DE1814565A1 - Process for the production of regenerated cellulose threads - Google Patents

Description

DA-3131

description

to the company's patent application

COURTAULDS LIMITED ■ ". 18, Hanover Square, London Vi. 1., Englend,

Regarding process for the production of regenerated cellulose threads

Priority dated December 13, 1967, Mr. 56 592/67, Great Britain

The invention relates to a method of manufacture of regenerated cellulose threads with a greater affinity for direct dyes and acid dyes.

In the production of regenerated cellulose threads which can be dyed with acid dyes, it is known to incorporate an amino-substituted cellulose into the cellulose mass or metric of the threads. For this purpose, the Xenthat an aminoethyl cellulose, which contains between 1.2 and 1.6 % Ami-

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Nitrogen has formed, whereupon the Xenthst in caustic soda dissolves and forms a bad viscose, the basic viscose mixed with a normal viscose and the mixture spun into threads of regenerated cellulose, which have sufficient basicity to allow the threads of Dyed with acid dyes or better by direct dyes can be colored.

Try a mixture of cellulose with an amino substituted one en to xanthate cellulose in order to obtain a mixed viscose in a one-step process can be spun because of the different xanthation speeds of the types of oil in question failed. It has therefore hitherto been necessary to carry out the xanthation of each type of cellulose separately and to combine the xanthates in order to obtain the modified viscose only then. This way of working has the Production of better dyeable fibers so complicated, that these have not been produced to a significant extent so far.

A simpler and cheaper method of making such threads has now been developed.

According to the present invention, there is a process for the production of regenerated cellulose

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sefäden therein, one Dess an aqueous solution of amino atnyicellulose having at least 2.0 wt .- # amino, ndt a mixed viscose and the modified viscose is spun through a spinneret into a spinning bath to form filaments ·

The solubility values of aminoethyl cellulose in aqueous media depend on the amino content. Below about 2.0 % nitrogen content, the types of cellulose per se are neither soluble in aqueous sodium hydroxide nor in water; rather, they have to be chemically modified, for example by conversion into the xanthate, in order to acquire the appropriate solubility. With a nitrogen content of around 2.0% , the aminoethylcelluloses are noticeably soluble in aqueous caustic soda solution at a concentration of 10% by weight. The solution does not have to be completely clear at the lower limit of the substitution, but the undissolved particles are gelatinous and give the solution only a slight turbidity or opalescence. If the nitrogen content increases further, the concentration of sodium hydroxide in the solvent can be decreased until finally the aminoethyl celluloses are soluble in water at about 4% nitrogen content and above. By selecting these types of aminoethyl celluloses that are soluble in aqueous caustic soda or water, and by eliminating those types that contain one

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Make xentation necessary so that they become redeemable, 'The process becomes aur the production of more easily discolored Threads simplified and cheaper. It is foreseen that the nitrogen content of the aminoethyl cellulose is 2 * 7-3 »5 Weight should be ~ # that the ether in aqueous caustic soda soluble, but insoluble in water,

The water-soluble amino ethers, which contain 4% or more nitrogen, can be washed out of the regenerated gelulos © - faxLen in which they have been incorporated, especially if the threads are immersed in hot, dilute acid solutions, such as those used in wet dyeing. However, this disadvantage can be overcome if the freshly coagulated threads are stretched by at least 60% of their original length, or by crosslinking the threads with one of the known cellulose crosslinking agents and in particular with the permanently soluble crosslinking agents described in US Pat. No. 3,038,777 and in British Patent 950 073, respectively.

In the production of aminoethyl cellulose by reacting cellulose with aminoethyl hydrogen sulfate and sodium hydroxide, it is uneconomical to want to achieve a nitrogen content of more than about 2.0% in one step while protecting the cellulose against excessive degradation,

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and it can probably be traced back to this® ÜJstsaofte surüok, which has led the previous brewers of this Fsc & @ ebi®ts to the suggestion to accept the Xsnthiewsng from Affliaoltbyloelluloee tror in order to make them soluble and compatible with viscose teas · It has now proven to be possible ? ₉ on the nitrogen content uplifting borrowed on the above-mentioned * What au increase by repeating the Verätheruagßreektion, converting the toinoäthyleelXulose ie with additional quantities of Aminoätbylhgrarogensulfst and liatriuaihydroxyd; matt received substituted geluloses, all of which dissolve in aqueous sodium hydroxide and some in water «,

Bio-opalescent solutions of some aminoethyl celluloses, those made in aqueous sodium hydroxide or in water can be added to the viscose without essentially their filtration and spinning properties affect, especially if mixing takes a few hours takes place before the modified viscose is pressed out. One can assume that the gelatinous particles that the opalescence of the aqueous solutions cause swollen gelulose agents or particles, in one for dl « rapid xanthation are appropriate condition and therefore • with excess carbon disulfide in the viscose or by transxanthation by contact with the viscose loose ·

