TW200530438A - Process for treating solvent-spun, cellulosic fibres - Google Patents

Abstract

The invention relates to a process for treating solvent-spun cellulosic fibres, wherein the fibres are contacted with a textile auxiliary agent. The process according to the invention is characterized in that a compound of general formula I, or a salt thereof is used as the textile auxiliary agent, wherein X=R1, R2 or R3, with R1=, wherein A=H, -COOH, -CONR4R5, alkyl, aralkyl, optionally substituted, or halogen; R4, R5=independently of each other, H, or alkyl, optionally substituted; n=0, 1 or 2; R2=, wherein B=H or alkyl; C=H or -SO3H; D=an activated alkene group, an SO2CH2CH2R6 group or an NHCOCHR7CH2R8 group; R6=R8=Cl, Br, -OSO3H, -SSO3H, -OPO3H2, 3-carboxypyridine or -OCOCH3; R7=H, Cl or Br; R3=a quaternary ammonium of formula -N+R9R10R11 or optionally a cyclic ammonium, wherein R9, R10, R11=independently of each other, a branched alkyl or an n-alkyl, wherein, if R9, R10 and R11 are n-alkyl, at least one of R9, R10 and R11 is -CH3; and Y=independently of X, a cellulose reactive group, in particular R1, R2 or R3.

Description

200530438 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for treating cellulose fibers, in which the fibers are brought into contact with a textile auxiliary to impart improved properties to the fibers. [Prior art] Regarding the alternative method of the fiber slime method, in recent years ϋ many methods have been described in which cellulose is dissolved in a combination of an organic solvent, an organic solvent and an inorganic salt or a saline solution without forming a derivative. The cellulose fibers made from this solution are "solvent-spun" fibers and have been included in the general name Lyocell by BISFA (International Organization for Standardization of Artificial Fibers). Regarding Lyocell, BISFA defines cellulosic fibers made by spinning in organic solvents. Regarding "organic solvents", BISFA understands the mixture of organic chemicals and water. It is assumed that "solvent spinning" means dissolving and spinning without meaning. However, so far, only one method of manufacturing lyocell fiber has reached the industrial scale. In this method, a tertiary amine oxide, particularly N-methylmorpholine-N-oxide (NMMO), is used as a solvent. This method has been described in, for example, U S-A 4, 2 4 6, 2 21, and can provide a distinction between high tensile strength, high wet modulus, and high winding strength. However, the applicability of textile fibers, such as spun fiber fabrics, is made from the above-mentioned fibers, which are greatly limited by the significant tendency of those fibers to fibrillate when wet. The fibril formation process indicates that the fiber collapses in the longitudinal direction when the fiber is under mechanical stress in a wet state, and thus the fiber exhibits a hairy, fur-covered appearance. When washed several times, dyed fabrics made from those fabrics -6- 200530438 (2) will lose a lot of color intensity. In addition, scrubbing and wrinkling will cause sharp breaks in the edges. Xian believes that the reason for the formation of fibrils is that the fibers contain filaments aligned in the direction of the fibers, and there is only a small amount of cross-linking among them. Many publications specifically discuss the possibility of treating the fabric with a substance having a cross-linking effect of cellulose to reduce the tendency of fibrillation. WO 92/0 7 1 24 discloses a method for producing a fiber that is newly spun, that is, dries, is dried, and the fiber has a tendency to reduce fibrillation. As for the polymer, mention may be made of polymers containing imidazole and acridine groups. In addition, an emulsifiable polymer such as ethylene or polyvinyl acetate may be used for further processing, or it may be crosslinked with glyoxal. In 1993, S. Moretimer gave a lecture at the CELLUCON conference in Lund, Sweden, mentioning the tendency of fibrillation due to stretching. WO 94/09 1 9 1 and WO 9 5/2 8 5 1 6 describe the φ method originally mentioned, in which a solution-spun fiber is contacted with a textile auxiliary to reduce the tendency of fibrillation. According to EP-A 0 5 3 8 97 7, the fibers are treated in an alkaline environment with an aqueous system. The fibers may be freshly woven or already dried. The aqueous system includes 2 to 6 functional groups that react with cellulose. Of chemical reagents. Derivatives of cyanuric chloride, particularly substituted dichlorotriazines, are referred to as, for example, suitable substances. W0 94/24343 describes a method for producing cellulose fibers with a reduced tendency to fibrillation, in which a cellulose solution is spun into fibers in a tertiary amine oxide-3-200530438 (3) dimension and the newly spun fibers are made with A spinning aid having at least two reactive groups is contacted and washed with a buffer solution, wherein glyoxal is not used as the textile aid. According to previously known methods, it is best to contact the newly spun fibers with a spinning aid in an alkaline environment. For example, from WO 97/49 8 5 6, Australian New No. 2527, and WO 99/1195 5 5 other methods for processing Lyocell cellulose fibers are known. B However, the methods proposed by the prior art for processing Lyocell-based cellulose fibers have many disadvantages: for example, the manufacturing processes of many textile auxiliaries so far have been too long and expensive. As for other textile auxiliaries, they may be found to hydrolyze in the alkaline environment required to react with cellulose. As a result, a loss due to hydrolysis occurs. Furthermore, many of the proposed textile auxiliaries are not sufficiently soluble in the necessary alkaline environment and can be used in the form of dispersions. This will lead to irregular processing effects. Finally, it must be mentioned that the use of some conventional textile auxiliaries becomes difficult because of their toxicity. The object of the present invention is to provide a method for processing lyocell fiber, which can be realized in a simple manner and leads to an efficient improvement of the fiber properties, especially the tendency of fibrillation. [Summary of the Invention] The method for treating a lyocell fiber according to the present invention, wherein the fiber is brought into contact with a textile auxiliary, and is characterized by a compound represented by the following general formula I: 8- (i) 200530438 (4) 〇

