby the ratio between fibre and treatment bath (kg/kg) may amount to from 1:1 to 1:50. In doing so, the textile auxiliary agent can be applied in a mixture with or separate from the catalyst which optionally is necessary.
- After impregnation, the fleece is squeezed to a defined moisture of from 50% to 500%, the squeezed treatment bath is returned to the impregnation cycle and the temperature of the fleece is adjusted by suitable means, preferably by hot water vapour, and is maintained, whereby the retention time may amount to about 2-15 min. In doing so, the fibre heats up along with the bath to the desired temperature and the cellulose reacts with the textile auxiliary agent. Preferably, the treatment is carried out such that the fibre is thereby not dried.
- Subsequently, the fibre is washed free from non-fixed reaction products, if possible under neutralization. With basically catalyzed crosslinking agents, an acidified washing bath may be used for that in the first washing stages. The number of washing stages complies with the employed concentrations and/or the washing efficiency of the individual stages.
- The textile auxiliary agents used according to the invention are excellently suitable also for the treatment of already dried fibres and for the treatment of fibre assemblies, such as yarns, woven or knitted fabrics, containing solvent-spun fibres. The fibres may be provided in dyed or undyed form.
-
- Thereby, the compounds of formula (I) are particularly suitable for decreasing the tendency to fibrillation of solvent-spun fibres.
- However, the compounds of formula (1), in particular those in which R1 is phenyl, were surprisingly also found to cause the increase of the ultraviolet absorption of solvent-spun fibres.
- The present invention furthermore relates to solvent-spun fibres which are obtainable in accordance with the process according to the invention as well as to fibre assemblies containing such solvent-spun fibres.
-
-
- if R4═—OH and R2 and R3 both are —CH═CH2, the two amide groups are not in para-position to each other,
- if R4═—SO3H, R2 and R3 both are —CH═CH2 and the two amide groups are in ortho-position to each other, the calcium salt is excluded.
- The N,N′-(2-hydroxy-1,4-phenylene)-bis-2-propenamide is registered in the “Chemical Abstracts” (American Chemical Society) under registration no. 105298-66-6.
- The calcium salt of the 3,4-bis-[(1-oxo-2-propenyl)amino]benzene sulfonic acid is registered in the “Chemical Abstracts” (American Chemical Society) under registration no. 58772-33-1.
-
-
-
- In a 5 l beaker with an automatic stirrer, 66 g of KH2PO4 and 3 g of Na2HPO4 were dissolved in 1. 5 l of H2O (pH=6.4). After adding 100 g (=0.53 mol) of 2,4-diaminobenzene sulfonic acid, the solution was cooled to <1° C. by the introduction of ice. Within 70 min, 260 ml (=233 g=2.58 mol) of acrylic-acid chloride was dropped in through a drip funnel, and by adding a 20% NaOH solution the pH value was adjusted to approximately 3.5 (pH values of below 3 and above 4 are to be avoided). By the introduction of ice, the temperature of the solution was kept at <1° C. When adding was completed (final volume=5 l), stirring was carried out for 1 h, whereby the solution was allowed to heat up to room temperature (RT).
- After the neutralization with NaOH, the small amount of white solid was filtered off from the black solution, enough NaCl was added to the filtrate for a 20% solution to emerge, and the solution was stirred slowly overnight. The nascent grey precipitate was filtered off, was washed with a 20% NaCl solution and dried in the drying cabinet at approximately 65° C. (for about 24 h).
- The final product was analyzed by means of HPCL and an NMR spectroscopy.
- Yield: 152 g (=90% d. Th.) 2,4-bis(acrylamido)benzene sulfonic acid-sodium salt.
- 38.8 g of 2,4-diaminobenzene sulfonic acid (manufacturer BASF) was dispersed in 600 ml of water and was stirred. The pH value was adjusted to 6.5 by means of dissolved NaOH.