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The criteria “whether the amisoethyloellulose is sufficiently soluble in its aqueous sodium hydroxide solution can be found less well on the basis of the opalescent behavior of the solution, but rather by making the solution with a viscose of the required composition and in the form required for production Proportions mixed and the Filtrierungsverhelten the viscose VOj? mixing and a certain amount of time after mixing, ss.B. up to 12 hours, measures · If the filtration behavior is not too different, the insoluble fraction that causes the opalescence of the solution does not contribute significantly to spinning problems * If the modified viscose is much more difficult to filter, however, an aminoethyl cellulose should be added a higher nitrogen content can be used for another experiment.

For the production of the aminoethyl cellulose according to the invention in separate reactions of cellulose with successive amounts of aminoethyl hydrogen sulfate and sodium hydroxide, it is advisable to remove the by-product impurities from the intermediate product Wash out Aminoäthylcelluiose before adding further reagents, as this will reduce the effectiveness of the next etherification reaction improved. However, one can leave the by-products of the last reaction in the aminoethyl cellulose,

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SAD ORJGINAi *

mväm> sollt® _fi so sollt © ®b 5 @ dö © h al eist erfcitst 3d ©? g © t ^ © Qta @ t apply this su a Vemetsung and & u © la © ® UnloOliehBdefcesi fflh— r © s. camouflage. The end product came from ussaittelbss? in dop auagewäal "th £ ₉ 5si2ngsmittel ie" wässrigee Istriuislgurosgrd or

Eefeat @ 1g1i inclined that regenerated® cell reading threads, produced by pressing the modified yiekose, and with @ in @ m handled from at least 0.06 # nitrogen, ± ά eiMm. Umfsng can be colored as that ice

regenerated cellulose with direct dyes, and that similar filaments containing at least 0.25 # nitrogen easily with acid dyes so far can be colored that the degree of color corresponds to that of Wool reaches or even exceeds »

The @ rfindungsgemse ferfehren has several special advantages. Ba the aminoethyl celluloses at least 2 wt .- ^ Containing nitrogen, they are per se soluble in the viscose, so there is no additional amount of carbon disulfide is required to remove the Aminoäthylcellulose / Ifiskoseai * · A second advantage is that the solution of the aminoethyl cellulose in aqueous caustic soda or is stable in water, in contrast to the solutions of XjQthatderivate von Aminoäthylcellulosen, which is less than

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2 wt .-; i contain nitrogen; they can therefore be manufactured and stored in considerable quantities. The aqueous solutions can be injected into the viscose just before the mixture is pressed using the methods developed for the injection of pigments in the so-called spin dyeing processes. Because the amino content of the substituted cellulose is so much higher than what has been attempted so far, a smaller proportion of aminoethyl cellulose is sufficient to achieve the desired improvement in colorability.

The invention is further illustrated by the following examples in which percentages are percentages by weight.

example 1

A viscose was made from 7.95% cellulose and 5.68 % sodium hydroxide. This mixture was aged for 40 hours until the salt count reached about 6.0. Then, a solution containing 5.0 # soluble aminoethyl cellulose and 9.5 # sodium hydroxide was indexed at a rate of 143.6 grams of solution per kilo of normal viscose. The percent nitrogen in the solid soluble aminoethyl cellulose was 5.0 #.

After the injection, the material was through immediately

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a 300/5 nozzle in @ ± n spinning bath 1.25 b®i @ in © r temperature. eatki®lt 9 «S3 ^ Seteefslsätip®, O ₉ Hsti? ium3ulf3 &» Die BintauahleBge nene Mst @ risl iwrd® ^ i 30 % · Sas Bad

«Nd 19 _t 5 %

63 c? M and the erspoa «

dsim in Fora

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Juipierwlisohe wlisqhei ^ 10 tsmsxüw Zusaaae ». 5 sour pre
Laundry 1 5 Rauüterope-
rature 32 oil koae «
Sohwttfelsiure
per liter
white water Alkaline
prewash 4th 20th Raueteape-
rature ized water Alkaline
prewash 2 5 Rautttenpe " Soft water Sulfide fcad 1 5 62 ⁰ O 339 »1. 8 pounds
BTatrluasulfide
per liter, in
soft water Sulphi & toad 4th 10 45 ⁰ O soft water Fade 1 5 HauBttenpe ·
rature soft water Acid bath 1 5 Hauateape » 32 ml, conc
Hydrochloric acid pro
Liter entMl & e * »
ralized
water de laundry 4th 15th 48 * 0 deninerali-
slert water,
pH 7 2 48 ° C demineralizing
old water
$ 0.1 Sodiumfcl-
carbonate equipment
(Finish) 1 40 ⁰ O echo neutral
sized Olein
acid old 0.2Ji
HatriuahTdroaqrd

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Di® Paser became 5 Hin. sentrifiägiert long and dried ^{at SO 0 O.} According to the Sroelmea, there was a percentage nitrogen content vcc in dw bone dry fiber. 0.28%. The exhaustion of a bath which contained azogeranine (0.2 g / l) was 55% compared to 5.5 % for a normal yarn which was spooned under identical conditions but without the aminoethyl cellulose was.