N ^ NH

People N and X or their salts are used as textile auxiliaries, where X = R !, R2 or R3, and

Ri =

-N

/ = \ / A n

In the formula, A = H, -C Ο Ο H, -C Ο NR 4 R 5, the base, if necessary, substituted aromatic base 'or halogen; R4' Rs = each independently, Η or as needed Substituted alkanes

C

D in the formula: B = fluorene or yuan; C = fluorene or -S03H; D = activated alkenyl group, S02CH2CH2R6 group or NHCOCHR7CH2R8 group; R6 = R8 = Cl, Br, -0SO3H, -SS03H, -〇P03H2, 3-carboxypyridine or -〇coch3; 200530438 (5) R7 = hydrazone, Cl or Br; R3 = tetravalent ammonium represented by formula -N + P ^ R ^ Rh or cyclic ammonium as required , Where R9, Rio, Rh = each independently branched alkyl or n-alkyl, wherein if R9, R1G and Rh are n-alkyl, at least one of R9, 111 () and Rn is -CH3; and Y = Regardless of X, cellulose-reactive groups, especially R1, R2, or ruler 3. Surprisingly, it has been found that the textile auxiliaries used according to the invention can be purchased at a lower cost and can improve the degree of improvement in the properties of the treated fibers to, for example, substances known from EP-A 0 5 3 8 977 , Its manufacturing is laborious, and it performs equally well or to a higher degree. Among the textile auxiliaries used according to the present invention, it is more desirable to treat the fibers with a compound that does not contain A OX. In addition to the improved degree of fiber properties according to the present invention, these compounds also provide the added benefit of being halogen-free. Y is preferably a cellulose-reactive group that does not contain ΑOX ("organic halogen that can be absorbed"). More preferably, A represents a COOH or CONH2 group. In a preferred embodiment of the present invention, A is in the meta position. According to another preferred embodiment, B is a hydrogen atom. The activated alkenyl group is preferably a 502 (:} 1 = 0112 or NHCOCR7 = CH2 group. R7 is more preferably hydrogen. R6 is more preferably an OS03H group. A preferred embodiment of the present invention is characterized in that R3 is 1,4-Diazabicyclo-10-200530438 (6) [2,2,2] Octane (DABCO), N-methylmorpholine, N.methylpyrrolidine, trimethylamine or dimethyl Ethylamine. Particularly preferred textile aids are compounds represented by the following formula II.