- After cooling down to 10° C., 5.3 g of 3-chloropropionyl chloride was added dropwise (0.5 h), whereby the temperature was kept at 5-10° C. and the pH value was kept at 3.0-3.5. When adding was finished, it was determined by thin-layer chromatography that traces of the monoacylated product were still present. Therefore, another 13 g of acid chloride was added in order to complete the reaction. After raising the pH value to 5, 20% w/v of a NaCl solution was used for salting out, and the grey solid formed was filtered off. The cake was washed with 150 ml of a sodium chloride solution (20% w/v) and was oven-dried at 65° C., wherefrom 146 g of a product was obtained.
- Solvent-spun fibres produced according to the process described in WO 93/19230 and having a titre of 1.3 dtex were treated as follows in the never-dried state: At a bath ratio of 1:10, the fibres were impregnated with a solution, containing 50 g/l of sodium salt of the 2,4-bis(acrylamido)benzene sulfonic acid and 100 g/l of sodium sulfate, for 4 minutes at 30° C. Thereupon, 4 g/l of NaOH was added, and impregnation was continued for another 2 minutes. The solution had a pH value of 12.7. Subsequently, the fibres were squeezed to a moisture content of 100%-110% by means of a squeezer and were heat-treated with saturated steam (100%) at 100° C. for 4 minutes, were washed out and dried.
- The degree of fibrillation of the fibres was determined by way of the wet abrasion resistance (testing method in accordance with WO 99/19555) of the individual fibres. According to this testing method, the sample treated according to the invention turns out to exhibit an average value of 560 revolutions. Compared with that, an untreated fibre exhibits a wet abrasion value of only 40-60 revolutions. The nitrogen content of the treated fibres amounts to 0.34%.
- At a bath ratio of 1:10, never-dried, solvent-spun fibres having a titre of 1.3 dtex were impregnated with a solution, containing 50 g/l of sodium salt of the 2,4-bis(acrylamido)benzene sulfonic acid and 50 g/l of sodium sulfate, to which shortly before impregnation 4 g/l of NaOH had been added, for 2 minutes at room temperature (RT) (pH value of the solution 12.7). Thereupon, the fibres were squeezed to a moisture content of 100%-110% by means of a squeezer (Foulard), were heat-treated with saturated steam for 6 minutes, were washed out and dried.
- The determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 1180 revolutions. The nitrogen content of the fibres amounts to 0.38%.
- A solution, containing 50 g/l of sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid, is mixed with 10 g/l of sodium hydroxide at 30° C. and is stirred for 20 minutes at this temperature. In that solution, never-dried, solvent-spun fibres (titre 1.3 dtex) were impregnated at a bath ratio of 1:10 for more than 2 minutes at 30° C. Thereupon, 100 g/l of sodium sulfate was dissolved in the impregnating solution, and after 2 minutes 4 g/l of NaOH was added. After another 4 minutes of impregnation at 30° C., the fibres were squeezed to a pick-up of 100%-110%, were heat-treated with saturated steam for 4 minutes, were washed out and dried.
- The determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 780 revolutions. The nitrogen content of the fibres amounts to 0.34%.
- A solution, containing 50 g/l of sodium salt of the 2,4-bis(3-chloropropionamido)benzene sulfonic acid, was mixed with 10 g/l of sodium hydroxide at 30° C. and was stirred for 20 minutes at this temperature. In that solution, 100 g/l of sodium sulfate and 4 g/l of NaOH were dissolved. At a bath ratio of 1:10, a piece of that fleece made of never-dried, solvent-spun fibres (titre 1.3 dtex) was impregnated in that solution for 4 minutes at 30° C.
- Thereupon, the piece of fleece was squeezed to a pick-up of 100%-110%, was heat-treated with saturated steam for 4 minutes, was washed out and dried.
- The determination of the wet abrasion resistance of the fibres treated in this manner yielded an average value of 570 revolutions. The nitrogen content of the fibres amounts to 0.39%.