Example 2 · · - ·

A viscose was prepared DI® 9 _t 13 # latriumo © - cellulose moistened, 6.29 # Katriumhydroxjd with a Salzssahl of 6.6 and a falling ball viscosity of 49 sec * temperature had at a 15 ⁰ O. 1.7% affinethyl cellulose, based on the cellulose of the viscose, was inlaid in a 5.9% solution in 9% strength sodium hydroxide solution. The solid aminoethyl cellulose prepared for the injector solution contained an average of 2.9 % nitrogen with a range of 2.7 to 3.2% nitrogen. The viscose was spun in a bath which, at 64 ⁰ O, contained 6.5% sulfuric acid, 1.3 % zinc sulphate and 23.0% lithium sulphate. A 75 °° ^x ^ ö ^ -se and an entry length of 68 em were used. The nitrogen value of the product after washing with the solutions given in Example 1 was $ 0.06 · The staple fiber thus obtained had a denier of 4 1/2 and was

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heavily ruffled. It contained insufficient aminoethyl cellulose to be dyed as clearly as wool, but it contained enough of the above-mentioned ingredients to be dyed satisfactorily by direct dyes. When dyeing with ßolephenyl Bleu-Green, calibrated an exhaustion of 50 % compared to an exhaustion value of 15 % of a fiber spun under the same conditions, but without aminoethyl cellulose.

Example 3

The procedure of Example 1 was repeated, with each » but the original aminoethyl cellulose solution by a 60 wt .- # - strength solution of aminoethyl cellulose with 4.3 Wt .- ^ nitrogen in water has been replaced. The replaced Solution was injected in an amount of 100 g per kg of viscose.

The nitrogen content of the bone-dry fiber was 0.25 # _t , but fell as soon as the fiber was washed out with 2 # aqueous sulfuric acid for 1 hour at 95.degree.

The procedure was repeated with freshly centrifuged fiber impregnated with a solution containing 3 * 5 # formaldehyde, 3.5 $ magnesium chloride. The fiber was made up to a liquid content of 75 %

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Cellulose squeezed out. Bensoh, the fiber was ^{dried at 82 0} O and cured for 4 minutes at 16O ⁰ O. "The nitrogen content of the fiber, which is 0.25 #" but could not be determined after the Feeer spent an hour in 2 $ o- sulfuric acid was immersed

example

The procedure of Example 3 was followed with the freshly coagulated en threads that had been drawn with a draw ratio of 1.6: 1 were repeated. The finished threads contained 0.28 wt. # Nitrogen and showed even without Crosslinking of the cellulose did not cause any significant loss of nitrogen when treated with 2 # sulfuric acid for 1 hour leached at 95 ° C for a long time.

Pat entana claims

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Claims (1)

Claims Iy method for producing regenerated cellulose threads with improved dye strength, wherein a Viscose, which contains a dissolved basic polymer, is pressed out, characterized in that an aminoethylcellulose with at least 2 wt .- ^ nitrogen is used as the basic polymer, which in water or aqueous caustic soda is soluble. 2. The method according to claim 1, characterized in that an aminoethyl cellulose is used which has between 2.3 and 2.7 wt .- # nitrogen and is soluble in aqueous caustic soda. 5. The method according to claim I ₁ characterized g β ke η η - «• lehnet, dees one uses an aqueous aminoethyl cellulose which has at least 4 wt .- # nitrogen and let soluble in water. 4. The method according to claim 1 to 3 »characterized g e k e η η - that one threads that should have better dyeability with direct dyes, old a nitrogen content of at least 0.06% by weight. -IA- 909830/1323 BATH 18U565 5. Method according to claims 1 to 4, characterized by deduroh, one ss threads that have a better dye strength with direct dyes, with a nitrogen content of at least $ 0.25 6. The method according to claim 5, characterized in that the threads by 50 # of their original Length stretches. 7. The method as claimed in claim 3, characterized in that the threads are coated with an oilulose crosslinking agent implements. 8. Regenerated cellulose thread, which is a basic polymer contain, characterized in that they as a basic polymer aminoethyl cellulose with a Considered to contain at least 2 wt .- # nitrogen and. the nitrogen content of the threads at least 0.06 wt. amounts to" 9. threads according to claim 6, characterized in that that their nitrogen content is at least $ 0.25 wt. 909830/1323 - 15 -