(Π)

COOH is particularly desirable to use a compound of formula III as a textile auxiliary.

In another preferred embodiment, a compound of the following formula IV is used as a textile auxiliary ("hydroxy-XLC").

H〇3S〇hbCH2C〇2S · χ · (IV) N ^ NH person N person N person J Η Η

S02CH2CH2〇S〇bH This textile auxiliary and its manufacturing method have been described by, for example, A. Η. M. Renfrew and D.A.S. Phillips (Coloring Technology, 2003). Relative to known, structurally related textile auxiliaries 4,6-bis (p-β-sulfate ethylsulfonyl) anilino-2-chloro-], 3,5 · triazine ("XLC") -11-200530438 (7) Compound IV has better water solubility in both neutral and alkaline environments. Thereby, more uniform application to fibers and textile aggregates can be achieved. The textile auxiliaries used according to the present invention are preferably used in the form of sodium, lithium and / or potassium salts. However, other salts, especially metal salts, can also be used. The textile auxiliary according to the present invention is ideally suitable for the treatment of dried fibers and also for the treatment of textile aggregates or formed bodies containing solution-spun fibers. The fibers may be provided in a dyed or undyed state. However, the method according to the present invention is also applicable to the treatment of fibers provided in a non-dried state. It is desirable to use the method according to the present invention for reducing the tendency of fibrillation. Furthermore, the present invention relates to the use of a compound of the following general formula I as a textile auxiliary for the treatment of cellulose fibers,