- At a bath ratio of 1:30, a dyed knitted fabric made of solvent-spun fibres was impregnated with an aqueous solution, containing 50 g/l of sodium salt of the 2,4-bis(acrylamido)benzene sulfonic acid and 50 g/l of sodium sulfate, to which shortly before impregnation 4 g/l of NaOH had been added, for 2 minutes at room temperature (RT) (pH value of the solution 12.7). By means of a Foulard, the excess solution was squeezed out at 1 bar. For 5 minutes, the knitted fabric was heat-treated with water vapour at 100° C. Subsequently, the knitted fabric was washed repeatedly with 2% acetic acid and water and was finally dried.
- Individual fibres of the knitted fabric were prepared and subjected to a wet abrasion test. The mean value of the wet abrasion test amounted to 650 revolutions.
- An undyed knitted fabric made of solvent-spun fibres was treated as described in Example 7 and was subjected to a wet abrasion test. The mean value of the wet abrasion test amounted to 620 revolutions.
- A solution, containing 60 g/l of bisacrylamido acetic acid, was mixed with 21 g/l of sodium hydroxide at 30° C., was stirred, and never-dried, solvent-spun fibres having a titre of 1.3 dtex were immediately added to that solution at a bath ratio of 1:10 and were then impregnated for 2 min. at 50° C. Thereupon, 100 g/l of sodium sulfate was added to that solution, and impregnation was continued for another 3 min. at 50° C. Thereupon, squeezing was carried out to a pick-up of 100-110%, and 4 minutes of heat-treatment with saturated steam, washing-out and drying were effected.
- The wet abrasion resistance of the individual fibre yielded an average value of 700 revolutions. The nitrogen content of the fibre amounted to 0.33%.
- A solution, containing 60 g/l of bisacrylamido acetic acid, was mixed with 21 g/l of sodium hydroxide at room temperature, was stirred, and never-dried, solvent-spun fibres having a titre of 1.3 dtex were immediately added to that solution at a bath ratio of 1:10 and were then impregnated for 2 min. at room temperature. Thereupon, 100 g/l of sodium sulfate was added to that solution, and impregnation was continued for another 3 min. at 50° C. Thereupon, squeezing was carried out to a pick-up of 100-110%, and 4 minutes of heat-treatment with saturated steam, washing-out and drying were effected.
- The wet abrasion resistance of the individual fibre yielded an average value of 400 revolutions. The nitrogen content amounted to 0.32%.
- A solution, containing 60 g/l of bisacrylamido acetic acid, was mixed with 21 g/l of sodium hydroxide at room temperature, was stirred, and never-dried, solvent-spun fibres having a titre of 1.3 dtex were immediately added to that solution at a bath ratio of 1:10 and were then impregnated for 5 min. at room temperature. Thereupon, squeezing was carried out to a pick-up of 100-110%, and 4 minutes of heat-treatment with saturated steam, washing-out and drying were effected.
- The wet abrasion resistance of the individual fibre yielded an average value of 320 revolutions. The nitrogen content of the fibre amounted to 0.31%.
Claims (28)
1-21. (Cancelled)
22. A process for treating solvent-spun, cellulosic fibers comprising contacting the fibers with a textile auxiliary agent in an alkaline environment, wherein the textile auxiliary agent has a general formula (I)
or is a salt thereof,
wherein R1 is a bridging link selected from the group consisting of a linear or branched chain comprising 1 to 4 C-atoms and phenyl,
wherein R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m=0 to 2, and
wherein R4 denotes a ionic group and/or a group ionizable in an alkaline environment.
23. The process according to claim 22 , wherein R4 is selected from the group consisting of —SO3H, —COOH, —OH and —SH.
24. The process according to claim 22 , wherein R2 and R3 are (CH2)m-CH═CH2.
25. The process according to claim 23 , wherein R2 and R3 are (CH2)m—CH═CH2.
38. The process according to claim 22 , wherein the textile auxiliary agent is in the form of the sodium, lithium, potassium, calcium or magnesium salt.
