NO125778B - - Google Patents
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- NO125778B NO125778B NO684969A NO496968A NO125778B NO 125778 B NO125778 B NO 125778B NO 684969 A NO684969 A NO 684969A NO 496968 A NO496968 A NO 496968A NO 125778 B NO125778 B NO 125778B
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- cellulose
- aminoethyl
- viscose
- filaments
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 229920002678 cellulose Polymers 0.000 claims description 50
- 239000001913 cellulose Substances 0.000 claims description 42
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 29
- 229920000297 Rayon Polymers 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004627 regenerated cellulose Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 description 45
- 239000000243 solution Substances 0.000 description 27
- 235000011121 sodium hydroxide Nutrition 0.000 description 20
- 239000000835 fiber Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 4
- 239000000980 acid dye Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 4
- 239000012991 xanthate Substances 0.000 description 4
- 239000000982 direct dye Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- WSYUEVRAMDSJKL-UHFFFAOYSA-N ethanolamine-o-sulfate Chemical compound NCCOS(O)(=O)=O WSYUEVRAMDSJKL-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009967 direct dyeing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical class NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/22—Cellulose xanthate
- C08L1/24—Viscose
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Description
Fremgangsmåte til fremstilling av regenererte Process for the production of regenerated
cellulosefilamenter med forbedret fargbarhet. cellulose filaments with improved dyeability.
Foreliggende oppfinnelse vedrører en fremgangsmåte til fremstilling av regenererte cellulosefilamenter som har stor affinitet for direkte fargestoffer og syrefargestoffer. The present invention relates to a method for producing regenerated cellulose filaments which have a high affinity for direct dyes and acid dyes.
Det er allerede foreslått (US patent nr. 3 305 377) å frem-stille regenererte cellulosefilamenter som kan farges med syrefargestoffer, ved å inkorporere en amino-substituert cellulose i celluloee-gruhnmassen av filamentene. Fremgangsmåten omfatter dannelse av xanthatet av en aminoetylcellulose inneholdende mellom 1.2 og 1.6 % amino-nitrogen, oppløsning av xanthatet i NaOH-oppløsning for dannelse av en baseomdannet viskose, blanding av denne viskose med en normal viskose og spinning av blandingen for oppnåelse av filamenter av regenerert cellulose forsynt med en tilstrekkelig basisitet til å gjøre filamentene fargbare med syrefargestoffer eller mer fargbare med direkte fargestoffer. It has already been proposed (US patent no. 3,305,377) to produce regenerated cellulose filaments which can be dyed with acid dyes, by incorporating an amino-substituted cellulose into the cellulose groundmass of the filaments. The process comprises forming the xanthate of an aminoethylcellulose containing between 1.2 and 1.6% amino nitrogen, dissolving the xanthate in NaOH solution to form a base-converted viscose, mixing this viscose with a normal viscose and spinning the mixture to obtain filaments of regenerated cellulose provided with a sufficient basicity to make the filaments dyeable with acid dyes or more dyeable with direct dyes.
Forsøk på å sulfidere en blanding av cellulose og en amino-substituert cellulose for i et trinn å oppnå en blandet viskose som er egnet for spinning, kullkastes på grunn av de forskjellige sulfi-deringshastigheter for de forskjellige cellulosefibre. Det har hittil vært nødvendig å fullføre sulfideringen av hver av cellulosetypene separat og deretter kombinere xanthatene for å oppnå den modifiserte viskose. Dette har komplisert prosessen såpass at mer fargbare fibre fremdeles ikke lages i særlig grad. Attempts to sulphide a mixture of cellulose and an amino-substituted cellulose in order to obtain in one step a mixed viscose suitable for spinning, are thrown away because of the different sulphidation rates of the different cellulose fibres. It has hitherto been necessary to complete the sulphidation of each of the cellulose types separately and then combine the xanthates to obtain the modified viscose. This has complicated the process to such an extent that more dyeable fibers are still not produced to any great extent.
Det er nå funnet en enklere og billigere prosess for fremstilling av slike filamenter. A simpler and cheaper process for the production of such filaments has now been found.