(I) wherein X and Y have the meanings as defined above, or a salt thereof. Therefore, the compound of formula (I) is particularly suitable for reducing the tendency of fibrillation. Furthermore, the present invention relates to a melt-spun fiber obtainable by the method of the present invention, and a textile aggregate or formed body containing the melt-spun fiber. -12- 200530438 (8) The compounds used as textile auxiliaries according to the present invention can be prepared by methods known in the art, for example, melamine chloride (see Example 1 and commercially available intermediates (see Implementation Examples 2 and 3) Manufacturing [Embodiment] Example: Example 1: 4-m-carboxypyridine-6- (p-β-sulfate ethylsulfonylρ-symmetric-triazine-2 -oxide ( (Formula 111) The solution of p-aminobenzene-β-sulfate ethyl ether in sodium carbonate was adjusted to a pH of 4 · 5 by sodium carbonate. The solution was filtered and cooled ° C. Dropwise A solution of melamine chloride in acetone (5.7 gt) was added to this solution, the temperature was maintained at 0 to 2 ° C and the pH was maintained at 4 · 5. A white precipitate formed. After a reaction time of about 2 hours The mixture was returned to room temperature and the pH was adjusted to 6.5 with a 2 M sodium carbonate solution and phosphoric acid. The mixture was stirred for another 20 hours Φ off. A portion of the white precipitate (t R 2 · 6) was added at room temperature and p 烟 solution of nicotinic acid in water (0.033 M). The pH was maintained at 4.5 by a 2 M solution. The reaction mixture was stirred for 25 hours to form a pale yellow color. Float. The suspension was filtered, washed with acetone and dried at 401. HP LC showed mass spectrometry at tR 0.80 at m / z 496 (MH) · (〗 00) and 452 (Μ · Η- ( 6) where ions are generated. There is a strong dimer at m / z 993 (2M-H)-(70). In the art 4) or ί.) Aniline in water to 0E 4 0ml ί at 3.5 , The anti-buffer was then filtered to 4.5 sodium carbonate, so that the precipitate has a peak. Co2) · place also -13- 200530438 (9) Example 2: 6-trimethylammonium 4-p-sulfate ethyl ether Preparation of propyl-symmetric-trifluorene-2-oxide With stirring, trimethylamine hydrochloride (7.0 g; concentration 98%; 0.07 2 m ο 1) was added to water (5 0 m 1) in 6-p-sulfate ethosyl-symmetric-dichlorotriazine (17 · 3 g; concentration 5 9 · 6 ° / 〇; 0 · 0 3 m ο 1). Add NaOH solution (2M) to reach pH 7.5, and heat the suspension to 30 ° C. The reaction heat caused the temperature to rise to 40 ° C, and 2 M hydrogen ρ sodium oxide was added to keep the pH 在 between 7.0 and 8.0. After 30 minutes, the suspension was dissolved, and the resulting solution was filtered and left to stand. The resulting white precipitate was collected by filtration, filtered in acetone (150 ml), then filtered and dried in a 55 t oven to give the product as a white solid (9.1 g). Mass spectrometry generates molecular ions at m / z 324 (M-H) ·. Example 3: Preparation of 6- (1,4-diazabicyclo [2,2,2] octylammonium-4-p-sulfate ethylsulfo-symmetric-triazine-2-oxide In the case of 1,4-diazabicyclo [2,2,2] octane (8.2 g; concentration 98%; 0.072 mol) is divided into several portions and added to water (50 ml) at 5 to 10 ° C 6-p-sulfate ethynyl-symmetric-dichlorotriazine (17 · 3 g; concentration 5 9 · 6%; 0 · 0 3 m ο I). Initially, 2 M hydrochloric acid solution was added To achieve the purpose of adjusting the pH7.5 to 7.5, once the reaction started (the pH decreased), use 2M sodium hydroxide to keep the pH 値 at 7.0 to 8. 0. A pale yellow solution was formed, and the reaction mixture was allowed to slow after overnight The ground temperature was warmed to room temperature. The reaction solution (about 100 ml) was poured into ethanol (300 ml) to produce a white precipitate, and the white precipitate-14-200530438 (10) precipitate was separated by filtration and used Washed with acetone (150 ml) and dried in an oven at 55 ° C to give the product (10.8 g) as a white solid. Mass spectrum at m / z 3 77 (MH) · (100) and 265 (MH-C6H12N2)-Ions are generated at (25) at m / z 777 (2M-H + Na) _ (4) and 7 55 (2M-H)-also has a dimer. Example 4: 4,6-bis (p-β-sulfate ethylamido) aniline-1,3,5-trigazine-2 (1Η ) -Ketone-"Hydroxy-XLC" 30.36 g of melamine chloride in 300 ml of acetone, followed by 300 ml of deionized water and phosphate buffer (pH 7) were added to the 11 test beaker. By the action of stirring 2M Na2CO3 was added dropwise to maintain the pH 在 between pH 6 and 7. The reaction mixture was stabilized at 25 ° C. The reaction was completed after nearly 1 hour and a clear solution with a green-yellow luster was formed. Add 9 3.7 6 g of p-aminophenyl-β-acetic acid ethyl acetate to a 400 m 1 test beaker and add