39. The process according to claim 22 , wherein the fibers are contacted with an alkaline solution of the textile auxiliary agent.
40. The process according to claim 22 , further comprising providing a compound of the formula (VII)
wherein R5 and R6 both are (CH2)n—X, n=2 to 4, X=halogen; reacting the compound of formula (VII) to a textile auxiliary agent according to formula (I) prior to or during contacting the fibers with the textile auxiliary agent according to formula(I), wherein R2 and R3 both mean (CH2)m-CH═CH2, wherein m=n−2.
41. The process according to claim 22 , wherein the fibers are provided in the never-dried state.
42. The process according to claim 22 , wherein the fibers are provided as fiber assemblies or as a component of a fiber assembly
43. Solvent-spun cellulose fibers treated by a process comprising contacting the fibers with a textile auxiliary agent in an alkaline environment, wherein the textile auxiliary agent has a general formula (I)
or is a salt thereof,
wherein R1 is a bridging link selected from the group consisting of a linear or branched chain comprising 1 to 4 C-atoms and phenyl,
wherein R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m=0 to 2, and
wherein R4 denotes a ionic group and/or a group ionizable in an alkaline environment.
44. A fiber assembly containing solvent-spun cellulose fibers treated by a process comprising contacting the fibers with a textile auxiliary agent in an alkaline environment, wherein the textile auxiliary agent has a general formula (I)
or is a salt thereof,
wherein R1 is a bridging link selected from the group consisting of a linear or branched chain comprising 1 to 4 C-atoms and phenyl,
wherein R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m=0 to 2,
wherein R4 denotes a ionic group and/or a group ionizable in an alkaline environment, and wherein the fibers are provided as fiber assemblies or as a component of a fiber assembly.
45. A compound having the formula (II)
or is a salt thereof, wherein R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m=0 to 2, R4 denotes a ionic group and/or a group ionizable in an alkaline environment provided that
if R4═—OH and R2 and R3 both are —CH═CH2, the two amide groups are not in para-position to each other,
if R4═—SO3H, R2 and R3 both are —CH═CH2 and the two amide groups are in ortho-position to each other, the calcium salt is excluded.
46. A process for the production of a compound according to claim 45 comprising reacting a compound having the formula (VIII)
with a compound having the formula (IX)
wherein R2 and R3 are the same or different and are selected from the group consisting of (CH2)m—CH═CH2 with m 0 to 2, R4 denotes a ionic group and/or a group ionizable in an alkaline environment.
47. The process of claim 46 , further comprising converting the compound obtained to the form of a salt.
48. A process for the production of a compound according to claim 45 comprising reacting in an alkaline solution a compound having the formula (X)
wherein R5 and R6 both are (CH2)n—X, n=2 to 4, X=halogen, with a compound having a formula (II),
wherein R2 and R3 both mean (CH2)m—CH═CH2, wherein m=n−2.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0173101A AT413824B (en) | 2001-11-02 | 2001-11-02 | METHOD FOR THE TREATMENT OF SOLVENT-SPUN CELLULOSIC FIBERS |
ATA1731/2001 | 2001-11-02 | ||