Ifølge foreliggende oppfinnelse er det således tilveiebragt en fremgangsmåte til fremstilling av regenererte cellulosefilamenter med forbedret fargbarhet, omfattende dannelse av en oppløsning av en aminoetylcellulose, blanding av denne med en viskoseoppløsning og eke-trudering av de kombinerte oppløsninger for dannelse av regenererte cellulosefilamenter inneholdende en aminoetylcellulose, og denne fremgangsmåte er kjennetegnet ved at det anvendes en aminoetylcellulose med et nitrogeninnhold på minst 2 vektprosent og ved at aminoetylcellulosen ved tilsetningen til viskosen er oppløst i vann eller i en vandig natriumhydroksydoppløsning. According to the present invention, there is thus provided a method for producing regenerated cellulose filaments with improved dyeability, comprising forming a solution of an aminoethyl cellulose, mixing this with a viscose solution and extruding the combined solutions to form regenerated cellulose filaments containing an aminoethyl cellulose, and this method is characterized by the fact that an aminoethyl cellulose with a nitrogen content of at least 2% by weight is used and that the aminoethyl cellulose is dissolved in water or in an aqueous sodium hydroxide solution when added to the viscose.
Oppløseligheten for aminoetylcellulose i vandige media er av-hengig av aminoinnholdet. Under omtrent 2.0 % nitrogeninnhold, er cellulosene i seg selv ikke oppløselige i verken vandig natriumhydroksyd eller vann, men må modifiseres kjemisk, f.eks. ved omdannelse til xanthat for å bli oppløselige. Ved et nitrogeninnhold på ca. 2.0 % er aminoetylcellulosene vesentlig oppløselige i vandig kaustisk sodaopp-løsning inneholdende 10 vektprosent kaustisk soda. Oppløsningen er kan-hende ikke helt klar ved det laveste substitusjonsnivå, men de uopp-løste partiklene er gelatinøse og gir bare en svak uklarhet eller opalisering til oppløsningen. Ettersom nitrogeninnholdet økes ytterligere kan konsentrasjonen av natriumhydroksyd i oppløsningsmidlet minskes inntil aminoetylcellulosene til slutt, ved omtrent 4 % nitrogeninnhold eller over dette, er oppløselige i vann. Ved å velge de aminoetylcellulosene1 som er oppløselige i vandig kaustisk soda eller vann og derved eliminere de som krever sufidering for oppnåelse av slike oppløselig-heter, gjøres fremgangsmåten til fremstilling av mer fargbare filamenter enklere og billigere. Det er foretrukket at. nitrogeninnholdet i aminoetylcellulosen er fra 2.7 til 3.3 vektprosent slik at eteren er opp-løselig i vandig NaOH og uoppløselig i vann. The solubility of aminoethyl cellulose in aqueous media depends on the amino content. Below about 2.0% nitrogen content, the celluloses themselves are not soluble in either aqueous sodium hydroxide or water, but must be chemically modified, e.g. by conversion to xanthate to become soluble. At a nitrogen content of approx. 2.0%, the aminoethylcelluloses are substantially soluble in aqueous caustic soda solution containing 10% by weight of caustic soda. The solution may not be completely clear at the lowest substitution level, but the undissolved particles are gelatinous and give only a slight cloudiness or opalescence to the solution. As the nitrogen content is increased further, the concentration of sodium hydroxide in the solvent can be reduced until finally, at about 4% nitrogen content or above, the aminoethyl celluloses are soluble in water. By selecting those aminoethylcelluloses1 which are soluble in aqueous caustic soda or water and thereby eliminating those which require suffidation to achieve such solubilities, the process for producing more dyeable filaments is made simpler and cheaper. It is preferred that. the nitrogen content in the aminoethyl cellulose is from 2.7 to 3.3 percent by weight so that the ether is soluble in aqueous NaOH and insoluble in water.