deionized water to 300 m. Add 2 M Na2C03 dropwise to adjust the pH to 4 and filter the solution. The filtrate thus prepared was slowly added to the previously prepared dichlorohydroxytriazine solution, and the pH was adjusted to 4.5 with 2M Na2C03. The reaction mixture was adjusted to 30 ° C and stirred separately until p Rhenium no longer drops and no correction is needed. The reaction mixture is allowed to stir overnight. The "industrial methanol denatured alcohol (industria 1 m e t h y 1 a t e d s p i r it) "was added to the reaction mixture, stirred for 30 min and then filtered off. The filter residue was rinsed with acetone and filtered again, followed by drying in an oven at 40 ° C. Yield: 1 0 3.6 6 g (8 0 · 9%). HPLC showed that the product had 100% organic purity. -15- 200530438 (11) Example 5 ······························································································································· Using hydroxy-XLC as the crosslinking agent initially at room temperature (25 ° C) based on atro fibre and a bath ratio of 1 ·· 10 (Liquor ratio) Wet (undried) 1.3 dtex Lyocell fibers in a bath containing 45 g / 1 hydroxyl-XLC and 25 g / 1 NaOH for 4 minutes at 3 bar in thin It was extruded in silk and then steamed with saturated steam at 100 ° C for 4 minutes; after washing and drying, the total wet abrasion resistance was 7 1 4 rpm. Example 6: Hydroxyl-XLC was used as a cross-linking agent. Initially at 50 ° C, based on atropine fiber, a wet 1.3 dtex Lyo cell fiber containing 36 g / 1 hydroxyl-XLC and 25 g / 1 NaOH in a bath for 2 minutes, extruded in a thin silk at 3 bar and then steamed with saturated steam at 100 ° C for 4 minutes; after rinsing and drying, total The wet abrasion resistance is 9 71 rpm. Example 7: Hydroxyl-XLC was used as a cross-linking agent. At 80 ° C, based on atropine fiber, a wet 1.3 dtex Lyocell fiber was immersed in a bath ratio of 1: 1 to 60. g / l hydroxy-XLC and 100 g / 1 Na2S04 in a bath for 10 minutes. After that, it was cooled to 50 ° C, NaOH was added to a final concentration of 22 g / 1, and another 2 minute incubation was performed at 50 ° C. After being extruded in a chiffon at 3 bar, the fibers were rinsed without a thermal steaming process. After drying, the total wet abrasion resistance was 42 1 rpm. -16- 200530438 (12) Example 8: Dried Lyocell fiber was immersed at 10C and 0 to 10g /: l hydroxyl-XLC in the ratio of 1: 1 to 10 by using the base-XLC as the parent crosslinker at 6CTC. 30 minutes in the bath. The pH was adjusted to 1 2.0 by the addition of NaOH, and the fibers were kept in the bath for another 30 minutes with stirring. After rinsing, test for wet abrasion resistance. N a 2 S Ο 4 Then, wash and dry at 60 ° C. Results: Based on atropine fiber, the demand for hydroxyl-XLC in% is 0 revolutions / dtex 42 89 198 3 52 4.17 395 479 .67 6 1] 10 725 The results are shown in 4 pull Q Λ ^ ττ ^ π +, soil. The protection of fibrillation at a temperature of 30 ° C within the PΗ range of 9 · 2 teaches ^ ^ ^ M $ 彳 worry about the stability. Thus, the compound of formula IV has significantly better color resistance to acid 忤. $ ΡΗ 値 and high temperature than NHDT. Examples are hydroxy 6 -bisnicotine 醯 chloride · 1,3,5 -trifluorene (, antagonistic compound: 〇 (Formula Π) -17- 200530438 (13) As a cross-linking agent, a bath of 100 ml of H20, 0.25 g of cross-linking agent and 5.0 g of Na2S04 of dried Lyocell fiber was heated from 40 ° C to 30 ° C, and then maintained at 70 ° C. 30 minutes at ° C. Immediately, the pH was maintained at pH 1 1 due to the result of the automatic metering of Na2S03. After rinsing and drying, test for wet abrasion. The total wet abrasion resistance of the untreated fibers was 47 rpm. The fibers treated with the cross-linking agent reached a wet abrasion resistance of 3 1 1 rpm. The advantages of the compound of formula Π over NHDT (sodium hydroxydichlorotriazine, for example £ 卩 -A 0 5 3 8 977) are that the cross-linking agent according to the invention is a compound which does not contain A OX and is required for the cross-linking reaction The pH is lower than that of NHDT, which is why it can be assumed that the fiber is crosslinked in a lower swelling state and then fixed. In order to evaluate the pH and temperature stability of the protective effect against antigenic fibrillation, the dried fibers according to Example 丨 were treated with 5% by weight of a crosslinking agent in the bath at 50 ° C, 6 ° C, 0, 7 ° C, 80 ° C, 90 ° C, 100 ° C,]] 0 φ ° C, 120 ° C, and 3 °. At a temperature of :, the bath was maintained in a buffer solution of pH 4, pH 7, and pH 9.2 for 30 minutes, and the wet abrasion resistance was measured before and after the treatment. -18-