PCT/AT2002/000306 WO2003038164A2 (en) | 2001-11-02 | 2002-10-30 | Method for treating solvent-spun cellulose fibers |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AT2002/000306 Continuation WO2003038164A2 (en) | 2001-11-02 | 2002-10-30 | Method for treating solvent-spun cellulose fibers |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050022310A1 true US20050022310A1 (en) | 2005-02-03 |
Family
ID=3688768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/832,693 Abandoned US20050022310A1 (en) | 2001-11-02 | 2004-04-22 | Process for treating solvent-spun, cellulosic fibres |
Country Status (14)
Country | Link |
---|---|
US (1) | US20050022310A1 (en) |
EP (1) | EP1440190B1 (en) |
JP (1) | JP2005507035A (en) |
KR (1) | KR100927184B1 (en) |
CN (1) | CN1270004C (en) |
AT (2) | AT413824B (en) |
AU (1) | AU2002342379A1 (en) |
BR (1) | BR0213716B1 (en) |
DE (1) | DE50213134D1 (en) |
ES (1) | ES2319623T3 (en) |
PT (1) | PT1440190E (en) |
TR (1) | TR200400926T2 (en) |
TW (1) | TW200300186A (en) |
WO (1) | WO2003038164A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180098099A1 (en) * | 2016-09-30 | 2018-04-05 | Disney Enterprises, Inc. | Real-time data updates from a run down system for a video broadcast |
US10995429B2 (en) * | 2016-02-11 | 2021-05-04 | Deutsche Institute Furtextil-Und Faserforschung Denkendorf | Method for producing carbon fibers from cellulose fibers treated with sulfonic acid salts |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531442A (en) * | 1967-03-02 | 1970-09-29 | Lubrizol Corp | Alpha-sulfo-n,n'-alkylidene bis-amide polymers |
US4068068A (en) * | 1975-05-05 | 1978-01-10 | Hoechst Aktiengesellschaft | Process for the manufacture of water-absorbing cellulose ethers |
US4336023A (en) * | 1980-12-30 | 1982-06-22 | Rohm And Haas Company | Formaldehyde-free durable press finish fabrics |
US5310424A (en) * | 1991-10-21 | 1994-05-10 | Courtaulds Plc | Process for reducing the fibrillation tendency of solvent-spun cellulose fibre |
US6241933B1 (en) * | 1997-10-15 | 2001-06-05 | Lenzing Aktiengesellschaft | Process for the treatment of cellulosic moulded bodies |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2273091A1 (en) * | 1974-05-30 | 1975-12-26 | Rhone Poulenc Textile | Non fibrillable polynosic fibres - obtd by treatment of fibres during prodn with acryloyl gp contg crosslinking agent |
GB9222059D0 (en) * | 1992-10-21 | 1992-12-02 | Courtaulds Plc | Fibre treatment |
GB9407496D0 (en) * | 1994-04-15 | 1994-06-08 | Courtaulds Fibres Holdings Ltd | Fibre treatment |
JPH1192435A (en) * | 1997-09-26 | 1999-04-06 | Toray Ind Inc | Benzene derivative and its production |
-
2001
- 2001-11-02 AT AT0173101A patent/AT413824B/en not_active IP Right Cessation
-
2002
- 2002-10-30 PT PT02778982T patent/PT1440190E/en unknown
- 2002-10-30 KR KR1020047006478A patent/KR100927184B1/en active IP Right Grant
- 2002-10-30 TW TW091132183A patent/TW200300186A/en unknown
- 2002-10-30 AU AU2002342379A patent/AU2002342379A1/en not_active Abandoned
- 2002-10-30 TR TR2004/00926T patent/TR200400926T2/en unknown
- 2002-10-30 ES ES02778982T patent/ES2319623T3/en not_active Expired - Lifetime
- 2002-10-30 CN CNB028217977A patent/CN1270004C/en not_active Expired - Fee Related
- 2002-10-30 EP EP02778982A patent/EP1440190B1/en not_active Expired - Lifetime
- 2002-10-30 DE DE50213134T patent/DE50213134D1/en not_active Expired - Fee Related
- 2002-10-30 BR BRPI0213716-0A patent/BR0213716B1/en not_active IP Right Cessation
- 2002-10-30 AT AT02778982T patent/ATE417952T1/en not_active IP Right Cessation