De vannopploselige aminoetrene inneholdende 4% eller mer av nitrogen, er tilbøyelig til å utlutes fra de regenererte cellulose-filamentene hvori de er inkorporert, særlig når filamentene nedsen-kes i varme oppløsninger av fortynnet syre av den type som anvendes i våtfarveprosesser. Denne ulempe kan imidlertid overkommes ved å strekke de nylig koagulerte filamentene i en grad av minst 60$ av deres opprinnelige lengde, eller ved å kryssbinde filamentene med hvilken som helst av de velkjente materialer for kryssbinding av cellulose, og spesielt de permanent opploselige kryssbindemidler som er angitt i US patent nr. 3 O38 777 (britisk patent nr. 95O O73). The water-soluble amino ethers containing 4% or more of nitrogen tend to leach from the regenerated cellulose filaments in which they are incorporated, particularly when the filaments are immersed in hot solutions of dilute acid of the type used in wet dyeing processes. However, this drawback can be overcome by stretching the newly coagulated filaments to an extent of at least 60% of their original length, or by cross-linking the filaments with any of the well-known materials for cross-linking cellulose, and in particular the permanently soluble cross-linking agents which are disclosed in US Patent No. 3038777 (British Patent No. 950073).
Ved fremstilling av aminoetylcellulose ved omsetning av cellulose med aminoetylhydrogensulfat og natriumhydroksyd, er det økonomisk gjennomforlig .å tilveiebringe et nitrogeninnhold på mer enn ca. 2% i et trinn, mens cellulosen beskyttes mot overdreven ned-brytning, og det er sansyneligvis dette faktum som hittil har ledet fagmannen på dette området til å foreslå sulfidering av aminoetylcelluloser for å gjore dem opploselige og forenelige med viskoser. Det er nå funnet at det er mulig å oke nitrogeninnholdet til -godt over ovenfor nevnte prosentmengde ved å gjenta foretringsreaksjonen, dvs. å omsette aminoetylcellulosen med ytterligere mengder aminoetyl-hydrogensulf at og natriumhydroksyd, og det er således oppnådd substituerte celluloser, som alle lar seg oppløse i vandig natriumhydroksyd og hvorav noen opploses i vann. In the production of aminoethyl cellulose by reacting cellulose with aminoethyl hydrogen sulphate and sodium hydroxide, it is economically feasible to provide a nitrogen content of more than approx. 2% in one step, while protecting the cellulose from excessive degradation, and it is probably this fact that has hitherto led those skilled in the art to suggest sulphiding aminoethyl celluloses to render them soluble and compatible with viscoses. It has now been found that it is possible to increase the nitrogen content to well above the above-mentioned percentage by repeating the etherification reaction, i.e. reacting the aminoethyl cellulose with further amounts of aminoethyl hydrogen sulphate and sodium hydroxide, and thus substituted celluloses have been obtained, all of which can dissolve in aqueous sodium hydroxide and some of which dissolve in water.
De opaliserende oppløsninger av noen aminoetylcelluloser dannet i vandig natriumhydroksyd eller vann, kan tilsettes til viskose uten i vesentlig grad å påvirke filtrerings- og spinningsegen-skapene til viskosen, spesielt hvis blandingen foretas noen timer for den modifiserte viskosen ekstruderes. Det antaes av de gelati-nose partiklene som forårsaker opaliseringen av de vandige oppløs-ningene, er svellede cellulosesegmenter eller'partikler i en til-stand som er egnet for hurtig sulfidering og derfor opplosning, ved omsetning med overskudd karbondisulfid i viskosen eller ved trans-sulfidering ved kontakt med viskosen. The opalescent solutions of some aminoethyl celluloses formed in aqueous sodium hydroxide or water can be added to viscose without significantly affecting the filtering and spinning properties of the viscose, especially if the mixing is carried out a few hours before the modified viscose is extruded. It is assumed that the gelatinous particles causing the opalization of the aqueous solutions are swollen cellulose segments or particles in a state suitable for rapid sulphidation and therefore dissolution, by reaction with excess carbon disulphide in the viscose or by trans- sulphidation on contact with the viscose.
Kriteriet for at aminoetylcellulosen skal være tilstrekkelig opploselig i dens vandige natriumhydroksyd-opplosningsmiddel, bestemmes ikke ut fra oppløsningens opalisering, men bestemmes ved å blande oppløsningen med en viskose av den nødvendige sammensetning og i den mengde som skal til for fremstilling, og ved å måle filtrer-ingsforlopet til viskosen både for og en viss tid etter blandingen, f.eks. opp til 12 timer. Hvis disse to filtreringsforlop ikke er fullstendig forskjellige, vil det uoppløselige stoff som forårsaker opalisering av oppløsningen ikke gjore spinningen særlig vanskeligere, men hvis den modifiserte viskosen er betydelig vanskeligere å filtrere, bor en aminoetylcellulose med hoyere nitrogeninnhold anvendes istedenfor den som benyttes i undersøkelsen. The criterion for the aminoethyl cellulose to be sufficiently soluble in its aqueous sodium hydroxide solvent is not determined from the opalization of the solution, but is determined by mixing the solution with a viscose of the required composition and in the amount required for manufacture, and by measuring filters -ing process of the viscose both before and for a certain time after the mixture, e.g. up to 12 hours. If these two filtration processes are not completely different, the insoluble substance causing opalization of the solution will not make spinning particularly difficult, but if the modified viscose is significantly more difficult to filter, an aminoethyl cellulose with a higher nitrogen content should be used instead of the one used in the investigation.
Ved fremstilling av aminoetylcelluloser ifølge foreliggende oppfinnelse ved adskilte reaksjoner av. cellulosen med suksessive mengder av aminoetylhydrogensulfat og natriumhydroksyd, er det til-rådelig å vaske biprodukt-urenhetene fra de urene aminoetylcelluloser for ytterligere mengde reagenser tilsettes, og dette forbedrer effektiviteten av den påfølgende foretringsreaksjon, men biproduktene fra den sluttlige reaksjon bor forbli i aminoetylcellulosen. Det urene produkt bor, selv om det kan vaskes, ikke oppvarmes e.ller torkes fordi dette kan fore til kryssbinding og uopploseliggjoring. Det sluttlige produkt kan oppløses umiddelbart i det valgte opplosningsmiddel, nemlig vandig natriumhydroksyd eller vann. In the production of aminoethyl celluloses according to the present invention by separate reactions of. the cellulose with successive amounts of aminoethyl hydrogen sulfate and sodium hydroxide, it is advisable to wash the by-product impurities from the impure aminoethyl celluloses before additional amounts of reagents are added, and this improves the efficiency of the subsequent etherification reaction, but the by-products of the final reaction should remain in the aminoethyl cellulose. The impure product, even if it can be washed, should not be heated or dried because this can lead to cross-linking and indissolving. The final product can be dissolved immediately in the chosen solvent, namely aqueous sodium hydroxide or water.
Det er funnet at regenererte cellulosefilamenter fremstilt ved ekstrudering av den modifiserte viskosen og inneholdende minst 0.06$ nitrogen, kan farves i storre grad enn filamenter av umodifi-sert regenerert cellulose, med direkte farvestoffer og at lignende filamenter inneholdende minst 0. 25% nitrogen lett kan farves med syrefarvestoffer i en grad som tilsvarer eller overgår ull. It has been found that regenerated cellulose filaments produced by extrusion of the modified viscose and containing at least 0.06% nitrogen can be dyed to a greater extent than filaments of unmodified regenerated cellulose, with direct dyes and that similar filaments containing at least 0.25% nitrogen can readily dyed with acid dyes to a degree equal to or greater than wool.
Fremgangsmåten ifolge foreliggende oppfinnelse har flere store fordeler. For det forste, fordi de aminoetylcellulosene som inneholder minst 2 vektprosent nitrogen i seg selv er opploselige i viskosen, trenges ingen ekstra mengde karbondisulfid for å gjore aminoetylcellulose/viskose-blandingen homogen. For det annet, opp-løsningen av aminoetylcellulosen i vandig kaustisk soda eller i vann er stabil i motsetning_ til oppløsningene av xanthat-derivater av aminoetylcelluloser inneholdende mindre enn 2% nitrogen; og slike stabile oppløsninger kan derfor lages i betydelige mengder og lagres. De vandige oppløsningene kan innsproytes i viskosen umiddelbart for blandingen ekstruderes ved benyttelse av den teknikk som anvendes for innsprøyting av pigmenter i de såkalte dysefarveprosesser. For det tredje, fordi aminoinnholdet i den substituerte cellulosen er så The method according to the present invention has several major advantages. First, because those aminoethylcelluloses containing at least 2% nitrogen by weight are themselves soluble in the viscose, no additional amount of carbon disulfide is needed to homogenize the aminoethylcellulose/viscose mixture. Second, the solution of the aminoethyl cellulose in aqueous caustic soda or in water is stable in contrast to the solutions of xanthate derivatives of aminoethyl celluloses containing less than 2% nitrogen; and such stable solutions can therefore be made in considerable quantities and stored. The aqueous solutions can be injected into the viscose immediately before the mixture is extruded using the technique used for injecting pigments in the so-called nozzle dyeing processes. Third, because the amino content of the substituted cellulose is so
mye storre enn det som hittil har vært forsokt, er det tilstrekkelig med en mindre mengde av aminoetylcellulosen for å oppnå den nødven-dige forbedring av farvbarheten. much larger than what has been attempted so far, a smaller amount of the aminoethyl cellulose is sufficient to achieve the necessary improvement in dyeability.
Oppfinnelsen illustreres ved følgende eksempler, hvor pro-sentangivelsene er ment som vektprosent. The invention is illustrated by the following examples, where the percentages are meant as percentage by weight.
Eksempel 1 Example 1
Det ble laget en viskose inneholdende 7-95 % cellulose og 5.68 % natriumhydroksyd og denne ble dampet i 40 timer inntil salt-tallet var ca. 6.0. Deretter ble det innsprøytet en oppløsning inneholdende 5.0 % oppløselig aminoetylcellulose og 9.5 % natriumhydroksyd. i en mengde på 143.6 g av oppløsningen per kilo av normal tiskose. Prosentmengden av nitrogen i den faste oppløselige aminoetylcellulose var 3.0 %. A viscose containing 7-95% cellulose and 5.68% sodium hydroxide was made and this was steamed for 40 hours until the salt number was approx. 6.0. A solution containing 5.0% soluble aminoethyl cellulose and 9.5% sodium hydroxide was then injected. in an amount of 143.6 g of the solution per kilogram of normal teacup. The percentage amount of nitrogen in the solid soluble aminoethyl cellulose was 3.0%.
Etter innsprøyting ble materialet spunnet umiddelbart gjen-nom en 300/5 dyse inn i et spinnebad med en spesifikk vekt på 1.25 og temperatur på 42°C inneholdende 9.63 % svovelsyre, 0.99 % sinksulfat og 19.5 % natriumsulfat. Nedsenkingslengden var 68 cm og materialet ble gitt en strekking på 30 %. Det ble deretter behandlet (i hespe-form) med følgende oppløsninger: After injection, the material was spun immediately through a 300/5 nozzle into a spinning bath with a specific gravity of 1.25 and a temperature of 42°C containing 9.63% sulfuric acid, 0.99% zinc sulfate and 19.5% sodium sulfate. The immersion length was 68 cm and the material was stretched by 30%. It was then treated (in hespe form) with the following solutions:
Fibrene ble sentrifugert i 5 minutter og tørket ved 80 C. Etter tørking var nitrogenmengden i den fullstendige tørre fiber 0.2 8 %. Ut-trekkingen av et bad inneholdende farge tc ""fet "Azogeranin" (0.2 g per liter) var 55$ sammenlignet med 5'5$ f°r et normalt garn spunnet under identiske betingelser, uten aminoetylcellulose. The fibers were centrifuged for 5 minutes and dried at 80 C. After drying, the amount of nitrogen in the completely dry fiber was 0.28%. The draw-out of a bath containing dye tc ""fat" "Azogeranin" (0.2 g per liter) was 55$ compared to 5.5$ for a normal yarn spun under identical conditions, without aminoethylcellulose.
Eksempel 2 Example 2
Det ble laget en viskose inneholdende ty. 13% natriumcellu-lose, 6.29$ natriumhydroksyd, og som hadde et salttall på 6.6 og en kulefall-viskositet på 49 sekunder ved en temperatur på 15°C. Til denne viskose ble det ved innsproyting tilsatt 1. 7% aminoetylcellulose, beregnet på cellulosen i viskosen, som en 5- 3% opplosning i 9-5$ kaustisk soda-opplosning. Den faste aminoetylcellulosen, som var laget for innsproytingsopplosningen, inneholdt et gjennomsnitt på 2.9$ nitrogen og inneholdt nitrogen i et område på 2.7 - 3-2$. Viskosen ble spunnet i et bad inneholdende 6.5$ svovelsyre, 1. 3% sinksulfat og 23.0$ natriumsulfat ved 64°C under anvendelse av en 7500 x 4 dyse og en nedsenkning på 68 cm. Nitrogenverdien i pro-duktet etter vasking med oppløsninger som i eksempel 1, var 0.06$. De således fremstilte stapelfibre var et 4 l/2 denier materiale og var meget krympet. Det inneholdt utilstrekkelig aminoetylcellulose for å gjore det vesentlig ull-farvende, men det var tilstrekkelig av dette additiv til å oppnå forbedrede direkte farvingsegenskaper. A viscose containing ty was made. 13% sodium cellulose, 6.29% sodium hydroxide, and which had a salt number of 6.6 and a drop viscosity of 49 seconds at a temperature of 15°C. To this viscose, 1.7% aminoethyl cellulose was added by injection, calculated on the cellulose in the viscose, as a 5-3% solution in 9-5% caustic soda solution. The solid aminoethyl cellulose, which was made for the injection solution, contained an average of 2.9% nitrogen and contained nitrogen in a range of 2.7 - 3-2%. The viscose was spun in a bath containing 6.5% sulfuric acid, 1.3% zinc sulfate and 23.0% sodium sulfate at 64°C using a 7500 x 4 die and an immersion of 68 cm. The nitrogen value in the product after washing with solutions as in example 1 was 0.06$. The staple fibers thus produced were a 4 l/2 denier material and were highly shrunk. It contained insufficient aminoethyl cellulose to make it substantially wool-dyeing, but there was sufficient of this additive to achieve improved direct dyeing properties.
Når nevnte materiale således ble farvet med "Solephenyl Blue-Green" ga det en uttrekking på $ 0% sammenlignet med en fiber spunnet under de samme betingelser, men uten aminoetylcelluloseadditivet, hvilket ga en uttrekking på 15$. When said material was thus dyed with "Solephenyl Blue-Green" it gave an extraction of $0% compared to a fiber spun under the same conditions but without the aminoethyl cellulose additive, which gave an extraction of $15.
Eksempel 3 Example 3
• Fremgangsmåten som angitt i eksempel 1 ble benyttet, men det ble anvendt en 60 vektprosent opplosning i vann av en aminoetylcellulose inneholdende 4*3 vektprosent nitrogen istedenfor den opprinnelige aminoetylcelluloseopplosning. Den førstnevnte opplosning ble innsproytet i en mengde på 100 gram per kilo viskose. • The method stated in example 1 was used, but a 60% by weight solution in water of an aminoethyl cellulose containing 4*3% by weight nitrogen was used instead of the original aminoethylcellulose solution. The former solution was injected in an amount of 100 grams per kilogram of viscose.
Nitrogeninnholdet i den fullstendig torre fiber var 0.25$, men dette innhold minket når fibren ble utlutet med 2% vandig svovelsyre ved 95°c i 1 time. The nitrogen content of the completely dry fiber was 0.25$, but this content decreased when the fiber was leached with 2% aqueous sulfuric acid at 95°c for 1 hour.
Fremgangsmåten ble -gjentatt med den nettopp sentrifugerte fiber impregnert med en opplosning inneholdende 3-5$ formaldehyd, 3.. 5$ magnesiumklorid og oppvridd til et væskeinnhold på 75 vektprosent beregnet på cellulosen. Fibren ble deretter torket ved 82°C og herdet ved l60°C i 4 minutter. Fibrens nitrogeninnhold var igjen 0.25$ og dette innhold ble ikke minsket etter at fibren var nedsen-ket i 2% svovelsyre i 1 time. The procedure was repeated with the just-centrifuged fiber impregnated with a solution containing 3-5% formaldehyde, 3-5% magnesium chloride and spun to a liquid content of 75% by weight calculated on the cellulose. The fiber was then dried at 82°C and cured at 160°C for 4 minutes. The fiber's nitrogen content was again 0.25$ and this content was not reduced after the fiber was immersed in 2% sulfuric acid for 1 hour.
Eksempel 4 Example 4
Fremgangsmåten i eksempel 3 ble benyttet, idet de nettopp koagulerte filamenter ble strukket i et strekkforhold på 1.1:1. De ferdige filamentene inneholdt 0.28 vektprosent nitrogen og viste selv uten kryssbinding av cellulosen intet vesentlig tegn på tap av nitrogen når de ble utlutet med 2 % svovelsyre ved 95°C i 1 time. The method in example 3 was used, with the newly coagulated filaments being stretched in a stretch ratio of 1.1:1. The finished filaments contained 0.28% nitrogen by weight and, even without cross-linking the cellulose, showed no significant sign of nitrogen loss when leached with 2% sulfuric acid at 95°C for 1 hour.
Claims (3)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB56592/67A GB1243194A (en) | 1967-12-13 | 1967-12-13 | The manufacture of more dyeable regenerated cellulose filaments |
Publications (1)
Publication Number | Publication Date |
---|---|
NO125778B true NO125778B (en) | 1972-10-30 |
Family
ID=10477029
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO684969A NO125778B (en) | 1967-12-13 | 1968-12-12 |
Country Status (10)
Country | Link |
---|---|
US (1) | US3608045A (en) |
AT (1) | AT293599B (en) |
BE (1) | BE725439A (en) |
CH (1) | CH509418A (en) |
FI (1) | FI49326C (en) |
FR (1) | FR1596083A (en) |
GB (1) | GB1243194A (en) |
NL (1) | NL153948B (en) |
NO (1) | NO125778B (en) |
SE (1) | SE361059B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4493177A (en) * | 1981-11-25 | 1985-01-15 | Grossman Stanley J | Composite, pre-stressed structural member and method of forming same |
ES2126794T3 (en) * | 1994-01-29 | 1999-04-01 | Dystar Textilfarben Gmbh & Co | AMINATED CELLULOSIC SYNTHETIC FIBERS. |
-
1967
- 1967-12-13 GB GB56592/67A patent/GB1243194A/en not_active Expired
-
1968
- 1968-12-10 FI FI683534A patent/FI49326C/en active
- 1968-12-10 NL NL686817704A patent/NL153948B/en unknown
- 1968-12-11 US US783098A patent/US3608045A/en not_active Expired - Lifetime
- 1968-12-12 SE SE17015/68A patent/SE361059B/xx unknown
- 1968-12-12 NO NO684969A patent/NO125778B/no unknown
- 1968-12-13 CH CH1862768A patent/CH509418A/en not_active IP Right Cessation
- 1968-12-13 BE BE725439D patent/BE725439A/xx unknown
- 1968-12-13 FR FR1596083D patent/FR1596083A/fr not_active Expired
- 1968-12-13 AT AT1217368A patent/AT293599B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FR1596083A (en) | 1970-06-15 |
BE725439A (en) | 1969-05-16 |
US3608045A (en) | 1971-09-21 |
DE1814565A1 (en) | 1969-07-24 |
FI49326B (en) | 1975-01-31 |
NL6817704A (en) | 1969-06-17 |
FI49326C (en) | 1975-05-12 |
GB1243194A (en) | 1971-08-18 |
SE361059B (en) | 1973-10-15 |
NL153948B (en) | 1977-07-15 |
AT293599B (en) | 1971-10-11 |
DE1814565B2 (en) | 1977-03-24 |
CH509418A (en) | 1971-06-30 |
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