Claims (1)

200530438 十 X. Scope of patent application 1 · A method for treating soluble spun cellulose fiber, wherein the fiber is contacted with a textile auxiliary, which is characterized by a compound of the following general formula I 〇 ® Or its salts as textile auxiliaries, where X = Ri, R2 or R3, and Ri η A where A = Η, -COOH, -CONR4R5, alkyl, optionally substituted aralkyl, or halogen; R4, R5-each independently Η or optionally substituted too complete 棊; n = 〇, 1 or 2; D where B = B or alkyl; C = Η or -S Ο 3 Η; D = activated alkenyl, S02CH2CH2R6 group or-19- 200530438 (2) NHC〇CHR7CH2R8 group; R 6 = R 8 = Cl, Br, -OSO3H, -SSO3H, -OPO3H2 '3-carboxypyridine or -〇coch3; R7 = H, Cl or Br; R3 = tetravalent ammonium or apparent as shown by the formula -N + RgR ^ Ru In the case, it is a cyclic ammonium, where = each independently is a branched alkyl or n-alkyl group, where if R9, R] 0 and Rh are n-alkyl groups, at least one of R9, RI0 and Rh is- CH3; and Y = independently of X are cellulose reactive groups, especially R !, R2 or R3. 2. The method according to item 1 of the patent application, wherein Y is a cellulose reactive group without AOX. 3. The method as claimed in item 1 or 2 of the patent application, where A is a COOH or CONH2 group. 4 · The method according to item 1 of the patent application scope, where A is in the middle position. 5 · The method according to item 1 of the patent application, wherein B is a hydrogen atom. 6 · The method of claim 1 in which the activated alkenyl group is a S02CH = CH2 or NHCOCR7 = CH2 group. 7) The method of claim 1 in which R7 is hydrogen. 8. The method of claim 1 in the scope of patent application, wherein R6 is an OS03H group. -20- 200530438 (3) 9. The method according to item 1 of the scope of patent application, wherein r3 is 丨, ^ diazabicyclo [2,2,2] octane (daBCO), N-methylmorpholine, formaldehyde Pyrrolidine, trimethylamine or dimethylethylamine. 1 ° * The method according to item 1 of the patent application scope, wherein the compound represented by the following formula II is used 11. The method according to the scope of patent application, wherein a compound represented by the following formula III is used 12. The method according to item 1 of the scope of patent application, wherein the compound (IV) represented by the following formula IV is used: H ^ SO ^ CHzCOzS ^ r ^ νΛνη ^^ S〇2CH2GH2〇SCbH Η Η -21-200530438 (4) • 13. The method according to item 1 of the scope of patent application, wherein the textile auxiliary is used in the form of lithium, sodium and / or potassium salt. 14. The method of claim 1 in which the fiber is provided in a state that it has not been dried. 15. The method according to item 1 of the patent application range, wherein the fiber is provided in a dry state. p 16. The method according to item 1 of the patent application, wherein the fiber is provided in the form of a textile aggregate or a shaped body. 1 7 The method according to item 1 of the scope of patent application, wherein the treatment is used to reduce the tendency of fibrillation. 1 8-Use of a compound represented by the general formula I, in which X and Y have the meanings specified in item 1 of the scope of patent application, or the use of a salt thereof ', which is used for treating lyocell fiber Textile additives. 19. The use of item 18 in the scope of patent application is for reducing the tendency of fibrillation of lysed cellulose fibers. 20 · —a type of solvent-spun cellulose fiber obtained by a method according to any one of claims 1 to 17 of the scope of patent application. 2 1 · ~ A kind of textile aggregate or formed body containing lyocell cellulose fiber ′ It is obtained according to the method in the 16th scope of the patent application. • 22-200530438 Qiming said that the single abbreviation symbol table is the definitive figure designation table of the original drawing table: the case drawing, the table, and the declaring one or two fingers / tv χίν No. 8. If there is a chemical formula in this case, please Reveal the chemical formula that best characterizes the invention: Formula I