- 2002-10-30 WO PCT/AT2002/000306 patent/WO2003038164A2/en active Application Filing
- 2002-10-30 JP JP2003540422A patent/JP2005507035A/en not_active Ceased
-
2004
- 2004-04-22 US US10/832,693 patent/US20050022310A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531442A (en) * | 1967-03-02 | 1970-09-29 | Lubrizol Corp | Alpha-sulfo-n,n'-alkylidene bis-amide polymers |
US4068068A (en) * | 1975-05-05 | 1978-01-10 | Hoechst Aktiengesellschaft | Process for the manufacture of water-absorbing cellulose ethers |
US4336023A (en) * | 1980-12-30 | 1982-06-22 | Rohm And Haas Company | Formaldehyde-free durable press finish fabrics |
US5310424A (en) * | 1991-10-21 | 1994-05-10 | Courtaulds Plc | Process for reducing the fibrillation tendency of solvent-spun cellulose fibre |
US5310424B1 (en) * | 1991-10-21 | 1998-04-07 | Courtaulds Plc | Process for reducing the fibrillation tendency of solvent-spun cellulose fibre |
US6241933B1 (en) * | 1997-10-15 | 2001-06-05 | Lenzing Aktiengesellschaft | Process for the treatment of cellulosic moulded bodies |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10995429B2 (en) * | 2016-02-11 | 2021-05-04 | Deutsche Institute Furtextil-Und Faserforschung Denkendorf | Method for producing carbon fibers from cellulose fibers treated with sulfonic acid salts |
US20180098099A1 (en) * | 2016-09-30 | 2018-04-05 | Disney Enterprises, Inc. | Real-time data updates from a run down system for a video broadcast |
Also Published As
Publication number | Publication date |
---|---|
PT1440190E (en) | 2009-03-20 |
ATE417952T1 (en) | 2009-01-15 |
EP1440190B1 (en) | 2008-12-17 |
TR200400926T2 (en) | 2004-12-21 |
JP2005507035A (en) | 2005-03-10 |
WO2003038164A2 (en) | 2003-05-08 |
ES2319623T3 (en) | 2009-05-11 |
CN1270004C (en) | 2006-08-16 |
BR0213716B1 (en) | 2012-10-02 |
DE50213134D1 (en) | 2009-01-29 |
TW200300186A (en) | 2003-05-16 |
KR20050042027A (en) | 2005-05-04 |
ATA17312001A (en) | 2005-10-15 |
BR0213716A (en) | 2005-01-04 |
KR100927184B1 (en) | 2009-11-18 |
EP1440190A2 (en) | 2004-07-28 |
AT413824B (en) | 2006-06-15 |
WO2003038164A3 (en) | 2003-09-12 |
AU2002342379A1 (en) | 2003-05-12 |
CN1578854A (en) | 2005-02-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0538977B1 (en) | Treatment of cellulosic fibres to reduce their fibrillation tendency | |
JP3336012B2 (en) | Fiber processing | |
US6241933B1 (en) | Process for the treatment of cellulosic moulded bodies | |
KR101548762B1 (en) | Antistatic acrylic fiber and method for manufacturing the same | |
SK112696A3 (en) | Fibre treatment | |
US5837184A (en) | Process for the production of cellulose fibres having a reduced tendency to fibrillation | |
EP3899113B1 (en) | Process for the treatment of lyocell fibres | |
AU721876B2 (en) | Process for treatment of cellulose fibres and of assemblies made from these fibres | |
WO2003040460A1 (en) | Method for flameproofing cellulose fibers | |
US20050022310A1 (en) | Process for treating solvent-spun, cellulosic fibres | |
DE102007014272A1 (en) | Process for the flameproofing of cotton | |
EP3775360B1 (en) | A process for preparing cationic regenerated cellulosic fibers | |
CA2202141A1 (en) | Cellulose fibre | |
AT2527U2 (en) | METHOD FOR TREATING CELLULOSIC MOLDED BODIES |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: LENZING AKTIENGESELLSCHRAFT, AUSTRIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:RENFREW, ANDREW HUNTER MORRIS;REEL/FRAME:015856/0405 Effective date: 20040923 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |